CA2202286A1 - The combinatorial synthesis of novel materials - Google Patents
The combinatorial synthesis of novel materialsInfo
- Publication number
- CA2202286A1 CA2202286A1 CA002202286A CA2202286A CA2202286A1 CA 2202286 A1 CA2202286 A1 CA 2202286A1 CA 002202286 A CA002202286 A CA 002202286A CA 2202286 A CA2202286 A CA 2202286A CA 2202286 A1 CA2202286 A1 CA 2202286A1
- Authority
- CA
- Canada
- Prior art keywords
- recited
- substrate
- materials
- component
- region
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
- C01G51/68—Cobaltates containing alkaline earth metals, e.g. SrCoO3 containing rare earth, e.g. La0.3Sr0.7CoO3
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C14/34—Sputtering
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C40—COMBINATORIAL TECHNOLOGY
- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B40/00—Libraries per se, e.g. arrays, mixtures
- C40B40/04—Libraries containing only organic compounds
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- C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
- C40B60/08—Integrated apparatus specially adapted for both creating and screening libraries
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- C40B80/00—Linkers or spacers specially adapted for combinatorial chemistry or libraries, e.g. traceless linkers or safety-catch linkers
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- G—PHYSICS
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- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
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- H—ELECTRICITY
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- H01F1/401—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4 diluted
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- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31931—Polyene monomer-containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
- Y10T436/2525—Stabilizing or preserving
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
- Y10T436/25375—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.]
- Y10T436/255—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.] including use of a solid sorbent, semipermeable membrane, or liquid extraction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
- Y10T436/25875—Gaseous sample or with change of physical state
Abstract
Giant magnetoresistive cobalt oxide compounds are produced by combinatorial synthesis. Combinatorial synthesis is done by using a substrate having an array of diverse materials thereon prepared by delivering components to predefined regions on a substrate and simultaneously reacting the components to form at least two materials. Other materials that can be prepared using these methods are covalent network solids, ionic solids and molecular solids. Examples are inorganic, organometallic, intermetallic, ceramic organic polymeric and composite materials. Once prepared, these materials can be screened for useful properties such as magnetoresistance. Thus, the present invention provides for the parallel synthesis and analysis of novel material having useful properties.
Description
-W O96/11878 PCTrUS95/13278 S
THE COMBINA7~0RLAL ,SYNTHESIS OF NOVEL MATERL~LS
This application is a c~ on-in-part of Serial No. 08/327,513, filed October 18, 1994, the tP~hinge of which are hereby incorporated by reference for all 10 yulyoses.
STATEMENT C)F GOVERNMENT INTEREST
This invention was made with Government ~UyyOll yul~ua~lt to Contract No. DE-AC03-76SF00098 awarded by the Department of Energy. The GovernmPnt has 15 certain rights in this invention.
FIELD OF l~lE INVENTION
The present invention generally relates to methods and apparatus for the parallel deposition, synthesis and screRning of an array of diverse m~tP.ri~le at known 20 locations on a single subs~rate surface. The invention can be applied, for example, to ylcy~ covalent network solids, ionic solids and molecular solids. More spel-ific~lly, the invention can be applied to prepare inorganic m~teri~le, intermetallic materials, metal alloys, cPr~mic m~tPri~le, organic m~tP.ri~le, organomP,t~llic m~t~.ri~l.e, non-biological organic yolymers~ composite m~t~.ri~l.e (e.g., inorganic composites, organic composites, 25 or combinations thereof), etc. Once yl~ d, these m~tPri~le can be screRned in parallel for useful ~lopellies inclllrling, for e~ample, electrical, thermal, mech~ni~
morphological, optical, magnetic, chemi~ ~l, and other yr~elLies.
o BACKGROUND OF THE INVENTION
., 30 The discov~ry of new m~tPri~l~ with novel chPmic~l and physical properties often leads to the development of new and useful technologies. Currently, there is a tremPn~lous amount of activity in the discovery and optimi7~tion of m~t~-.ri~l.e, such as ~upel~i~ductors, _eolites, m:lgnPtic m~tPri~ls, phosphors, nonlinear optical m~tPri~le, thermoelectric materials and high and low iiçlectric m~tPri~le Unfortunately, W O96/11878 PCTrUS95113278 even though the çhPmi.ctry of eYtrn-le~ solids has been extensively explored, few gene~
prinriplrs have emerged that allow one to predict with cG~ y the collll,osilion,structure and reaction paLllways for the synthesis of such solid state co-,-~u--ds.
Morwvel, it is difficult to predict a prion the physical pr~,Lies a particular three 5 rlimrncional structure will possess. Consider, for ey~mple~ the synthesis of the YBa2Cu307~ ~u~Glco~ ctor in 1987. Soon after the discovery of the La2 ,~Sr"CuO4 ~u~lconductor, which adopts the K2NiF4 structure (ReAnnr7, J.G. and K.A. Muller, Z.
Phy. B 64:189 (1986), it was observed that the application of ~les~ increased the tr~ncition t~ , (Chu, et al., Phys. Rev. Lett. 58:405 (1987)). As such, Chu, et 0 al. aUe~ ed to synthrci7~ a Y-Ba-Cu-O compound of the same stoichiometry in the hope that substitution of the smaller Pl,o.m-q.nt, i.e., yttrium, for lAntl.Anl- .. would have the same effect. Although they found su~Glcollductivity above 93K, no phase with K2NiF4 structure was observed (Wu, et al., Phys. Rev. Lett. 58:908 (1987)). Even for the relatively simple intermrt~llic compounds, such as the binary colllpounds of nickel and ~ir~olliulll (NisZr, Ni7Zr2, Ni3Zr, Ni2Zr8, NilOZr7, NillZrg, NiZr and NiZr2), it is not yet ndPrstood why only certain stoichiometries occur.
Clearly, the p,G~ Lion of new materials with novel c~lernir~l and physical ~ro~lLies is at best hapFenct~nce with our current level of underst~nding. Consequently, the discovery of new m~trri~l.c ciepen~1c largely on the ability to synth~oci7~ and analyze 20 new compounds. Given a~l.loAimately 100 elements in the periodic table which can be used to make C(Jlll~osiLions concisting of three, four, five, six or more elemPntc, the univG,~e of possible new col..pounds remains largely unexplored. As such, there exists a need in the art for a more efficient, economical and systematic approach for the synthesis of novel m~tf~ri~lc and for the screelling of such materials for useful ~ro~,Lies.
One of the processes whereby nature produces molecules having novel functions involves the gen~r~tion of large collections (libraries) of molecules and the sy.ct~.m~tic scl~ening of those collections for molecules having a desired p,~ ,Ly. An O
eY~mple of such a process is the humoral immune system which in a matter of weeks sorts through some 10l2 antibody moleculPs to find one which sperifir~lly binds a foreign pathogen (Nisonoff, et al., The Antibody Molecule (~ mic Press, New York, 1975)).
This notion of generating and screening large libraries of molecules has ,~cenLly been applied to the drug discovery process. The discovery of new drugs can be likened to the process of finding a key which fits a lock of unknown structure. One solution to the W O 96/11878 PCTrUS95/13278 problem is to simply produce and test a large number of different keys in the hope that one will fit the lock.
Using this logic, methods have been developed for the synthesis and S~.1Ge1~llg of large libldlics (up to 1014 molecules) of peptides, oligonucleotides and other 5 small mnl~~ .c. Geysen, et al., for example, have developed a method wherein peptide syntheses are carried out in parallel on several rods or pins (see, J. Immun.
Meth. 102:259-274 (1987), inco,~lnted herein by reference for all pul~oses).
~nPr~lly, the Geysen, e~ al. methocl involves function~li7.in~ the termini of polymeric rods and sequentially immer~ing the termini in solutions of individual amino acids. In 10 addition to the Geysen, e~ al. method, techniques have rGcel~lly been introduced for synthe.~i7in~ large arrays of different peptides and other polymers on solid surfaces.
Pirrung, et al., have developed a technique for generating arrays of peptides and other m~ cll1es using, for example, light-directed, spatially-addressable synthesis techniques (see, U.S. Patent No. 5,143,854 and PCT Publication No. WO 90/15070, inccl~ldted15 herein by referenoe for all purposes) In addition, Fodor, et al. have developed, among other things, a method of g~thP.ring fluoresce.nce intensity data, various photosen~itive pn~ling groups, m~c~ing techniques, and au~ ,lated techniques for p~ ning light-directed, spatially-addressable synthesis techniques (see, Fodor, et al., PCT
Publication No. WO 92/10092, the t.~çhing~ of which are incorporated herein by 20 reference for all p~ oses).
Using these various m,ethods, arrays cont~ining thousands or millions of dirrelG~ emPnt.~ can be formed (see, U.S. Patent Application No. 805,727, filed Deoe.mher 6, 1991, the te~rhing~ of which are incorporated herein by referenoe for all purposes). As a result of their relationship to semiconductor fabrication techniques, these metho~ls have come to be refer]red to as "Very Large Scale Immobilized Polymer Synth~si.~," or "VLSIPS~" te~.hnology. Such techniques have met with substantialsuccess in, for e ~mple, screening various ligands such as peptides and oligonucleotides to dete-rmine their relative binding affimity to a receptor such as an antibody.The solid phase synthesis techniques currently being used to ~1G~)~hG such 30 libraries involve the stepwise, i.e., sequential, coupling of building blocks to form the compounds of interest. In the Pirrung, et al. method, for example, polypeptide arrays are synth~ i7~d on a substrate by ~tt~ching photoremovable groups to the surface of the substrate, exposing sele~ted regions of the substrate to light to activate those regions, W O96/11878 PCTrUS95113278 u~ an amino acid ~ wi~ a ~hol~l_....... ov~ble group to ~e activdt d region, aI~d ",~5,t;.~, the st~ps of activa~on and ~ t~ .~1 until l oly~!;d~s of ~e desired length and ~u~ccs aD synth~s;7~ These solid phase synthesis lccl~ ucs, which ~e ~u~llial ~url;~p of b~ n~ blocks (e.g., amino acids) to form the 5 ~ l~u~ ~lc of ,nt~t, cannot readily be used to ~,p~, many lnOl`~;an~C and ~ ;C
CO...~ l.c From the above, it is seen that a m~thod and al.~K ~tl.c for syntheci~
and scl~ ~mg 1;1,.,~ ;P S of m~t~ri~l~, such as inolE;~ic m~tPn~ls~ at known ~ ;OnC on a ~bs~., t are ~Pci~A
SUMMARY OF THE INVENTION
The present i.~ iol~ provides .. ~-II.~s and al~ Js for the ~ ;nn and use of a ~ having an array of diverse m~tPri~lc in plc~r.i-~d regions thereon.
A s-~ te having an array of diverse m~t~Pri~ls thereon is p.~aLcd by ddi~ g 15 co~ of m~tPri~lc to ~ r~rd regions on the s..l,sl.,~le, and cimull;-n~u;,ly l~r.~;"g the ccl...~nf~ to form at least two m~tPn~lc M~tPn~lc which can be p using the ~-rll-~s and a~ Js of the present invention inc]u-l~P, for Py~mple~ covalent l~clw~ solids, ionic solids and ~le~ solids. More particularly, m~tPri~lc which can be pl~)alC~i include inorganic m~tPri~l~, ;ntf ~ ic m~t~.ri~lc, metal alloys, CP~mir, 20 m~t.-.ri~lc organic m~t~.ri~l~, ol~ o~ ic m~tPri~lc, non-biolo~ organic polymers, co...l~;t, m~tPri~lC (e.g., ihlOl~ iC cc,...l~s;t~ 5, organic ccsn~ f ~ or comhin~tinnc thercof), etc. Oncc ~ cd, these mate~i~1C can be scr~ned in parallel for useful es ;,,~1,l,1;ng, for ~ ~f e1p~ thprm~l"~f~ niç~ "ul~holngj~
optical, m~lptic~ chpmi~l and other plOpC~lifeS. As such, the present invention 2S provides ..I~ c and ~alus for the para~el ~ e~;s and analysis of novel m~t~.n~
having new and useful plop~.Lies. Any m~tPri~l found to possess a useful ~lU~ty can --be ~u_.~lly ~ d on a hrge-scale. ' --In one e."bo~ of the present invention, a first cc~ of a first m~tPri~l is de~ .vd to a first region on a ;~ sl.~.lr., and a first co~ P~I of a second 30 m~tPri~l is del;~. d to a second region on ~e same S.ll,s~.i.t~.. ThGI~, a second col..~n~ ~1 of the first m~tPn~1 is delivered to the first region on the ~vl~s~ , and a second co~ n~ of the second m~tPn~l is delivered to the second region on the ~ I,s~ le The p~ccss is ~ption~11y l~ d, with ?~litinn~1 cO...l~l-f ~l~, to form a vast W O96/11878 PCTnUS95/13278 s array of C~lllponents at ~ d, z.e., known, locations on the ~-,I,sl ~te. Thereafter, the coll,~l-ents are ciml~lt~nPously reacted to form at least two m~tPri~lc The co.~ enl~ can be sequentially or ~iml-lt~nPl!usly delivered to prPA~Pfin~P~ regions on the ,l.,.t~ in any str)ichiometly, inrl~ inp a gr~ nt of stoichiomPtriçs, using any of a 5 ~,1,1 e- of diLr~ei t delivery techniques.
In another embodiment of the present invention, a mPthod is provided for forming at least two dirrelel~t arrays of m~tPri~lc by delivering subst~nti~lly the same reaction colll~onents at ~,ubsl;~ lly ident~ conr~ntr~tions to reaction regions on both first and second substrates and, thereafter, subjecting the co.,.ponents on the first 0 SUbSildte to a first set of reaction conditions and the co~-ponents on the second substrate to a second set of reaction conditions. Using this method, the effects of the various reaction p~r~mp~tprs can be studied on many m~teri~lc simultaneously and, in turn, such reaction ~ can be optimi7~~ ction parameters which can be varied in~ de7 for PY~mpl~P, redctant amounts, reactant solvents, r_action ~-I~peldlù~es, reaction times, the ples.7~ at which the re~rti~ are carried out, the atmospheres in which the rP~rtionc are con-~uctP~l, the rates at which the reactions are quenrh-PIi, the order in which the re~ct~ntc are deposited, etc.
In the delivery systems of the present invention, a small, precisely metered amount of each reactant coll.~,nent is delivered into each reaction region. This may be accomplished using a variety of delivery techniques, either alone or in combination with a variet~ of m~cking techniques. For example, thin-film deposition techniques incombination with physical m~.cking or photolithographic techniques can be used to deliver various re~rt~nt~ to S-PlPCt-P~ regions on the substrate. ~e~ct~ntc can be delivered as amorphous films, e~i~ial films, or lafflce and superlattice structures. Moreover, using such techniques, re~t~t~nt~ can be delivered to each site in a unirollll distribution, or in a ~r~liPnt of stoichiomPtries. .Altern~lively, the various reactant components can be deposited into the reaction regions oiF interest from a ~licperlcPr in the form of droplets or powder. Suitable ~licpPn~Prs in~lud~P, for example, micn~pip~Ues, mP~h~nicmc adapted from inkjet printing technology and electrophoretic pumps.
Once the cGIIlponents of interest have been delivered to pre~efinP11 regions on the substrate, they can be reacted using a number of difrLrent synthetic routes to form an a~ay of m~tPri~l~ The components can be reacted using, for example, solution based sy~ esis techniques, photochP-mic~l techniques, polymerization techniques, template W O 96/11878 PCTrUS95/13278 directed synthesis techniques, epit~xi~1 growth techniques, by the sol-gel process, by tht-rm~1, inLd.t;d or microwave heating, by c~l~in~tion~ .cintf.ring or ~nn~linf~, by yd~ P-rm~1 mlothQ 1s, by flux methods, by cryst~lli7~tion through vaporization of solvent, etc. Th~;r~r~r, the array can be screened for m~tPri~l.c having useful S ~l~lies.
In another embodiment of the present invention, an array of inorganic m~tP.ri~l.c on a single substrate at pred.~.fin~ regions thereon is provided. Such an array can consists of more than l0, 102, 103, 104, l05 or l06 different ino~gallic cGI--~ui~ds.
In some embollimP-ntc, the density of regions per unit area will be greater than .04 l0 regions/cm2, more preferably greater than 0. l regions/cm2, even more preferably greater than 1 region/cm2, even more preferably greater than l0 regions/cm2, and still more preferably greater than l00 regions/cm2. In most ~rert;ll~d emb~1im~nt~, the density of regions per unit area will be greater than l,000 regions/cm2, more preferably l0,000 regions/cm2, çven more preferably greater than l00,000 regions/cm2, and still more preferably l0,000,000 regions/cm2.
In yet another aspect, the present invention provides a m~t~ri~1 having a useful plU~ y ~r~yar~d by: forming an array of materials on a single sul ~lldle;sc,ee~ g the array for a m~tP.ri~1 having a useful property; and making ~Ariihon~l amounts of the m~tt-ri~1 having the useful plo~lly. As such, the present invention 20 provides methods and apparatus for the parallel synthesis and analysis of novel m~t~ri~1 having new and useful prope,Lies.
Using the fc,regoing method, a new family of giant m~nelc~ Li~le (GMR) cobalt oxides has been discovered. Arrays of materials con~ dirrerent compositions and st~-ic~ metries of Lnl xMxCoOz, wherein Ln is, for example, Y and La, M is, for 25 example, Pb, Ca, Sr and Ba, x has a value ranging from about 0.l to about 0.9 and z has a value r~nging from about 2 to about 4, were formed using thin film deposition techniques in combination with m~.cking techniques. Once formed, the arrays of m~teri~ were screened for those m~teri~1~ among them having useful ~ro~llies. More particularly, the arrays of m~t~.ri~1~ were screened for specific m~t~ri~1~ having giant 30 m~gn~$Qresistive (GMR) pn~lLies, among others. In doing so, large m~gnto.torç~i~t~n~
(MR) was found in Lal x-(Ba, Sr, Ca)x-CoOz ~mples, wherein x has a value r~n~in~ ~
from about 0. l to about 0.9, and z has a value r~nging from about 2 to about 4. Once W O 96/11878 PCTnUS95/13278 the m~tt~ri~lc having useful ~lu~lLies were i~1~ntifiPA additional a--lou--l~ of such m~t~.ri~l~ were ~lcL)~ed.
In doing so, it has been determined that the co~ uullds in this new family of GMR cobalt oxides have the following general formula: Ay~ )M~ CoOz~ wherein A is S a metal ~l~tP~ from the group con~icting of l~ U-l~ (La), yttrium (Y), cerium (Ce), rrac~lyllliulll (Pr), neody...iu... (Ncl), prom~thi~m (Pm), ~ i ;~ . (Sm), ~ ;Ulll (Eu), ~ 1inillm (Gd), ~ iUlll (Tb)l, dy;!~JlU:iiUlll (Dy), h()lmillm (Ho), erbium (Er), th~ lm (Tm), yLLt;lbiulll (Yp) and l~ ; . (Lu); M is a metal sPl~ct~d from the group c~ ncicting of c~killm (Ca), ~Lr~nliu,ll (Sr), barium (Ba), lead (Pb), th~llium ~I1) and bicmuth (13i); y has a value r~n~ing from about 1 to about 2; x has a value r~ngin~ frûm about 0.1 to about 0.9; and z has a value ranging from about 2 to about 4. Moreover, it has been ~ettorrninPA that the compounds in this new family of GMR cobalt oxidesgenerally have a layered, perovskite--related structure.
A further lm~lPrst~nl1in~ of the nature and advantages of the inventions herein may be realized by reference to the ~ portions of the speçific~tion and the ~tt~rhPA drawings.
B~IEF DESCRIPIION OF THE DRAWINGS
FIG. 1 illllCtrAtPS m~ckin~ of a substrate at a first location; the S-lbSLldle is shown in cross-se~tion;
FIGS. 2A-2I illustrate the use of binary m~cking techniques to generate an array of re~t~ntC on a single substraLte;
FIGS. 3A-3I illllctr~tP the use of physical m~ling techniques to genPr~tP
an array of re~t~ntc on a single substrate;
FIGS. 4A-4M illustrale the use of physical m~ ing techniques to gPnPr~te an array of re~ct~ntc on a single substrate;
FIG. 5 displays the elPmPntC of a typical guided droplet dispenser that may be used to deliver the reactant solution(s) of the present invention;
FIG. 6 illnctr~tPs an example of a reaction system employing an eight RF
m~gnPtrûn sputt~ring gun and a carrousel;
FIG. 7 illustrates an example of a reaction system employing an eight RF
m~gnPtron i~ullr ;llg gun and a c~c~ett~P;
W O96/11878 PCTrUS9S/13278 FIG. 8 i1l~-$tr~tP~ an example of a reaction system a pulsed laser and a c~.sett~; -FIG. 9 illllctr~tes an eY~mple of a reaction system employing a pulsed laser and a sliding and shutter m~kin~ system;
FIGS. 10A-lOD illllstr~tPs various masks which can be used in carrying out the mPtho-l~ of the present invention. FIG. 10A ilhl~tr~tes an eY~mple of an X/Y
shutter mask; FIG. 10B illllstr~tP~s S m~king p~tt~rn~ which can be used to create S
se~ columns along a substrate for 5 dirrt;le t reaction co~ onents; FIG. 10C
rs an example of how the X/Y shutter mask can be used to create a thickn 10 ~ nt of one coll,~onent across the substrate; and FIG. 10D a mask which when ~n~l~t~ across the substrate, 5 different components are deposited in each half of the substrate.
FIG. 11 illustrates an examply of a flat sheet col,ti.ining thereon both binary masks and an X/Y shutter.
FIG. 12 illllstr~t~ an example of temperature control in a library through resistive heating;
FIG. 13 illll5tr~tes an example of a Sc~nning RF Susceptibility Detection System which can be used to detect the ~ulJelcollductivity of an array of m~tPri~
FIG. 14 is a map of the reactant components delivered to the 16 pre~lefinP~ regions on the MgO substrate;
FIG. 15 is a pho~ogM~h of an array of 16 different compounds on the 1.25 cm x 1.25 cm MgO substrate;
FIGS. 16A-16B illustrate the resi~t~nce of the two conducting materials as a function of Lelll~el~ture;
FIG. 17 illustrate the binary masks used to generate the library of m~tPri~l~; numbers in lower left hand and upper righthand comers in-lic~te position of each member in the library; M0 corresponds to no secondary mask;
FIG. 18 is a photograph of the 128 member binary library prior to ~intPring; the color of each site is the natural color of reflected light from a white light source;
FIGS. 19A-19B illustrate resistivity vs. temperature plots:
(A) 13iCuSrCaO; and (B) BiCuSrCaCuCaO and BiCuCuSrCaCaO;
FIG. 20 illustrates the masks used to generate the YBCO-BSCCO library.
W O96/11878 PCTrUS95/13278 FIGS. 21A-21C ill~ P.c resistivity vs. ~ `.f..AI~ plots: (A) BiCuSrCaO; (13) YBaCaO; and (C) YBa2Cu3O";
FIG. 22 illllctr~tPs the masks used to generate the libr~riPs of cobalt oxide (CoO) thin-film m~tPri~lc9 S FIG. 23 illustrates a map of compositions and stc ichiometries (Ln,~MyCoO3 ~b~ where Ln = La and Y, and M = Ba, Sr, Ca and Pb) of thin film ~m~le~ in lihrariP.s L2 and L3. .~mrlPs are labeled by index (row mlm~er, col~mn llu~ ) in the text and figure legend. The first number in each box in~ tP.~ x and the second y. Black, solid circles int1ir~tç the ~mrlPs that show ci~nificant MR effects (>5%);
FIGS. 24A and 24B illllctr~tP. MR ratios of .~.e~G~ ;ve samples in L2 (19A) and L3 (19B) as a function of m~netic field;
FIGS. 2~A and 2~B illustrate the resistance of sample L3(13, 2) under OT
and 10T and the MR ratio (H = 10T) as a function of temperature (20A), and MR ratios of the sample for different m~gnetic fields as a function of t~ dtUlc; (20B). The solid lines are guides to the eye;
FIGS. 26A, 26B and 26C illllctrat~o the X-ray diffraction p~tternc (in-l~
for cubic perovskite structure) for Ba~ Sr and Ca doped bulk samples, l~c~-Jely; ~e X-ray tliffr~ction p~tternC in~ te that the structure of this new class of cobalt oxides is cubic perovskite with some slight distortion; and FIG. 27 illllctr~t~.s the l~gn~.ti7~tic)n of the bulk sample La058Sr0.4lCoO~s under lT field as a function of ~~ eJ~dture. The solid line is a guide to the eye. The inset in FIG. 22 ilhl.ctr~t~q.s the MR ra~ios of the sample at different t~ pe~dLures as a function of m~gnetic field.
DETAILED DESCRIPTION OF THE lNVENTlON
AND PREFERRED EMBODIMENTS
CONTENTS
S I. Glossary II. General Overview m. ~ol~tion of Reaction Regions on The Substrate IV. MP.tho l~ For Delivery Of Pe~ct~nt Components A. Delivery Using Thin-Film Deposition Techniques B. Delivery Using A Dispenser V. Multi-Target, Thin-Film Deposition Systems VI. Moving The Dispenser With Respect To The Substrate VII. Synthetic Routes For RP~-.ting The Array Of Components VIII. Methods For Screening An Array Of Materials IX. , .~llr~ e Embodim~nt~
X. F.Y~mr11~S
A. Synthesis of An Array of 16 Copper Oxide Thin-Film ~teri~
B. Synthesis of An Array of 128 Copper Oxide Thin-Film M~tP.ri~l~
C. Synthesis of An Array of 128 Copper Oxide Thin-Film ~t~.ri~
Con~ .g BiSrCaCuO and YBaCuO Superconducting M~tP.ri~
D. Synthesis of Arrays of Cobalt Oxide Thin-film ~t~.ri~l~
E. Synthesis of An Array of 16 Different Organic Polymers F. Synthesis of An Array of Different Zeolites G. Synthesis of An Array of Copper Oxide Compounds Using Spraying Deposition Techniques H. Synthesis of An Array of 16 Different Zinc Silicate Phosphors I. Synthesis of An Array of Copper Oxide Thin-Film M~t~.ri~l~ Using Sputtering Techniques In Combination With Photolithography M~clrin~
Techniques XI. Conclusion W O 96/11878 PCT~US95/I3~78 1. Glossary The following terms are intPn~P~ to have the following general ....-~nil.
as they are used herein.
5 1. Sul,slldle: A m~tPri~l having a rigid or semi-rigid ~urf~e In many emb~imPntc, at least one suIface of the sL~ dle will be ~ubs~ 11y flat, although in some emb~limPntc it may be desirable to physically sep~dte synthesisregions for different m~tPri~ls with, for PY~mple, ~lim~hPs~ wells, raised regions, etched trenches, or the like. In some embo-iimPntc, the substrate itself contains wells, raised regions, etched trenches, etc. which form all or part of the synthesis regions. According to other emb~impnt~ small beads or pellets may be provided on the surface within dimples or on other regions of the surface or, ely, the small beads or pellets may thPmcelves be the substrate.
15 2. Predefined Region: A pre~ltqfin~cl region is a lO(`~li71y~ area on a substrate which is, was, or is intPnd~PCl to be used for formation of a srlP~t~d m~tPri~l and isotherwise r~r~ d to herein in the ~ltPrn~tive as "known" region, "reaction"
region, a "SPl~P~tP~1" region, or simply a "region." The prPAefinPcl region may have any convenient shape, e.g., linear, circular, rectangular, elliptical, wedge-shaped, etc. Additionally, the pre~lefined region, i.e., the reaction site, can be a bead or pellet which is coated with a reactant component(s) of interest.
In this embo-limPnt7 the bead or pellet can be identifi~d with a tag, such as anetched binary bar code that can be used to in~ tP the history of the bead or pellet, i.e., to identify which co-,-~nents were deposited thereon. In some emb~limPntc, a predefined region and, therefore, the area upon which each distinct m~tPri~l is synthPci7~ is smaller than about 25 cm2, preferably less than 10 cm2, more preferably less than S cm2, even more preferably less than 1 cm2, still more preferably less than 1 mm2, and even more preferably less than 0.5 mm2. In most pr~r~ d emb~im~ntc, the regions have an area less than about 10,000 ~m2, preferably less than 1,000 ~Lm2, more preferably less than 100 ~m2, and even more preferably less than 10 ~m2.
W O96/11878 PCTrUS95/13278 3. Radiation: Energy which may be selectively applied inclu-ling energy having a wavelength between 10-14 and 104 meters inclurling, for example, electron beam r~ tion, gamma r~ tion, x-ray radiation, ultraviolet r~i~tion, visible light, infrared r~ tion, microwave radiation and radio waves. "Trradi~tion" refers to S the appli~tion of r~ tion to a s~ re 4. ~o~ on~nt "Component" is used herein to refer to each of the individual chPrnir~l substances that act upon one another to produce a particular m~tPri~l and is otherwise lc;r~ d to herein in the ~lt~"-~ re as "reactant" or "reactant component." That is to say, the colllponents or, ~ltPrn~tively, react~nt~ are the m~ cul.os that act upon one another to produce a new molecule(s), i.e., product(s); for example, in the reaction HCl + NaOH NaCl + H2O, the HCl and the NaOH are the co,nponents or re~ct~nt~. -15 5. Material: The term "m~t~ri~l" is used herein to refer to solid-state co,llpounds, eYt~n~e~ solids, eYt~nded solutions, clusters of molecules or atoms, crystals, etc.
6. (~ovalent Network Solids: Solids that consist of atoms held together in a large network of chains by covalent bonds. Such covalent network solids inl.lude, but are not limited to, tli~mond, silicon nitride, graphite, b-lnkmi~terfullerene and --organic polymers which cannot be synth~i7Pd in a stepwise fashion.
7. Isnic Solids: Solids which can be modeled as cations and anions held together by el~ctri~l attraction of opposite charge. Such ionic solids in~ludç, but are not rçstrict~d to, CaF2, CdCl2, ZnCl2, NaCl2, AgF, AgCl, AgBr and spinels (e.g., ZnAl2O4, MgAl2O4, FrCr2O4, etc.).
-8. Molecular Solids: Solids con~isting of atoms or molecules held together by intermolecular forces. Molecular solids indude, but are not limited to, extendedsolids, soiid neon, organic compounds, synthetic or organic metals (e.g., tetrathiafulvalene-tetracyanoquinoneAim-oth~ne (I IF-TCNO)), liquid crystals (e.g., cyclic siloxanes) and protein crystals.
-W O96/11878 PCTrUS95tl3278 9. Inorganic ~te~ M~tP.ri.~l~ which do not contain carbon as a ~
el~mPnt The oxides and snlrhitlP-~ of carbon and the mPt~llic carbides are considered inorganic m~ten~ Examples of inorganic con.~llnds which can be synth~i7~d using the mPtho-ls of the present invention inclu~e, but are not S restricted to, the following:
(a) Tntprmpt~1lics (or TntPrmPAi~te Con~*tuPnt~ ntPrm~t~l1ie compounds cQ~ ule a unique class of m~t~llic m~t~ri~l~ that form long-range o~e~d crystal structures below a critical ~ u~,. Such m~tPri~l~ form when atoms of two metals combine in certain pro~Gllions to form crystals with a dirr~,clll structure from that of either of the two metals (e.g., NiAl, CrBe2, CuZn, etc.).
(b) Metal Alloys: A substance having met~llic ~r~llies and which is col-l~sed of a Illi~lUlc; of two or more chemical elemPnt~ of which at least one is a metal.
(c) M~nPtic Alloys: An alloy exhibiting Çellon~gn~ti~m such as silicon iron, butalso iron-nickel alloys, which may contain small amounts of any of a number of other el~m~onts (e.g., copper, aluminum, chromium, molybdenum, v~n~lium, etc.), and iron-cobalt alloys.
(d) ~Pr~mic~s Typically, a cPr~mic is a metal oxide, boride, carbide, nitride, or a llli~Ult~ of such m~tPri~l~. Ce~mics are inorganic, nonmPt~llic, nonmolecul~r solids, in~ lu-ling both amorphous and crystalline m~tPri~l~. Cer~mics are t~tive of m~teri~l~ that can be formed and screened for a particular ~ y using the present invention. Such m~t-ori~l~ include, for example, ~lnmin~, coniulll, silicon carbide, aluminum nitride, silicon nitride, the YBa2Cu307 8 ~u~ clllctor, the La2"Sr~CuO4 supe conductors, the Bi2CaSr2Cu208+"
sup~ ctors~ the Bal "K"B;03 superconductors, the ReBaCu ~u~ondllctors, ferrite (BaFe~20,9), Zeolite A (Nal2t(SiO2)~2(Al02)]-27H20), soft and perm~n~nt magnets, high dielectric constant materials (BaTiO3), piezoelectric m~tP.r~ (e.g., lead zirconate titanate (PZT), NaNbO3, and NaTaO3), electro-optic m~tPri~l~
- (e.g., lithium niobate (LiNbO3)), giant magnetoresistant m~t~ (GMR), etc. A
"giant m~gnPtoresistant" m~tPli~l, as used herein, refers to a m~tPli~l having achange in re~i~t~nre when exposed to a m~gnetic field that is greater than S
percent relative to the re~i~t~nce it had when no field was applied. That is to say, the absolute value of the percentage change in re~i~t~nce is greater than 5 percent, W O96111878 PCTrUS95/13278 i.e., ¦~R¦ > 5%. Thechangeinreci~t~nceisd~ "l,hedby:
~R z [Resist~nc6~ Mlen A Fiold I~ AppliedJ - [Resist~nCe ~en No Field I6 Appli~
R . [Resi~tance When No Field Is Appliedl 10. Or~anic Materia~s: Co~ uullds, which generally consist of carbon and hydrogen, with or without oxygen, nitrogen or other elPm~ntc, except those in which carbon does not play a critical role (e.g., carbonate salts).
F.Y~mplPs of organic m~tPri~l.c which can be synth~ci7~1 using the methods of the present invention inc.lllcle, but are not restricted to, the following:
(a) Non-biological, organic polymers: Nonmpt~ c m~tPri~lc c~ ncictin~ of large macromolecules composed of many repe~fing units. Such m~t.o.ri~l.c can be either natural or synthetic, cross-linked or non-crocclinkPrl, and they may be homopolymers, copolymers, or higher-ordered polymers (e.g., terpolymers, etc.). By "non-biological," a-amino acids and nucleotides are ~Y~ le l. More particularly, "non-biological, organic polymers" eyc~ p those polymers which are synthesized by a linear, stepwise coupling of building blocks. Examples of polymers which can be d using the methods of the present invention include, but are not limited to, the following: polyurethanes, polyesters, polycarbonates, polyethylPnPiminPs, poly~çet~tPs, polystyrenes, polyamides, poly~nilinPs, polyacetylenes, polypyrroles, etc.
11. Or~nometallic Materials: A class of compounds of the type R-M, wherein carbon atoms are linked directly with metal atoms (e.g., lead tetraethyl (Pb(C2Hs)4), sodium phenyl (C6H5-Na), zinc dimethyl (Zn(CH3)2), etc.).
12. Composite Materials: Any combination of two m~tPri~ liffPrin~ in form or composition on a macroscale. The con~tit~le-nt~ of composite m~t~ri~l~ retain their ~ o.nti~iP~s~ i:e., they do not dissolve or merge completely into one another although they act in concert. Such co~ osite materials may be inorganic, organicor a combination thereof. Included within this definition are, for example, doped m~tPri~l~, dispersed metal catalysts and other heterogeneous solids.
W O 96/11878 PCT~US95~I3278 II. General Overview The present invention provides methods and a~)~aldtus for the ~,r~p~ ;on and use of a ~ubsLIdlG having an array of m~tt~ri~l~ in predPfinP~1 regions thereon. The invention is ~IP~rihecl herein prim~rl ly with regard to the ~re~ ;on of inolE;~Iic S m~tP.ri~l~, but can readily be applied in the ~,lG~ ;on of other m~t-ori~l~ M~tPri~l~
which can be ~le~alc d in accord~ ce with the methods of the present invention in~ltlde, for eY~mple, covalent network solids, ionic solids and mnlPc~ r solids. More particularly, m~tPri~l.c which can be l~lGl~alGd in acco~ ce with the mPth~ls of the present invention inclu-lP, but are nol: limited to, il~Ol~ iC m~tPri~1~, intermPt~llic 10 m~tPri~, metal alloys, CP.r~miC m~t~ri~l.c, organic m~tPri~l~, organomPt~llic m~tPri~
non-biological organic polymers, composite materials (e.g., inorganic COIll~OSi~organic composites, or combin~tion~ thereof), or other m~tPri~lc which will be a~ t;nt to those of skill in the art upon review of this disclosure.
The resulting substrate having an array of m~tt-ri~l.c thereon will have a 15 variety of uses. For eY~mple, once ~lGpar~d, the substrate can be screened for m~tPri~l~
having useful pl.)~ies. Accordingly, the array of m~teri~l~ iS preferably synthP~i on a single substrate. By synthPsi7in~ the array of mateAals on a single ~ul~sL~screening the array for m~tPri~l~ having useful properties is more easily carried out.
Properties which can be screened for include, for example, elP~tric~l, thermal 20 mech~nic~l, morphological, optical, m~gnP,tic, chP.miç~l, etc. More particularly, properties which can be screened for inclllde, for example, conductivity, super-conductivity, resistivity, thermal conductivity, anisotropy, hardness, crystallinity, optical tr~n~r~renCy, m~netoresi~t~nce, permeability, frequency doubling, photoemi~ion, coercivity, ~ plp-ctric strength, or other useful properties which will be appalcllt to those 25 of skill in the art upon review of this disclosure. I~ ntly, the synthe~i7ing and screening of a diverse array of m~tPri~lc enables new compositif)n~ with new physical properties to be itiPntifiP~i Any material found to possess a useful ~r~lty can be subsequently ~r~a,cd on a large-scale. It will be a~a- nt to those of skill in the art that once useful m~tPri~l~ have been idPntifiPd using the methods of the present invention, a 30 variety of different methcl-ls can be used to ~lcpalc such useful m~teri~ on a large or bulk scale with es~nti~lly the same structure and ~lopel~ies.
~ PnPr~lly, the array of materials is yl~ucd by succes~ively delivering components of m~tPri~l~ to pre~e-finPA regions on a substrate, and siml-lt~n~usly reacting _ _ W O96/11878 PCTrUS95/13278 the co--,~nents to form at least two m~tPr~ In one emb~imP-nt, for example, a first component of a first m~tPri~l is delivered to a first prefGl.ed region on a substrate, and a first col--~onent of a second m~t~Pri~l is delivered to a second ~lGrGllGd region on the same substrate. Thereafter, a second component of the first m~tPri~l is delivered to the S first region on the substrate, and a second co--,~onent of the second m~tPri~l is delivered to the second region on the substrate. Each cor"ponent can be delivered in either a l...;r.,.... or gradient fashion to produce either a single stoichiometry or, alternatively, a large number of stoiçhiometries within a single preAçfinPA region. Moreover, re~rt~nt~
can be delivered as amorphous films, e~it~ial films, or lattice or su~ e structures.
10 The process is repe~tPA, with additional co",~nents, to form a vast array of components at predP-finP~i, i.e., known, locations on the substrate. Thereafter, the components are ~imlllt~nPously reacted to form at least two m~tPri~ As eYrl~inP11 hereinbelow, the co"~nents can be sequentially or simultaneously delivered to predefine~ regions on the substrate using any of a number of dirrelt;J~t delivery techniques.
In the mPtho-ls of the present invention, the components, after being delivered to pre~lPfine~ regions on the substrate, can be reacted using a number of different synthetic routes. For example, the components can be reacted using, for example, solution based synthesis techniques, photoch~mir~l techniques, polymPri7~tion techniques, tP-mpl~tP- directed synthesis techniques, epitaxial growth techniques, by the sol-gel process, by thermal, infrared or microwave heating, by c~lcin~tion, ~intrrin~ or ~nnP~linF~, by hy~ hermal methods, by flux methods, by cryst~lli7~tion through vaporization of solvent, etc. Other useful synthesis techniques that can be used to ~imlllt~nPously react the components of interest will be readily apl)a,c~"l to those of skill in the art.
Since the reactions are con~luctP~ in parallel, the ~u~ber of reaction steps can be minimi7Pcl. Moreover, the reaction con~iti()nS at dirr~,cl t reaction regions can be controlled intlepen-lently. As such, reactant amounts, reactant solvents, reaction le".pel~lult;s, reaction times, the rates at which the reactions are qllenched, deposition order of re~ct~nt~, etc. can be varied from reaction region to reaction region on the substrate. Thus, for example, the first co",ponent of the first m~tPri~l and the first co",~onent of the second m~teri~l can be the same or different. If the first component of the first m~tPri~l is the same as the first co",ponent of the second m~tPri~l~, this co",~nent can be offered to the first and second regions on the subst~te in either the W O 96/11878 PCT~USg~/13278 same or dir~c~l~ amounts. This is true as well for the second col,l~onent of the first m~t~.ri~l and the second component of the second m~ttq.ri~l, etC. As with the first cc,.-.l~ol~ent of the first and second m~t~ , the second co.~onent of the first m~t~
and the second component of the second m~t~ri~l can be the same or dirr~lci l and, if the S same, this co~ onent can be offered to the first and second regions on the sul,slldte in either the same or different amounts. Moreover, within a given preAefinPA region on the substrate, the cGl..~l~ent can be delivered in either a uniform or gr~rliPnt fashion. In hnn~ if the same co..,~onents are delivered to the first and second regions on the ~ul)slld~e at id~-ntic~l concentrations, then the reaction conditions (e.g., reaction 10 tem~ es, reaction times, etc.) under which the reactions are carried out can be varied from reaction region to reaction region.
Moreover, in one embodiment of the present invention, a method is provided for forming at least two different arrays of m~teri~l~ by delivering subst~nt~ y the same reactant co."ponents at subst~nti~lly identic~l con~ntr~tions to re~action regions on both first and second substrates and, thelc~~ , subjecting the col"~onents on the first ~ulJsLLdte to a first set of reaction con~litions and the co-"l~onents on the second substrate to a second set of reaction conditions in a wide array of co",~o~ on~. Using this method, the effects of the various reaction p~r~mPtPrs can be studied and, in turn, optimized. Reaction p~r~mPtPrs which can be varied include, for example, reactant amounts, reactant solvents, reaction le."~t;-dtures, reaction times, the pl~S .UlC;S at which the reactions are carried out, the atmospheres in which the re~tion~ are con-luct~P~, the rates at which the reactions are qu~Pn~hP~l, the order in which the re~ct~nt~ are deposited, etc. Other reaction p~r~mPtP~s which can be varied will be a~ t to those of skill in the art.
The reactant col"~nerlts in the individual reaction regions must often be prevented from moving to ~ e-nt reaction regions. Most simply, this can be ensured by leaving a sl-fficient amount of space between the reaction regions on the substrate so that the various components cannot interdiffuse between reaction regions. Moreover, this can be ensured by providing an al~pro~liale barrier between the various reaction regions on the ~UbsLldte. In one approach, a me~h~ni~l device or physical structure defines the various reaction regions on the substrate. A wall or other physical barrier, for example, can be used to prevent the reactant col~lponents in the individual reaction regions from moving to adjacent reaction regions. This wall or physical barrier can be removed after W O96/11878 PCTrUS9~113278 the synthesis is carried out. One of skill in the art will ap~rec;ate that, at times, it may be benPfici~l to remove the wall or physical barrier before scl~n-ng the array of m~tP.ri~
In another approach, a hydrophobic m~tPri~l, for example, can be used to S coat the region surrounding the individual reaction regions. Such m~tPn~1S prevent aqueous (and certain other polar) solutions from moving to ~ rPnt reaction regions on the substrate. Of course, when non-aqueous or nonpolar solvents are employed, different surface co~ting~ will be required. Moreover, by choosing ap~.u~liate m~tPri~1~ (e.g., substrate m~tPri~l, hydrophobic co~ting~ reactant solvents, etc.), one can control the 10 contact angle of the droplet with respect to the substrate surface. Large contact angles are desired because the area surrounding the reaction region remains un~velled by the sol~ltion within the reaction region.
In the delivery systems of the present invention, a small, precisely metered amount of each reactant col"pollent is delivered into each reaction region. This may be 15 ~complished using a variety of delivery techniques, either alone or in combination with a variety of m~ ing techniques. For example, thin-film deposition techniques in comhin~tion with physical m~clring or photolithographic techniques can be used to deliver the various reactant components to s~ ted regions on the substrate. More particularly, ~u~ g systems, spraying techniques, laser ablation techniques, electron beam or 20 th~rm~l evaporation, ion im~ nt~tion or doping techniques, t~h~mi~l vapor deposition (CVD), as well as other techniques used in the fabrication of integr~ted circuits and epitaxially grown m~tçri~l~ can be applied to deposit highly uniform layers of the various reactant components on selected regions on the substrate. ~ltPrn~tively, by varying the relative geometries of the mask, target and/or substrate, a gradient of reactant25 c~ ponents can be deposited within each predefined regions on the substrate or, ~lt~rn~tively, over all of the predefin~qA regions on the substrate. Such thin-film deposition techniques are generally used in combination with m~ing techniques toensure that the reactant co",pollents are being delivered only to the reaction regions of interest. ~ -Moreover, in addition to the foregoing, the various reactant components can be deposited on the reaction regions of interest from a dispenser in the form of droplets or powder. Conventional micr~il)ellillg apparatuses can, for eY~mple, be --adapted to dispense droplet volumes of 5 nanoliters or smaller from a capillary. Such W O 96/11878 PCTrUS95/13278 droplets can fit within a reaction region having a (1i~m~.ter of 300 ~m or less when a mask is employed. The ~iicpencp~r can also be of the type employed in convention~l ink-jet ~r;.~ . Such inkjet licp~n~Pr systems include, for example, the pulse pres~ule type ~licI~encpr system, the bubble jet type ~lisrPnc~r system and the slit jet type ~li.cp~n~.r 5 system. These inkjet tii~pen~r systems are able to deliver droplet volumes as small as S
picr-liters. Moreover, such llicp~n~l systems can be manual or, ~ ;vely, they can be ~ulollla~d using, for eY~mple, robotics techniques.
The ~li.cI-e.ncer of the present invention can be aligned with respect to the a~lupliate reaction regions by a variety of conventional systems. Such systems, which 10 are widely used in the microelectronic device fabrication and testing arts, can deliver droplets of reactant col-,ponents to individual reaction regions at rates of up to 5,000 drops per second. The tr~ne1~tional (X-Y) accuracy of such systems is well within 1 ~um.
The position of thLe dispenser stage of such systems can be calibrated with respect to thLe position of the substrate by a variety of methods known in the art. For example, with 15 only one or two reference points on the substrate surface, a "dead reckoning" method can be provided to locate each reaction region on the substrate. The reference marks in any such systems can be accur~t~oly idçntifi~1 by using capacitive, resistive or optical sensors.
vely~ a "vision" system employing a camera can be employed.
In another embodiment of the present invention, the dispenser can be 20 aligned with respect to the reaction region of interest by a system analogous to that employed in m~gnetic and optical storage media fields. For example, the reaction region in which the reactant co-llponent is to be deposited is jdentifilod by its track and sector location on the disk substrate. The di~peneer is then moved to the app-~liale track while the disk substrate rotates. When the applopriate reaction region is poeitiol-~d 25 below the dispenser, a droplet of reactant solution is rele~eed.
In some embo-lim~-nte, the reaction regions may be further defined by dimples in the substrate surface. This will be especially advantageous when a head or other sensing device must contact or glide along the substrate surface. The dimples can also act as id~ntific~tion marks direcl:ing the dispenser to the reaction region of interest.
W O96/11878 PCTrUS95/13278 III. Isolafion of R~n~fion Regions On A Substrate In a ~lGrG lGd emb~impnt~ the methods of the present invention are used to prG~e an array of diverse m~teri~l~ at known ~ tiOnC on a single substrate surf~ce.
F.~P.nti~1ly, any conceivable substrate can be employed in the invention. The substrate can be organic, inorganic, biological, nonbiological, or a combination of any of these, PYi.cting as particles, str~n-ls, preripit~tes, gels, sheets, tubing, spheres, cont~inPrs, c~pill~riPs, pads, slices, films, plates, slides, etc. The substrate can have any convenient shape, such a disc, square, sphere, circle, ~tc. The substrate is preferably flat, but may take on a variety of ~lt~rn~tive surface configur~tionc For example, the substrate may contain raised or dGprGssed regions on which the synthesis of diverse m~tPri~l.c takes place. The substrate and its surface preferably form a rigid support on which to carry out the re~rtinnc described herein. The substrate may be any of a wide variety of m~tPr~ in~ in,~, for e~mple, polymers, plastics, pyrex, quartz, resins, silicon, silica or silica-based m~tPri~ls, carbon, metals, inorganic ~1~CSeS, inorganic crystals, membranes, etc. Other substrate m~t~ri~l~ will be readily aL~ar. n~ to those of skill in the art upon review of this ~li.celosllre. Surfaces on the solid substrate can be composed of the same m~tPri~l~ as the substrate or, alternatively, they can be dirrGlc.lt, i.e., the substrates can be coated with a different m~tPri~l Moreover, the substrate surface can contain thereon an adsorbent (for example, cellulose) to which the components of interest are delivered. The most a~)r~liate substrate and substrate-surface m~tPri~l~ will depend on the class of m~tPri~l.c to be synthesi7çd and the selection in any given case will be readily a~a,enl to those of skill in the art.
In some embo limPnt~, a predçfinPd region on the substrate and, the,cfore, the area upon which each distinct material is synthP.si7Pd is smaller than about 25 cm2, preferably less than 10 cm2, more preferably less than 5 cm2, even more preferably 1 cm2, still more preferably less than 1 mm2, and still more preferably less than 0.5 mm2.
In most ~ref~lled embo-limPntc, the regions have an area less than about 10,000 ,um2, preferably less than 1,000 ,um2, more preferably less than 100 ~m2, and even more preferably less than 10 ~Lm2.
In plt;Ç~ d embo limPnt~, a single substrate has at least 10 different m~tPri~l~ and, more preferably, at least 100 different m~t~qri~l~ synthP~i7Pd thereon. In even more p~erc~ d embo-limçnt~, a single substrate has more than 103, 104, 105, 106, or more m~t-~ri~ synthesized thereon. In some embo~iimPnt~ the delivery process is W O96/11878 PCTnUS95113278 ed to provide m~t~ri71~ with as few as two ccjl-.~nents, although the process can be readily ~rl~rtP~ to form m~tPri~l~ having 3, 4, S, 6, 7, 8 or more co.llponents therein. The density of regions per unit area will be greater than .04 regions/cm2, more preferably greater than 0.1 regions/cm2, even more preferably greater than 1 region/cm2, 5 even more preferably greater than 10 regions/cm2, and still more preferably greater than 100 regions/cm2. In most pl~r~llcd embl!dim~nt~, the density of regions per unit area will be greater than 1,000 regions/cm2, more preferably 10,000 regions/cm2, even more preferably greater than 100,000 regions/cm2, and still more ylcÇ~l~bly 10,000,000 regions/cm2.
In other embo~lim~nts~ the substrate can be a series of small beads or pellets (hereinafter "beads"). The number of beads used will depend on the number of m~teri~l~ to be synthrsi7~d and can range anywhere from 2 to an infinite number of beads. In this emboclim~nt, each of the beads is uniformly coated with the reactant co~ onent(s) of interest and, thereafter, reacted. This is readily done, for eY~mple, b 15 using a series of vessels each of which contains a solution of a particular reactant component. The beads are equally divided into groups colle~ollding to the nllmber of ccslllponents used to generate the array of materials. Each group of beads is then added to one of the vessels wherein a coating of one of the cor.,ponents in solution forms on the surface of each bead. The beads are then pooled together into one group and heated to 20 produce a dry component layer on the surface of each of the beads. The process is repe~tPA several times to generate an array of different reaction col~L~nents on each of the beads. Once the components of interest have been deposited on the beads, the beads are reacted to form an array of m~te~ . All of the beads may or may not be reacted under the same reaction conditions. To determine the history of lthe components25 deposited on a particular bead, mass specLIuscopic techniques can be used.
ely, each bead can have a tag which intlir~tes the history of colllponents deposited thereon as well as their stc;chiometries. The tag can be, for eY~mple, a binary tag etched into the surface of the bead so that it can be read using spe.;lloscopic techniques. As with the single substrate having an array of m~tPri~1~ thereon, each of0 the individual beads or pellets can be screened for m~tPri~l~ having useful l~ro~lies.
More particularly, if an array of m~tP~ is to be g~nP~tPd based on Bi, Cu, Ca and Sr using a series of beads as the substrate, for example, four vessels co~ g aqueous solutions of Bi(NC)3)3, Cu(NO3)3, Ca(NO3)3 and Sr(NO3)3 would be W O96/11878 PCTnUS9S113278 employed. A portion of the beads are added to the vessel cont~ining the Bi(N03)3solution; a portion of the beads are added to the Cu(NO3)3 solution; a portion of the beads are added to the vessel co~ g the Ca(NO3)3 solution; and, finally, a portion of the beads are added to the vessel con~ -g the Sr(NO3)3 solution. Once the beads are 5 ul-iro~ ly coated with the reactant component con~ ed in the vessel, the beads are removed from the vessel, dried, etched, pooled together into one group and, th~l~f~l, ~ubse luently divided and added to the vessels cont~inin~ the for~going l~;L~u~Lco~ ~nents of interest. The process is optionally re~eated, with ~d~1ition~l reactant components, to form a vast array of coll-pollents on each of the beads. It will be readily 10 ~al~nt to those of skill in the art that a number of variations can be made to this technique to generate a vast array of beads cou~ -g a vast array of colll~nents thereon. For example, some of the beads can be coated with only two cGIllponents, others with more than two components. Additionally, some of the beads can be coated two or more times with the same con.ponent, whereas other beads are coated a single 15 time with a given component.
As previously e~q)l~inP~1, the substrate is preferably flat, but may take on a variety of ~ltern~tive surface configurations. Regardless of the configuration of the ~ubsLI~Le surface, it is imperative that the reactant components in the individual reaction regions be prevented from moving to ~ljac~nt reaction regions. Most simply, this can be 20 ensured by leaving a sufflcient amount of space between the regions on the substrate so that the various components cannot interdiffuse between reaction regions. Moreover, this can be ensured by providing an a~luyliate barrier between the various reaction regions on the ~ubsLI~te. A merh~ni~l device or physical structure can be used to define the various regions on the substrate. For example, a wall or other physical barrier can be 25 used to ~rt;vent the reactant col.lponents in the individual reaction regions from moving to ~dj~nt reaction regions. Alternatively, a dimple or other recess can be used to prevent the reactant components in the individual reaction regions from moving to çnt reaction regions.
If the substrate used in the present invention is to contain ~imrlPs or other 30 reces~P.s, the dimples must be suffici~pntly small to allow close p~king on the substrate.
Preferably, the dimples will be less than 1 mm in di~metPr~ preferably less than 0.5 mm in diameter, more preferably less than lO,OOO ~m in ~ m~tPr, even more preferably less than 100 ~m in ~ mPter, and still more preferably less than 25 ~m in rli~mPt~Pr.
W O96111878 PCTrUS95/13278 23 Dimples having these ~h~ teri~tirs can be produced by a variety of techniques inrlll-lin~ laser, pressing, or etching techniques. A suitable rlimpl~ substrate surfaoe can, for e~mrle, be provided by pressing the substrate with an i 1lll.. ;..1~
"master" such as those commonly used to ~lep~ compact optical disks. In addition, an 5 isotropic or anisotropic etching technique employing photolitho~ hy can be employed.
In such techniques, a mask is used to define the reaction regions on the substrate. After the ~sl-dLe is irra~ t~d through the mask, selPct~d regions of the ~)hoL~)lcsist are removed to define the arrangement of reaction regions on the substrate. The dimrlPs may be cut into the substrate with standard plasma or wet etching techniques. If the 10 ~ul,s~"dte is a glass or silicon m~teri~l, suitable wet etch m~tPri~l~ can include hydrogen fluoride, or other common wet etch~nt~ used in the field of semicon-luctnr device fabrication. Suitable plasma elc-~ commonly used in the semiconductor device fabrication field can also be employe~. Such plasma etchants include, for f Y~mp~, lu,Gs of halogen cont;~il-in~ gases and inert gases. Typically, a plasma etch will 15 produce ~limrlps having a depth of less than 10 ~Lm, although depths of up to 50 ~Lm may be obtained under some Con~ition~
Another method for p~ g a suitably dimpled surface employs photoçhPmic~lly etchable glass or polymer sheets. For example, a photoch~mic~llyetchable glass known as "FOTOFORM" is available from Corning Glass Company (New 20 York). Upon exposure to r~ tinn through a mask, the glass becomes soluble in aqueous sclution~. Thelear~r, the exposed glass is simply washed with the a~lu~liale soll-tinn to form the dimpled surface. With this material, well-defined iimrles can be made having aspect ratios of 10 to 1 (depth to ~ m~tt~r) or greater, and depths of up to 0.1 inches. Dimple ~ mPtt~rs can be made as small as 25 ~m in a 250 ~m thick glass 25 layer. Moreover, the rlimpl~ surface can contain thereon an adsorbent (for Py~mple, cellulose) to which the co---ponents of interest are delivered.
Even when a ~impled surface is employed, it is often illl~l~l to ensure that the substrate m~teri~l is not wetted beyond the reaction region parameters. Most simply, this can be ensured by leaving a sufficient amount of space between the regions 30 on the substrate so that the various components cannot interdiffuse between reaction regions. In addition, other techniques can be applied to control the physical interactions that affect wetting, thereby en~urinp~ that the solutions in the individual reaction regions do not wet the ~ull~unding surface and cont~min~t~o other reaction regions. Whether or CA 02202286 1997-04-lX
WO 96/11878 PCT/US9~113278 not a liquid droplet will wet a solid surface is governed by three tensions: the surface tension at the liquid-air intPrface, the intt-rf~ei~l tension at the solid-liquid int~o.rf~ and the surface tension at the solid-air interface. If the sum of the liquid-air and liquid-solid tensions is greater than the solid-air tension, the liquid drop will form a bead (a 5 phenomenon known as "lensing"). If, on the other hand, the sum of the liquid-air and liquid-solid tensions is less than the solid-air tPn~ion~ the drop will not be confinP~ to a given location, but will instead spread over the sl-rf~re. Even if the surface tensions are such that the drop will not spread over the surface, the contact or wetting angle (i.e., the angle between the edge of the drop and the solid substrate) may be sufficiently small 10 such that the drop will cover a relatively large area (possibly e~ctending beyond the confines of a given reaction region). Further, small wetting angles can lead to formation of a thin (appro~cim~trly 10 to 20 A) "precursor film" which spreads away from the liquid bead. Larger wetting angles provide "taller" beads that take up less surface area on the substrate and do not form precursor films. Speeific~lly, if the wetting angle is 15 greater than about 90, a pl~ul:.ur ~llm will not form.
M~.tho ls for controlling chPmic~l compositions and, in turn, the local surface free energy of a substrate surface include a variety of techniques a~aç~nt to those in the art. Chrmiç~l vapor deposition techniques as well as other techniques applied in the f~hrir~tion of i~-le~ ed circuits can be applied to deposit highly uniform 20 layers on stol~ted regions of the substrate surface. If, for eY~mple, an aqueous reactant solution is used, the area surface inside the reaction regions may be hydrophilic, while the surface surrounding the reaction regions may be hydrophobic. As such, the surface çherni.~try can be varied from position to position on the substrate to control the surface free energy and, in turn, the contact angle of the drops of reactant solution. In this 25 manner, an array of reaction regions can be defined on the substrate sl-rf~r~.
Moreover, as previously rYrl~ined, the reactant colll~nents in the individual reaction regions can be prevented from moving to adjaçent reaction regions by leaving a suffiçient amount of space between the regions on the substrate so that the various components çannot interdiffuse between reaction regions.
W O96/11878 PCTrUS95/13278 IV. Methods For Delive~ y Of i~n~t~t Components In the delivery systems of the present invention, a small, precisely metered amount of each reactant co~ onent is delivered to each reaction region. This may be accomr1i~hPfl using a variety of delivlo~ry techniques, either alone or in combination with S a variety of physical m~ing or phot~lithographic techniques. Delivery techniques which are suitable for use in the meth~s of the present invention can generally be broken down into those involving the use of thin-film deposition techniques and those ~nvolving the use of lisp~n~ers.
A. Delive1y Usin~ Thin-FSlm Deposition Technigues Thin-film deposition techniques in combination with physical m~lrinp techniques or photolithographic techniques can be used to deposit thin-films of the various re~ct~nt~ on predefin~d regions on the substrate. Such thin-film deposition techniques can generally be broken down into the following four categc,lies: t;vd~oldli~e 15 methods, glow-discharge processes, gas-phase chemi~l processes, and liquid-phase cilP~ techniques. Tnclll~Pd within these ~leg~j.ies are, for example, ,~u~
techniques, spraying techniques, laser ablation techniques, electron beam or thPrrn~l ~vd~uldlion techniques, ion implanta~;on or doping techniques, çhPmic~l vapor deposition techniques, as well as other techniques used in the fabrication of il~te~ p~d circuits. All 20 of these techniques can be applied to deposit highly u~ layers, i.e., thin-films, of the various re~ t~nt~ on selectçd regions on the substrate. Moreover, by adjusting the relative geometries of the masks, the delivery source and/or the substrate, such thin-film deposition techniques can be used to generate uniform gra~lient~ at each reaction region on the substrate or, ~lt~rn~tively, over all of the reaction regions on the substrate. For 25 an overview of the various thin-film deposition techniques which can be used in the m~th~ of the present invention, see, for example, Handbook of Thin-Film Deposition Processes and Techniques, Noyes Publication (1988), which is incollJol~ted herein by reference for all L,ul~oses.
Thin-films of the various r~ t~nt~ can be deposited on the substrate using 30 e~ e methods in combination with physical m~ ing techniques. Generally, in thermal evaporation or vacuum evaporation methods, the following sequential steps take place: (1) a vapor is gçnt-r~ted by boiling or subliming a target m~tPri~l; (2) the vapor is transported from the source to a substrate; and (3) the vapor is conden~ed to a solid film O96/11878 PCTrUS95/13~78 on the substrate surf~ce. E~d~)old~ i.e., target rn~tP-n~le, which can be used in the evaporative methods cover an extraoldin~y range of chP-mi~l reactivities and vapor ~ iSUlCS and, thus, a wide variety of sources can be used to vaporize the targetm~t.ori~lc. Such sources inçlude, for example, resict~nce-heated fil~m~ntc, electron beams; crucible heated by conducticn, r7di~tic)n or rf-inductions; and arcs, exploding wires and lasers. In ~r~rellcd embo-limPntc of the present invention, thin-film deposition using ~v~ldlive methods is carried out using lasers, fil~mPntc, electron beams or ion beams as the source. In further ~l~rt;llcd embo~limentc of the present invention, thin-film deposition using evd~ldLive methods is carried out using lasers as the source. In such laser ablation techniques, an eYçim~r or YAG laser, having snffici~nt power to cause evapnr~tinn, is directed through a viewport to a target m~t~ri~l held under vacuum.
The target m~t~ri~l is vaporized, the vapor is transported from the source to a substrate, and the vapor is con-l~need to a solid, thin-film on the substrate snrf~ e Successive rounds of deposition, through different physical masks, using the r~l~Oi~g e-vdp.,ldLiv-e methode can be used to gC;ne;ldle an array of reactants on a substrate or parallel synthPsie.
~ olec~ r Beam ~i~xy (MBE) is an e~,al)oldLi~e method that can be used to grow epit~ l thin-films. In this method, the films are formed on single-crystal substrates by slowly evaporating the elPmPnt~1 or molecular conetitu~nte of the ~llm from separate Knudsen effusion source cells (deep crucibles in furnaces with cooled shrouds) onto substrates held at ten.pe dtures a~.u~.iate for chemic~l reaction, epitaxy and re-evaporation of excess re~t~nte The Knudsen effusion source cells produce atomic or mnlPc~ r beams of relatively small ~ mPt~r which are directed at the heated substrate, usually silicon or g~ lm arsenide. Fast shutters are interposed between the source cells and the substrates. By controlling these shutters, one can grow supPrl~ttices with precisely controlled uniformity, lattice match, composition, dopant concentrations, hi~ nes~ and intPrf~eS down to the level of atomic layers.
In ~lrlition to e~/dl,u-a~ e methods, thin-films of the various re~ct~nt~ can be deposited on the substrate using glow-discharge processes in combination withphysical m~ inE techniques. The most basic and well known of these processes is S,L~ullP~ g, i.e., the ejection of surface atoms from an electrode surface by moment-.m transfer from bombarding ions to surface atoms. Sp~ l irlE or sputter-deposition is a tenn used by those of skill in the art to cover a variety of processes, all of which can be used in the methods of the present invention. One such process is RF/DC Glow O 96/11878 PCTrUS95/13278 Discl~ e Plasma Spul(P-~;n~. In thi~ process, a plasma of energized ions is created by applying a high RF or DC voltage between a c~th~le and an anode. The energized ions from the plasma bombard the target and eject atoms which are then deposited on asubsl-dle. Ion-Beam S~UIIP~;n~ is another eY~mrle of a ~ull~ cess which can be used to deposit thin-films of the various reactant co",~onents on a substrate. Ion-Beam Spu~ is similar to the for~going process except the ions are supplied by an ion source and not a pl~cm~ It will be app~llt to one of skill in the art that other~ull~ g techniques (e.g., diode ~ul~ g, reactive sputtPrinP~ etc.) and other glow-discharge processes can be used in the methods of the present invention to deposit thin-films on a substrate. Successive roun,ds of deposition, through different physical masks, using ~~ e~ g or other glow-discharge techniques can be used to generate an array of reactants on a substrate for parallel syntht-cic.
In addition to e~/dL~ldli~te methods and sputtPrin~ techniques, thin-films of the various re~rt~ntc can be depositecl on a substrate using Chernic~l Vapor Deposition (CVD) techniques in combination with physical m~cking techniques. CVD involves the form~tion of stable solids by decomposition of gaseous ch~-mic~lc using heat, pl~cm~
ultraviolet, or other energy source, or a combination of energy sources. Photo-Fnh~nr~d CVD, based on activation of the reactants in the gas or vapor phase by electrom~gnPtic tic)n, usually short-wave ultraviolet r~ tion, and Plasma-Assisted CVD, based onactivation of the re~rt~ntc in the gas or vapor phase using a plasma, are two particularly useful chP-mi~l vapor deposition techniques. Successive rounds of deposition, through diLr~lenl physical masks, using CVD technique can be used to generate an array of re~ct~ntc on a substrate for parallel synthPcic.
In addition to evaporative methods, sputtPring and CVD, thin-films of the various reactants can be deposited on a substrate using a number of different mP~h~nic~l techniques in combination with physical m~cking techniques. Such mPrh~nir~l techniques inrhlde, for Py~mple, spraying, spinning, dipping, draining, flow coating, roller coating, ~les~ule-curtain coating, brushing, etc. Of these, the spray-on and spin-on techniques are particularly useful. Sprayers which can be used to deposit thin-films inclnde, for example, ultr~conic nozzle sprayers, air atomizing nozzle ~ldyel~ and atomizing nozzle s~ldyel~. In ultrasonic sprayers, disc-shaped cP-r~mic piP7Oe1P~t-ic ~ncducPrs covert electrical energy into mech~nic~l energy. The tr~nc-iucers receive electrical input in the form of a high-frequency signal from a power supply that acts as a W O96/11878 PCTrUS95/13278 combination ose~ tQr/~mrlifiP-r. In air ~lo~ ing slJldyel~, the no771es inlclll~i~ air and liquid streams to produce a comrl~ptply atomized spray. In atomizing sprayers, the nozzles use the energy from a ~ræ~i",;7~d liquid to atomize the liquid and, in turn, produce a spray. Successive rounds of deposition, through different physical masks, 5 using mPrh~nir~l techniques, such as spraying, can be used to generate an array of re~ct~ntc on a substrate for parallel synthP~
In addition to the folcgoillg techniques, photolit~ rhic techniques of the type known in the semiconductor industry can be used. For an overview of such techniques, see, for exarnple, Sze, VLSI Technology, McGraw-Hill (1983) and Mead, et 0 al., Introdu~tion to VLSI ~ystems, Addison-Wesley (1980), which are incorporated herein by reference for all purposes. A number of different photolithographic techniques known to those of skill in the art can be used. In one embo-limPnt, for e~mple, a photoresist is deposited on the substrate snrf~re; the photoresist is selectively exposed, i.e., photolyzed; the photolyzed or exposed photoresist is removed; a reactant is deposited on 15 the PYposed region(s) on the substrate; and the rem~ining unphotolyzed photoresist is removed. ~llr. ~ rely, when a negative photoresist is used, the photoresist is deposited on the substr~tP s~ re; the photoresist is selectively exposed, i.e., photolyæd; the unphotolyzed photoresist is removed; a reactant is deposited on the exposed region(s) on the sllbstr~te; and the r~ g photoresist is removed. In another emb~limprlt~ a 20 reactant is deposited on the substrate using, for es~mrle, spin-on or spin-coating techniques; a photoresist is deposited on top of t~e re~rt~nt; the photoresist is selectively exposed, i.e., photolyzed; the photoresist is removed from the exposed region(s); the exposed region(s) are etched to remove the reactant from that region(s); and theining unphotolyzed photoresist is removed. As with the previous embo-limPnt a 25 negative photoresist can be used in place of the positive photoresist. Such photolithographic techniques can be repeated to produce an array of re~rt~ntc on a substrate for parallel synthesis.
It will be readily a~ar~nt to those of skill in the art that the foregoing deposition techniques are intPnded to illustrate, and not restrict, the ways in which the -30 re~rt~nt~ can be deposited on the substrate in the form of thin-films. Other deposition techniques known to and used by those of skill in the art can also be used.
FIG. 1 and FIG. 2 illustrate the use of the physical m~ckin~ techniques which can be used in conjunctions with the aforementioned thin-film deposition W O 96/11878 PCTrUS95/13278 techniques. More particularly, FIG. 1 illll~tr~tP~ one embodiment of the invention di~l( se~ herein in which a substrate 2 is shown in cross-section. The mask 8 can be any of a wide variety of different m~tPri~lc inclu-ling, for eY~mple, polymers, pl~.~ti~, resins, silicon, metals, inorganic g1~S~P~;, etc. Other suitable mask m~tPri~l~ will be S readily a~cllt to those of skill in tlle art. The mask is brought into close proximity with, im~gP~ on, or brought directly into contact with the ~sLIdtc surface as shown in FIG. 1. "OpPnin~" in the mask cc~ ~nd to regions on the substrate where it is desired to deliver a re~ct~nt The op~enings in the mask can take on a variety of dirrclcl.
sizes and shapes. Typically, the openings are circular, rectangular or square.
~ ely, however, they can be linear such that the co~ ents are delivered in a linear fashion from one end of the s~l~sLldLe to the other. This "linear" arrangement f~cilit~t~s screening or ~etPctic)n in certain in~t~nces, such as when thermoelPctric m~tPri~l~ are being discovered and optimi7p~ Conventional binary m~ekin~ techniques in which one-half of the Imask is exposed at a given time are illustrated hereinbelow. It will be readily ap~a,c,-t to those of s~kill in the art, however, that m~cking techniques other than col,~/elllional binary m~cking techniques can be used in the rnethods of the present invention.
As shown in FIG. 2A, the substrate 2 is provided with regions 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50 and S2. Regions 38, 40, 42, 44, 46, 48, 50 and 52 are m~ckPcl, as shown in FIG. 2B, and co",~ollent A is delivered to the exposed regions in the form of a thin-film using, for example, spraying or s~u~e~
techniques, with the res-llting structure shown in FIG. 2C. Thereafter, the mask is repositioned so that regions 26, 28, 34, 36, 42, 44, 50 and 52 are m~kP~i, as shown in FIG. 2D, and component B is delivered to the exposed regions in the form of a thin-film, with the reslllting structure shown in FIG. 2E.
As an ~ltPrn~tive to repositioning the first mask, a second mask can be used and, in fact, multiple masks are frequently required to generate the desired array of reactants. If multiple m~Ling steps are used, ~lignmPnt of the masks may be pelr~ led - using conventional ~lignment techniques in which ~lignmPnt marks (not shown) are used 30 to ~curAtP~y overly succes~ive masks with previous p~lle~ing steps, or more sophi~ticAtPA techniques can be used. Moreover, it may be desirable to provide separation between exposed areas to account for ~ nmPnt tolerances and to ensureseparation of reaction sites so as to prevent cross-cont~min~tinn. In addition, it will be W O 96/11878 PCTrUS95/13278 llnderstQod by those of skill in the art that the delivery techniques used to deliver the various re~t~nt~ to the regions of interest can be varied from reactant to re~ t~nt but, in most in~t~n~s~ it will be most pr~ ti~l to use the sarne deposition technique for each of the re~ct~nt.~.
After co,l,~,-ent B has been delivered to the substrate, regions 30, 32, 34, 36, 46, 48, S0 and 52 are m~.clr~l, as shown in FIG. 2F, using a mask different from that used in the delivery of co,ll~onents A and B. Component C is delivered to the exposed regions in the form of a thin-film, with the resl-ltinE structure shown in FIG.
2G. Th~;rearlel, regions 24, 28, 32, 36, 40, 44, 48 and S2 are m~cl~d, as shown in FIG. 2~I, and component D is delivered to the exposed regions in the form of a thin-film, with the reslllting structure shown in FIG. 2I. Once the c~lllponents of interest have been delivered to ap~r~-iate predefined regions on the substrate, they are ~imllltAn~ously reacted using any of a number of different synthetic routes to form an array of at least two m~t~ri~
lS As previously mentioned, m~.~king techniques other than conventional binary m~ckinE techniques can be employed with the aforementioned thin-film deposition techniques in the met~oll.e of the present invention. For example, FIG. 3 illust~tP.s a m~ckinE technique which can be employed to generate an array of m~t~o.ri~ , eachcon.~ tinE of a comhin~tion of three different col,-pollents, formed from a base group of four dirr~lc.~t colll~vllents. In non-binary techniques, a separate mask is employed for each of the different colllpollents. Thus, in this example, four different masks are employed. As shown in FIG. 3A, the substrate 2 is provided with regions 54, 56, 58 and 60. Region 56 is m~.~k~.d, as shown in FIG. 3B, and colllponent A is delivercd to the exposed regions in the form of a thin-film using, for P~mple, spraying or s~ul~r~ ;~'E --25 techniques, with the resultin.~ structure shown in FIG. 3C. Thereafter, a second mask is employed to mask region 54, as shown in FIG. 3D, and component B is delivered to the exposed regions in the form of a thin-film, with the resulting structure shown in FIG.
3E. Thereafter, region 58 is masked using a third mask, as shown in FIG. 3F, andcomponent C is delivered to the exposed regions in the form of a thin-film, with the resultin~ structure shown in FIG. 3G. Finally, a fourth mask is employed to maskregion 60, as shown in FIG. 3H, and component D is delivered to the exposed regions in -the form of a thin-film, with the re.~ulting structure shown in FlG. 3I. Once the components of interest have been delivered to a~lo~liate preclefined regions on the wo 96/11878 PcT/uss~Jl3278 substrate, they are sim~ nP~usly rea.cted using any of a number of different synthetic routes to form an array of four dirr~fen~ m~tPri~
FIG. 4 i~ sl~.t~s another m~kin~ technique which can be employed to ~.ner~t~ an array of m~tP.ri~l.c, each ~Qn~i.ctin~ of a combination of three dirrt;lc~lt S cG~ onents~ formed from a base group of SiA dirre~ t col--ponents. As shown in FIG.
4A, the substrate 2 is provided with regions 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98 and 100. Regions 64, 68, 72, 76, 80, 84, 88, 92, 96 and 100 are m~lrPd, as shown in FIG. 413, and cG---ponent A is delivered to the .A~osed regions in the form of a thin-film using, for example, spraying or s~ g techniques, 10 with the res-lltin~ structure shown in FIG. 4C. Thereafter, a second mask is employed to mask regions 62, 66, 7~, 74, 80, 82, 88, 90, 96 and 98, as shown in FIG. 4D, and component B is delivered to the exposed regions in the form of a thin-film, with the resultin~ structure shown in FIG. 4E. Thereafter, regions 64, 66, 70, 74, 78, 82, 86, 92, 96, and 100 are m~ P~l using a third mask, as shown in FIG. 4F, and co.l.pol~ent C
lS is delivered to the exposed regions in the form of a thin-film, with the resulting structure shown in FIG. 4G. Thereafter, a fourth mask is employed to mask regions 64, 66, 70, 76, 78, 84, 88, 90, 94 and 98, as shown in FIG. 4H, and co.-,ponent D is delivered to the exposed regions in the form of a thin-film, with the resultin~ structure shown in FIG.
4I. Thelc~rler, regions 62, 68, 70, 74, 80, 84, 86, 90, 94 and 100 are m~Pcl with a.
20 fifth mask, as shown in FIG. 4J, and co~pol-ent E is delivered to the exposed regions in the form of a thin-film, with the resnlting structure shown in FIG. 4K. Finally, a sixth mask is employed to mask regions 62, 68, 72, 76, 78, 82, 86, 92, 94 and 98, as shown in FIG. 4L, and co---ponent F is delivered to the exposed regions in the form of a thin-film, with the reslllting structure shown in FIG. 4M. Once the co...ponents of interest 25 have been delivered to a~liate pre~r.fin~ regions on the substrate, they are ~imlllt~neously reacted using any of a, number of different synthetic routes to form an array of 20 difrelGnt m~tPri~l~
It will be readily appal:ent to those of skill in the art that prior to reactingthe fol~going co---ponents, an additional reactant colll~nent can be delivered to the 30 pre~lefinP~ regions on the substrate in a gradient of stoichiomPtries. For example, once the six co-ll~onents have been delivered to app,opliate pre~efinP~ regions on the substrate, a seventh component can be delivered in a gradient fashion across the entire substrate or across portions of the substrate. The seventh co-llponent can, for ex~mr1e, W O96/11878 PCTrUS95113278 be de~osiled ll~u~h an ~ o~liate mask from left to right as a ~ pnt layer r~n~in~
from about 100 A to 1,000 A in thi~knP.ss Thereafter, the reactant co.,-pollents can be .cimlllt~ne~usly reacted using any of a number of different synthetic routes to form an array of dirrt;lc,~t m~tPri~lc.
In ~rl~1itinn, it will be readily ap~arent to those of skill in the art that ~ltPrn~tive m~Cl~in~ techniques can be employed to gentldle an array of m~tPri~lc, each cnnCistin~ of a combination of 3 or more co-"ponents, formed from a base group of four or more components. In fact, the present invention provides a general method which can be used to gP.nP.r~te coml-in~tc-i~l m~Clrin~ p~tternc for eYI-erimPntC involving the use of 10 distinct groups of reaction components, wherein the members of each group are related in such a way that it would not be desirable for them to interact with one another. In this mP.th~l, a vector is used to lei.lesellt each of the subgroups of col-lponents. For ~Y~mpl~o, a ~Ubg~vu~ of colllponents, such as the lanth~ni~1es, is l~ csented by a vector An~ = [Al, A2, A3, ... Aml = [La, Y, Ce, .... Lu], wherein m ranges from 1 to p, and p is the total number of members within the subgroup. It should be noted that the colll~onents can be placed in any order. Moreover, if a particular component of a subgroup is present at different stoichiometries, each of the dirrereilt stoichiometries would be .~r~ senled in the vector (e.g., Al 2 would correspond to a different stoit~hiometry than Al.,).
Once each of the subgroup of co.npollents is l~.es~ ed by a vector, a dyad of vectors is formed. For example, if there were two subgroups of co.nl,onents, e.g., subgroup A and subgroup B, the vector L~l~sentin~ the A subgroup of co..,pollents would be written Am = tA" A2, A3,.... Am]~ and the vector ~ es~l-tng the B subgroup of colllponents would be written Bn = [Bl, B2, B3,.... Bn]. A dyad of these two vectors 25 would be written A,nBn. This dyad is equal to the tensor of second order illll~t below.
Al Bl Al B2 ..... Al Bn A2 Bl A2 B2 ... - A2 Bn Am Bl A~n B2 .. - Am Bn --W O96/11878 PCTrUS95/13278 The dyad of vectors ADl and Bn results in producing all of the combin~tio~.
belweel~ ~e co~ P~ in subgroup A and the co,-l~ont~ in ~ubgç~u~) B. If the abovedyad is written in vector form, i.e., AmBn = [AlBl, AIB2,...AlBD, A2B" A2B2,...A2Bn, A~DBl, ~DB2~ AmB~ and another dyad is formed between this vector and a vector C~ =
S [Cl, C2, ...CJ, ~ g subgroupl C, then the following matrix cQn~ini~ every ternary combination be~ween subgroups A, B and C is formed.
Al Bl Cl Al Bl C2 .~- Al Bl Ck Al B2 Cl Al B2 C2 ~ Al B2 Ck Al Bn Cl Al Bn C2 ~ Al Bn Ck Am Bn Cl Am Bn C2 -- Am Bn Ck As such, given subgroups A~D~ BD~ C~C~ Dj, .. , all of the combinations using one coll,~onent from each group can be generated in an array format using the following method:
A. l[n the array, each subgroup will either be deposited along a row or along a column of the array. Therefore, the subgroups which co les~ond to the rows and the subgroups which collesl)ond to the columns must be sel~t~d The choice of subgroups will not alter the number of sites in the array, but it will affect the shape of the array. For example, either a 4 x 4 array or a 16 x 1 array can be created without ~ltPring the total number of sites in the array. Typically, the choice of geometry will depend on the configuration available for the library.
B. The rest of the method involves forming dyads within the Row cluster and C'olllmn cluster as illustrated above with subgroups A, B, and C. It should be noted that every dyad in array forrn is converted to a vector form before pr~ding to form the next dyad. There will be a point where only one vector will be present in each of the clusters. These vectors can be de~ign~t~1 the Row and Coll-mn vectors, re.,~ilively. When a dyad is formed between the Row and Column vectors, the res-llting array is the final format of the combin~tori~l library.
W O96111878 PCTrUS95/13278 34 C. The order of components within any of the vectors or arrays does not affect the result, but it does alter the m~ ing p~ttPrn~ needed to ~enPr~t~ the sarne result. If the final array of combinations is arranged as ill~sl.,.~ed in the above eY~mrle using subgroups A, B and C, then only masks with bars along columns or rows 5 will be needed to create a combinatorial library.
In non-m~thPm~t~ l terms, choosing :.Ul~gl'OU~)s ~ u~lCS that all of the rl~-n~ in a subgroup be deposited side by side across either the rows or the columns of the library. With a group of 4 el~mçntC, for example, the array would be subdivided into qu~ir~nt~ along either the rows or columns and then each col,-ponent would be 10 deposited in one of the quadrants. If the rows or columns were already subdivided into let us say thirds, then each of those thirds would be subdivided into qu~l1r~ntc and all 4 colll~nents would be deposited evenly across each of the three larger subdivisions.
It will be readily a~e.lt to those of skill in the art that the fol~oillg mPth~ can be used to generate combinatorial m~ing patterns for any ~ i...Pnt 15 given a set of predPfinP~ coll.~onents.
B. Delive~ Usin~ A Dz~penser In addition to the foregoing delivery techniques, AicrPncçrs can be utilized to g~nPr~t~P diverse combin~tions of reactant components in the form of droplets or 20 powder on a single substrate. As explained above, commercially available miclupi~ lg a~dtus can be adapted to dispense droplet volumes of S n~nolitPrs orsmaller from a capillary. Such droplets can fit within a reaction region having a meter of 300 ,um or less when a non-wetting mask is employed. In some embo iimpntc~ the mi~;l~ipeL~e is accurately and precisely positioned above the reaction, 25 as described below, before the reactant soll1tion is deposited.
In a dirr~re-~t ~,cr~lled embodiment, the present invention employs a solution de~osiling a~dlus that resembles devices commonly employed in the inkjet printing field. Such inkjet dispensers include, for example, the pulse ~r~s~ type, the bubble jet type and the slit jet type. In an inkjet dicpPncPr of the pulse pl~,S;~ll`e type, 30 the prinhng ink is jetted from a nozzle according to a change in plG~i~iUIG applied by a pi~7~P]çctrit~. device. In an inkjet ~icp~ncPr of the bubble jet type, bubbles are gPntr~tP~
with heat generated with a rçci.ct~nce device embedded in a nozzle, and printing ink is jetted by using the force due to the expansion of a bubble. In an inkjet riicpP,ncçr of the O 96/11878 PCTnUS9S/13278 slit jet type, printin~ ink is filled within a slit-like orifice wherein recording electrodes are aligned in coll~;s~~ Pnce to pixels, and a DC voltage pulse is applied bGlween a ~ r~ g electrode and a euu-l~el eleetrode arranged behind a lGcol.lillg paper. In this system, the printing ink around the to]p of the record electrode is charged el~ctric~lly so that the ink is ejected tuw~ds the recording paper with an electrostatic force to record a dot on the paper.
Such inkjet ~ tel~ can be used with minor mo ~ tion by simply substit ltin~ a reactant c~ g solution or reactant con~ ni~-g powder for the ink. For eY~mI~le, Wong, et al., Eul~ope~ Patent Application 260 965, incùll,vl~ted herein by reference for all purposes, describes t~e use of a pulse ~les~ure type inkjet printer to apply an antibody to a solid matri~c. In the process, a solution cont;,i~ the antibody is forced through a small bore no_zle that is vibrating in a manner that fr~mP-nt~ the solution into discrete droplets. The droplets are subsequently charged by passing through an electric field and then deflect~d on~o the matrix m?~teri~l For illustrative pul~oses, a convPntion~l ink drop printer of the pulse ~ssure type in~ des a reservoir in which ink is held under pr~s~iu~e. The ink reservoir feeds a pipe which is conn~cted to a nozzle. An electromPrh~ni~l t~n~d~lcer is employed to vibrate the no771e at some suitably high frequency. The actual structure of the nozzle may have a number of different constructions, incl~ in~ a drawn glass tube which is vibrated by an external tr~n~ducPr, or a metal tube vibrated by an eYt~-m~
~n~ducf~r (e.g., a pie7oPlP~tric crystal), or a m~gnPtostrictive metal tube which is m~gnPtostrictively vibrated. The ink accordingly is ejected from the nozzle in a stream which shortly thereafter breaks into individual drops. An electrode may be present near the nozzle to impart a charge to the d;roplets.
A sçhPm~tic drawing of an ink drop dispenser of the pulse ~ iUle type (such as is described in U.S. Patent Mos. 3,281,860 and 4,121,222, which are incol~ldled by reference herein for all purposes) which may be employed in the present invention is shown in FIG. 5. This a~aldtus comprises a reservoir 210 which contains a solution under pressure. Tubing 212 is connect~P~ to the reservoir 210 and termin~t~ in a metal nozzle 242. No_zle 242 is disposed within a hole provided in pie7~Pl~ctric crystal 240. The end of the metal tube and of the pie7oPlP~tric crystal are made to coincide. The tubing and the pie7OPlectric crystal are soldered together to form a perm~nPnt wa~elp~oof ~t~chmPnt. The coincident ends of the crystal and the tubing are W O96/11878 PCTrUS9S/13278 covered with a washer 244 which is termed an orifice washer. This washer has an opening 246 drilled thGlGlhrough through which the solution is emitted under P1~1rG.
A source of os~ tirn~ 218 is connPctP~l between the outside of the metal tubing 242 and the outside of the pie7oPlP~tric crystal 240. The construction is such that hPrmPti~
5 sealing can be employed which plO ~;~S against electror~lP-miç~l and atmosphPnc attack of the coll,~onents.
The piezoelectric crystal 240 is vibrated subst~nh~lly at the fr_quency of the source of oscill~hon~ c~ in~ the tubing and nozzle to vibrate whereby the solution stream breaks down into droplets 246. A signal source 224 which is syncLol~ized by the 10 source of os~ tions is connPcte~ between the nozzle and the charging cylinder 226. As a result, each of the drops, which should be subst~nti~lly the same mass, receives a charge, the amplitude of which is determined by the amplitude of the signal applied from the source 224 and the charging cylinder 226.
The charged drops, after passing through the charging cylinder, pass into an electric field which is established between two plates respectively 230 and 232 which are conn~t~1 to a field potential source 234. As a result of the action between the field and the charge of each drop, the drops are ~lefl~tçd from their center line path bGl~ce.
the plates in accol.lance with the charge which they carry. Thus, when they fall on an optionally moving writing medium 236, a deposition pattern occurs on the writing20 mt-Aillm l~l5;se~ tive of the information in the signals.
Although the inkjet printer of the pulse pressure type has been described in greater detail herein for purposes of illustration, it will be readily ap~alcnt to those of skill in the art that inkjet lJlinlGl~7 of the bubble jet type and the slit jet type can also be used, with only minor mo~lifi~tirns, to deliver reactant components to pre~efinP~
25 regions on the substrate. Moreover, although the ror~going rli~cu~ n refers to a single nozzle, in a ~lc;rGll~d emb~imt-nt inkjet ylintGl~ having multiple nozzles are used to deliver m~lltiple reactant components to a single preclPfin~ region on the substrate or, ~ltPm~tively, to multiple predefined regions on the substrate. In addition, as improvements are made in field of inkjet plil~ " such improvements can be used in the -30 methods of the present invention.
In other embodiment~, the reactant solutions can be delivered from areservoir to the substrate by an electrophoretic pump. In such a device, a thin capillary connects a reservoir of the reactant with the nozzle of the dispenser. At both ends of the capillary, electrodes are present to provide a potential dirrer~ -ce. As is known in the art, the speed at which a chPmir~l sl~ecies travels in a potential ~ lient of anelectrophoretic mPAillm is governed by a variety of physical pl~,Lies, inr.lurling the charge density, size, and shape of the species being transported, as well as the physical S and ~h~Pmic~l properties of the trans~ort mP~ lm itself. Under the proper conditions of potential gr~tliPnt capillary ~limpn~ and transport mPAillm rheology, a hydrodynamic flow will be set up within the capillary. Thus, bulk fluid Co~ the reactant of interest can be pumped fiom a lcis~ oir to the substrate. By adjusting the ~
position of the substrate with respect to the electrophoretic pump nozzle, the reactant 10 solution can be precisely delivered to pre~lefinPd reaction regions on the substrate.
Using the aforP~mPntinned dispenser systems, the reactants can be delivered to predPfinP~l regions on the substrate either sequentially or ~imlllt~n~usly. In a presently pief~.led emborlimPnt the re~rt~nt~ are simultaneously delivered to either a single pre~lefinP,d region on the substrate or, ~lle. ..~tively, to multiple pred~P-finPA regions 15 on the substrate. For eY~mrlç, using an inkjet ~ pçn~er having two noz71~os~ t~,vo dirr~ t reactants can be ~imlllt~nPously delivered to a single pre lPfin~ region on the substrate. ~ ely, using this same inkjet dispenser, a reactant can be .~imlllt~n~ously delivered to two dirr~ t predPfin~d regions on the ~ul s~l~te. In this in~t~n~e, the same reactant or, ~ltçrn~tively, two different react~nt~ can be delivered. If 20 the same reactant is delivered to both of the pre~lPfin~P~ regions, it can be delivered in either the same or dirrt;,~;nl amounts. Similarly, using an inkjet dispenser having eight nozzles, for example, eight different reactants can be ~imlllt~neously delivered to a single predefined region on the substrate or, ~l~ern~tively, eight re~t~n~.~ (either the same or dirî~l~nl) can be ~imlllt~nt-Qusly delivered to eight different predrfin~l regions on the 25 substrate.
VI. Multfi-Target, Thin-Film J:)eposifion Systems The reaction systems used in carrying out the previously desçrihe~ thin-- film deposition techniques can vary widely and will depe.nd, in large part, on which thin-30 film deposition technique is being employed. The present invention provides a number of different multi-target, thin-film deposition systems which can be used in carrying out the mf thofls of the present invention. Many embodiments and variations of the systems W O96/11878 PCTrUS95/13278 disclosed herein will become a~c;nt to those of skill in the art upon review of this ~li cr.l~,sllre.
A. A Sputtenng System Wi~h A Carrousel An eY~mple of an eight RF m~gnPtron s~u~lP~ g gun system which can be employed in the mPtho-~c of the present invention is illustrated in FIG. 6. This system compricP~c eight R~ m~gnPtron ~u(~ lg guns 110, each of which contains a reactant co",ponent of interest. The eight RF m~gnPtron sputtP-ring guns are located about 2 to about 5 inches above a disk 112 col.~inin~ thereon eight m~ng p~ttPrnc 114 as well as 10 eight film-thi~l~nPcc monitors 116. In this system, the eight RF m~gnPtron ~-"~e~ g guns as well as the disk are fixed. The substrate 118, however, is coupled to a substrate manipulator 120 which is capable of linear and rotational motion and which engages the substrate with the particular mask of interest so that the substrate is in contact with the mask when the s~u~leling begins. Combinations of the eight components are genPr~t~
15 on the sub~lldle by the sequential deposition of each component through its respective mask. This entire system is used in vacuo.
It is also possible to give the disk 112, which contains thereon the eight m~cking patters 114, rotational motion, thereby providing the flexibility needed to match any of the 8 reactant co~ ,onents with any of the eight m~Ckinf~ p~ttPrnC 114. With this 20 flPYihility, it would be advantageous to increase the capacity of the disk 112 to more than eight m~king p~ttt-rn~ 114 so that a reactant component can be deposited throughmultiple m~cking p~tt~rn.~ This is particularly useful when different film thicknPsses of a given reactant component are needed at different sites within the library. In addition, this system can be converted from a polar coordinate system to a X-Y coordina~ system 25 wberein the s~u~le~ g guns, tbe masks and the substrate are in a rectangular configuration.
B. A Sputtering System wi~h A C~ ette An alternative design for a combinatorial sputtt-nn~ system is illustrated in 30 FIG. 7. This system compri~es eight RF m~n~tron sputt~ring guns 110, each of which contains a react~nt component of interest, inserted from the side of the reaction chamber in a complete circle. The substrate is ~tt~rhPd to a shaft 130 having linear and rotational motion. As such, during deposition, the substrate can be tr~n~l~t-Pcl and rotated to face W O 96/11878 PCT~US95113278 any one of the eight RF m~n~tron ~u~ ;nP: guns 110. The subs~tP is locatRd within a ~ul)sll~le holder 132 which, in ~-i(1ition to hok~in~ the sl~bs~tP~ also locks one secondary m~1ring pattern 134 firmly above the substrate 118 (the pfilll~y mask is the grid which defines the size and density of the reactions sites on the substrate and which S is held fixed during the entire experimPnt). After deposition of a reactant co",~nc;lll, a manipulator 138 is used to remove the ~P~onr~ry mask, to place it in a Ç~c!~:Pttp 140, to remove the next desired secondary mask, and to place this mask above the substrate holder 132. The locking mP~h~ni~m on the substrate holder will assure the ~lignmtont of the mask preferably within 25 ~m. ~It will be readily ap~a~ent to those skilled in the art 10 that there are mnltirle schçmes and designs for locking me~h~ni.sm~ which will align a sul~sll~te to a mask with an ~ecur~cy better than 25 ~Lm.) In the configuration illll~tr~t in FIG. 7, the manipulator 138 has linear motion in the vertical direction, and the c~ettç 140 has linear motion in the horizontal direction. With this format, the manipulator 138 can be used to translLate any of the secondary masks in the c~ett~P 140.
15 This design applies preferably to the use of 2 masks, more preferably to the use of 8 masks, even more preferably to the use of 20 masks, and still more preferably to the use of more than 20 masks. Using this system, all of the reactant colllponents of interest can be deposiled through distinct m~ in~ patterns, thereby creating a combinatolial library of layered thin-film plt;~;Ul~iUl~i.
C A Pulsed L~zser Depositzon System With A Cns~ffe A system related to the one described above is that of the pulsed laser deposition system having a c~Ptte eYçh~nge mP~h~ni~m. This design is i1lustr~tP~d in FIG. 8. The reactant colll~nents are placed in a carrousel wheel which can hold at least 25 4 reactant col-.ponents and, more preferably, at least 8 reactant co,-l~onents. An ~ltPrn~tive approach is to place each reactant co--.ponent on a dirr~ t face of a polygon 142 (see, FIG. 8). If, for example, 1he polygon is a decagon, then ten reactant col,lponents can be mounted upon it. With either design, the goal is to be able to rapidly - move a reactant component in front of a laser beam 144 for a specific period of time, 30 and then change reactant colllponents almost in~t~nt~neously. In the carrousel embo limtont, the reactant col..ponents can be quickly rotated to int~l~e.;l the laser beam 144. In the polygon embodimPnt the reactant co...ponents can be interçh~ngP~l by.Spinning the desired polygon face to the front where the laser beam 144 is fixed.
W O 96/11878 PCTrUS9~13278 In co",p~. ;con to ~ h~g thin-film deposition techniques, pulsed laser thin-film de~o~;lioll techniques provide greater flexibility and speed in terms of in~lG~ ing the reactant co~lpol ents, but have reduced unirollllity over areas greater than 1 cm2. However, several techniques are cullclltly being used with lasers to yield S un;r~,s~ s of up to 100 cm2. The first and most common of such techniques is to move the substrate in a pl~nPt~ry motion during the deposition of a reactant component.
The ~lane~uy motion insures that the plume of material ejected by the reactant co",~onent is spread evenly throughout the substrate. The cost of moving the SUbSL,dle during deposition is a reduction in speed since, in effect, many 1 cm2 depositions are required to evenly cover a circle of, for example, 5 cm in ~ m~t~r.
Another approach to achieving uniformity over large areas during the deposition of thin-films is a technique that uses a rastered laser beam. In this design ctr~t~i in FIG. 8, a programmable mirror 146 allows the laser beam to be rastered over the entire ~ m~ter of the ablation target, i.e., the reactant cc,--,~onent. By varying the speed of the r~ct~ring laser beam as a function of position, the ablation plume can be g~n~or~t~ for longer periods of time near the outer edge of the substrate to yield uniform films. This technique also has the advantage of always producing a concictent plume as a function of time.
For the system illustrated in FIG. 8, the substrate is mounted on a shaft 130 which can be rotated and tr~ncl~t~1 vertically. Moreover, in addition to using a racttoring laser beam, each ablation target, i.e., reactant component, rotates so as to expose the entire surface of the target to the laser beam. This improves the uniformity of the deposition for areas greater than 1 square inch. As described above with respect to the system illustrated in FIG. 7, the substrate is placed within a sample holder 132, -and a secondary mask 134 is ~tt~rhe l to the substrate holder 132 above the substrate.
The secondary mask 134 is aligned correctly with the substrate through the use of a locking mto~h~nicm. The ~cur~y of the locking mPrh~ni~m should preferably be better than 25 ,um. In between deposition steps, a mask is interchanged, without breaking the vacuum, with one of the other secondary masks held in the c~cs~tte within the reaction chamber. The general procedure used to exchange the masks was described above.
W 096/11878 ~_1ru~3Srl3278 D. A Pulsed L~er D~, ~r~n System With A Sliding & Shu~ter ~ s~g System When lih~rie5 conl~in;~g more than 1,000 m~t~.ri~l.Q are ~huc~ul~;d to only - S contain ternary, ~''A~ 'y and q.. ;~ .y .. ~ , for e~mr'- the .~.-.. ke. Of dirr~.~n~ m~Q~ steps involved Call easily reach 30. Moreover, each library will likely require the use of some crigin~l m~ in~ p~ttPm~ Thus, it would be adv~nt~eouc to have a system which has the ability to create one of hundreds of dirr~ m~c~in~
p~ c in front of a s.ll~slr, ~e, each within a few sec~n~1~ Such a system is ill..~l. .t~d in FIG. 9.
In this design, the l~ co~ on~-nt targets and laser can be configured as il1--~ A in FIG. 9. The ;~ dle in a s~-bst-~t~- holder 132 is ~tt~h~A to a shaft 130 which has t~nsl~tiQn capabilities in the X, Y and Z directions as well as rotational c~r~biliff~-s The S~sL~ate iS placed below a fixed plate with an a~.lul~ 150 which will preferably be greater than 1 cm2, mlore ~l~f~l~bly greater than 6 cm2, and most f~dbly greater than 50 cm2. Above the a~.Lul~, plate 150 is a flat sheet 152 c~ h~ g thereon mllltir'~ masks. This sheet 152 is ~n~h~ to a manipulator or shaft 130 which can t~ncl~t~ any mask ~ cCLly over the a~.lu~ plate 150. Typically, there is little or no space ~et~ - the a~ ~Lul~ plate 150 and the sheet 152.
One of the masks on the sheet 152 will consist in its most general form of nine slu~s, each of which is a~l)f~;m~t~ly of the same lim~n~i~nC as the a~ u~e in the ap~Lur~ plate 150. Only the middle square is empty. This mask is shown in FIG.
10A. When ~tt~l-h~ to a flat sheel: which can be t~n~l~t~ in the X and Y directi~ns, this mask effectively be~o ~,FS an X/Y shutter mask. As such, it can create dirr~ t size s~lu~es, rect~ngl~s, 'L' shapes and bars in either the X or Y dil~l;nnc Given that the S~SLIdle can also t~ncl~t~ in the X and Y directinns, a two shutter ...,~ ni~m iS formed in this configuration It can readily be seen by those skilled in the art that there are other arrangements (such as an 'L' shaped mask instead of a square mask) which can create a two shutter sys~em that ~L~llllS as the one des~libed herein.
- 30 Using the X/Y shutter mask and svbs~ o comhin~ti~ n, hundreds of .lirr~ m~l ing configl~r~ti~n~ can be gæ~ t~l, each within a few se~ s. For eY~mrle the 5 m~lring p~tte~n~ set forth in FIG. 10B create 5 5~ lr Co]llmn~ along a s~lbs~ for 5 different reactant components. This id~ntit~l design can be eY~uted with the X/Y shutter mask by first slidhlg the mask to the right to form an opening 1/S the W O 96/11878 PCTrUS95/13278 size of the substrate, with the right side of the ~GlLule plate (as shown in the first mask in FIG. lOB), and then moving the substrate to the left after every deLo~it;ol . Ihus, in the same number of deposition steps, i.e., 5, an identir~l pattern is created without the need to eYrh~nge masks. Mo~eove, when a thirknPcc gr~liPnt of one component across S the library is desired, the X/Y shutter can, for eY~mI~le, be tr~ncl~tP~I at a constant speed from right to left as s4Own in FIG. 10C.
The ~o~Ggoing X/Y shutter system can adv~nt~geously be used in comhin~tion with more traditional binary m~cking techniques. For exarnple, when the mask set forth in FIG. 10D is tr~nQl~tP~d across the substrate, 5 different co"l~ollents are deposited in each half of the substrate. However, with the X/Y shutter system, twice the number of steps are nee~. Therefore, it is frequently adv~nt~geQus to incolpo binary masks in addition to the X/Y shutter on the flat sheet lS2 which sits directly above the ~ wt; plate 150. An eY~mpl~ of such a sheet configuration is ill--~t~te~ in FIG. 11. Notice that by rotating the substrate 90, it is possible to apply the m~clrin~;
15 p~ttPrn~ in both the X and Y directions which reduces the number of nece~.y masks by half. If the sheet is fixed in one-~imPncinn (e.g., the X direction), the ~ubsll~le must be given a ro~tion~l degree of freedom so that it can be roated 90.
In ~-ltlition to being used in combination with traditional binary m~cking techniques, the X/Y shutter system can be advantageously used in combination with other 20 m~cking techniques. In paticular, it can be used with the previously described method for genPr~ting m~king strategies for experiments involving the use of distinct groups of reaction co.,lpollents, wherein the members of each group are related in such a way that it would not be desirable for them to interact with one another. The following sets forth an eY~mple of how this can be carried out.
In this example, there are three groups of reactant co,ll~onents, i.e., group 8, group 5 and group 3, each of which contains 8, S, and 3 elempnt~
respectively. Moreover, group 8 has 5 settings per elemçnt, group S has 3 settings per elPment and group 3 has 1 setting per element. As such, the number of reaction sites on the array would be 1800 or (8 x 5) x ( 5 x 3) x (3 x 1). To plG~LlG an array having 1800 reaction sites, one could use a rectangular substrate having 40 rows running across the width of the substrate, and 45 columns running down the length of the substrate.
Group 8, having 8 elements and 5 settings per elçmP-nt7 would be deposited along the rows, whereas group S, having S elements and 3 settings per elemPnt, and group 3, W O96/11878 PCTnUS95/13278 having 3 el~mPnt~ and 1 seffing per elpment~ would be depo~i~d along the coll-mn~.
Using the laser system described in FIG. 9 and ~.~.c~lmin~ the deposition time is about 5 A/s for a 1" x 1" area and the deposition thichn~ for each layer is 2 A, the mlmher of m~ in~ steps required would be 34 fior a total deposition time of 23 ~ ..Y~s. This value S does not take into account the transfer time needed to eYch~n~e the 34 masks. Using the X/Y shutter system described above, 90 steps would be lc luircd for a total deposition time of 1 hour. However, using two masks in combination with the X/Y shutter system, the llulllb~ of m~Cl~ing steps required would be reduced to 50 and the deposition time would be reduced to 33 ..,i.u~es The folego;ng is an .oY~mple of the many different multi-target, thin-film deposition systems which can be used in carrying out the methods of the present invention. Such systems provide general st~t~gies and designs for the systems used to .nlo~r~te coml)inal~,ial libraries of layered thin-film m~t~ri~l~. It will be readily a~nl to those of skill in the art that the rc,lc;going systems can be modified and optimized in 15 minor ways to work with any of the different thin-film deposition techniques.
VII. Moving The Dispenser fi~th Respect To The Substrate To deposit reactant droplets conci~tPntly at precisely specified regions using a ~i~ren~r~ a frame of referenee common to the delivery instrument and the20 substrate is required. In other words, the reference coordinales of the instrument must be accurately mapped onto the reference coordinates of the substrate. Ideally, only two reference points on the substrate are required to completely map the array of reaction regions. The di~pen~rr instrument locates these reference points and then adjust its int.o.rn~l reference coordinales to provide the nece~.y mapping. After this, the25 ~ n~Pr can move a particular tli~t~nc~e in a particular direction and be positionrd dil~11y over a known region. Of course, the ~ )en~r instrument must provide precisely repeatable movemrnt~. Fulther, the individual regions of the array must not move with respect to the reference marks on the substrate after the reference marks have - been formed. Unfo,~u"ately, pressing or other mrrh~nic~l operations commonly 30 encoun~led during fabrication and use of a substrate may warp the substrate such that the correspordenre between the reference marks and the reaction regions is altered.
To allow for this possibility, a substrate CO,.~ both "global" and "local" reference marks is preferably employed. In l"cf~"cd emborlim~nt~, only two W O96111878 PCTrUS95/13278 44 global reference marks are conveniently located on the substrate to define the initial frame of reference. When these points are located, the ~ p~Pnser instrument has an a~r~ te map of the substrate and the predefinP~ regions therein. To assist in locating the exact position of the regions, the substrate is further subdivided into local S frames of reference. Thus, in an initial, "course" adju~tmtont the ~ pçn~Pr is po~itionecl within one of the local frames of lere ence. Once in the local region, the ~ pen~ing instrument looks for local reference marks to define further a local frame of reference.
From these, the 1ispen~lor moves exactly to the reaction region where the reactant is to be deposited. In this manner, the effects of warpage or other defoll"aLion can be 10 ...;ni...i,~xl. The number of local reference marks is determined by the amount of defol,nalion expected in the substrate. If the substrate is sllffiçi~ntly rigid so that little or no defull~laLion will occur, very few local reference marks are required. If substantial deformation is expected, however, more local reference marks are required.
Starting at a single reference point, the micruyi~LLe or other Iiy)çn~er is 15 ~n~l~t~ from one reaction region to another reaction region on the substrate by a correct tli~t~nre in the correct direction (this is the "dead reckoning" navigational technique). Thus, the di~ren~er can move from region to region, rli~rPncin~ correctly metered amounts of re~t~nts In order to initially locate the reference point and align the rli~ren~r directly over it, a vision or blind system can be employed. In a vision 20 system, a camera is rigidly mounted to the ~1icpçncer nozzle. When the camera locates the reference point(s), the di~pen~r is known to be a fixed ~ t~nce and direction away from the point, and a frame of reference is established. Blind systems locate the reference point(s) by capacitive, resistive, or optical techniques, for example. In one eY~mple of an optical technique, a laser beam is tr~n~mitted through or reflected from 25 the substrate. When the beam encounters a reference mark, a change in light intensity is det~ted by a sensor. C~r~citive and resistive techniques are simil~rly applied. A sensor registers a change in c~p~cit~nce or resistivity when a reference point is encountered.
For purposes of this invention, the spacing between the individual regions will vary in accord~ce with the size of the regions used. For PY~mple, if a 1 mm2 30 region is used, the sp~ring between the individual regions will preferably be on the order of 1 mm or less. If, for PY~mple, a 10 ~m2 region is used, the spacing between the individual regions will preferably be on the order of 10 ~m or less. Further, the angular relation between the cells is preferably con~i~te~lt, to within 0.1 degrees. Of course, the W O96/11878 PCTrUS95/13278 photolithn~r~rhic or other process used to define the ~rr~ngem~nt of cells will ~ccllr~tPly define the angle and sr~ein~. Howe~er, in subsequent processes (e.g., pressing pr~sses), the angle can be distorted. Thus, in some embo limPntc, it may be n~e~.y to employ "local" reference points throughout the array.
Tr~ncl~tional mPch~ni~m~ capable of moving with the desired precision are preferably equipped with position fe~lb~ mer,h~ni.cm.c (i.e., encoders) of the type used in devices for semicond~ctor device m~nuf~chlnn~ and testing. Such mP~h~nicmc will preferably be closed loop ~y~GIlls with inci~nifi~ ~nt bacl~l~ch and h~ sis. In lJlerellGd emb~lim~nt~, the tr~nCl~tion mPrh~nicm will have a high rescllltion, i.e., greater than five motor ticks per çnrod~r count. Further, the electro-mto~h~ni~lmP~h~nicm will preferably have a high repeatability relative to the region ~ mP~ter travel f~ict~nce (preferably, + 1-5 ~m).
To deposit a drop of reactant solution on the subslldte accurately, the dispenser nozzle must be placed a correct list~nce above the surface. The di.~pen~r tip preferably should be located about .1 cm to about 6 cm above the substrate surface when the drop is relP~Pd The degree of control neces~ry to achieve such accuracy can be ~tt~in~ with a repeatable high-resol~ltion translation mP~h~nicm of the type dPc~rihed above. In one emborlimPnt the height above the substrate is determined by moving the ~licpPncPr toward the substrate in small incremP~tc, until the dispenser tip touches the ~ dle. At this point, ~he ~iicrPn~r is moved away from the surface a fixed number of increments which coir~sl onds to a specific dict~nce~ From there, the drop is released to the cell below. Preferably, the increments in which the dispenser moves will vary in accordance with the size of the regions used.
In an ~lte. .~ e embor1imPnt the ~ pencçr nozzle is encircled by a sheath that rigidly extends a fixed rlict~nre beyond the licpenCPr tip. Preferably, this ii.ct~nce collG~nds to the rli~ct~n~ e at which the solution drop will fall when delivered to the sele~te~l reaction region. Thus, when the sheath contacts the substrate s~rf~ce, the movement of the licpencPr is halted and the drop is rP~ P~. It is not neces~,y in this - embodiment to move the ~licpPncer back, away from the substrate, after contact is made.
30 In this embodimPnt as well as the previous embodimPnt, the point of contact with the surface can be determined by a variety of techniques such as by monitoling the c~p~çit~nce or recict~nce between the tip of the dispenser (or sheath) and the ~L~sLI~dtG
W 096tll878 PCTtUS95/13278 below. A rapid change in either of these l,r~ellies is observed upon contact with the surf~ce To this point, the dispenser delivery system has been described only in terms of tr~nc1~tional movemPnt~ However, other systems may also be employed. In5 one emb~imPnt, the rli~pen~r is aligned with respect to the region of interest by a system analogous to that employed in m~gnPtic and optical storage media fields. For eY~m~1e, the region in which reactant is to be deposited is identified by a track and sector location on a disk substrate. The ~ ren~çr is then moved to the a~ro~iate track while the disk substrate rotates. When the a~l,l~liate cell is positioned below the 10 ~ pen.~tq.r (as referenced by the a~l~liate sector on the track), a droplet of reactant s~ tion is relP~ed.
Control of the droplet size may be accomplished by various techniques known to those of skill in the art. For example, in one embo~1imPnt, a convçnti~ n~1 mic~u~ g instrument is adapted to dispense droplets of five n~nolitPrs or smaller 15 from a capillary. Such droplets fit within regions having di~metPrs of 300 ,um or less when a non-wetting mask is employed.
Although the above embodiments have been directed to systems employing liquid droplets, minl1~cule aliquots of each test substance can also be delivered to the reaction region as powders or mini~tl1re pellets. Pellets can be formed, for example, 20 from the compound or component of interest and one or more kinds of inert binding m~tPri~1 The composition of such binders and methods for the plepal~tion of such"pellets" will be a~arent to those of skill in the art. Such "mini-pellets" will be co.. l.d~ible with a wide variety of test substances, stable for long periods of time and --suitable for easy withdrawal from the storage vessel and dispensing.
VI. Synthetic Routes For R~ fing The Array of Components Onçe the array of components has been delivered to pre~PfinPIi regions on the substrate, the components can be simultaneously reacted using a number of dirrelellt synthetic routes. The col"~nents can be reacted using, for example, solution based 30 synthesis techniques, photoçhtomi~1 teçhniques, polymeri7~tit)n teçhniques, temp1~tP
direçted synthesis techniques, epitaxial growth techniques, or by the sol-gel process, by thP,rm~l, infrared or microwave heating, by c~lcin~tion, sintPring or ~nnP~1ing, by hydlulllermal methods, by flux methods, by cryst~11i7~tion through v~oli~ion of W O 96tll878 PCTnUS95/13278 solvent, etc. Other useful synthesis techniques will be a~arc. t to those of skill in the art upon review of this disclosure. lMoreover, the most ap~ropliate synthetic route will depend on the class of m~tPri~lc to be synthPci7~p~ and the selection in any given case - will be readily a~ L to those of skill in the art. In addition, it will be readily 5 app~S;nt to those of skill in the art ~hat, if nto~Pc~ry~ the reactant components can be mixed prior to being reacted using, ~or eY~mple, ultr~cQnic techniques, mP~h~ni-~l techniques, etc. Such techniques Call be applied di~Lly to a given pred~.fin~d region on the substrate or, ~llr~ ely, to all of the predefined regions on the subslldte in a cimlllt~nP~us fashion (e.g., the substr~tP can be merh~nic~lly moved in a manner such 10 that the co~ onents are effectively mixed).
Traditional routes to solid-state synthesis involve the ~intPring of solid re~t~nt~. The standard method used to synth~i7P superconductors, for example, is to grind several metal-oxide powders together, co~ ess the Illi~LUie and, thereafter, bake at a te~ r~nging from 800 C to about 1000 C. The el~mPnt~ in the powder 15 llli~LUlC sinter, i.e., they react chPrnic~lly to form new compounds and fuse into a solid, without passing through the liquid or gaseous phase. Gaseous elemPnt~, such as oxygen, can be taken up during ~intPrin~ or, ~ltPrn~tively, in a subsequent step, and the ~it;S:iUl'~
of the system can be varied during ~e synthesis process. Unfortunately, using t~liti~n~l ~intPrin~ techniques, reac~ion rates are limited by the slow diffusion of atoms 20 or ions through solid re~t~nt~, intermPAi~tP~ and products. Moreover, high l~lll~ldLu~es are frequently required to accelerate diffusion and to thermodyn~mi~lly drive the formation of a stable phase.
In contrast to such traditional routes, in the present invention, new routes to solid-synthesis focus on the synthesis of compounds at lower l~ eldtures. It has 25 been found that reaction ~ates can be increased at lower ~lll~t;ldLures by drastically shortening the ~i~t~nce required for Idiffusion of the re~t~nt~ and by increasing the surface to volume ratio. This can be achieve,d by depositing the re~t~nt~ on thesubstrate in the form of very thin-films or, alternatively, by using solution based synthesis techniques wherein the re~t~nt~ are delivered to the substrate in the form of a 30 solution. Moreover, when the synthesis reaction is to be carried out at a temperature r~ngin~ from about 200 C to about 600 C, a molten salt can be employed to dissolve the reactant components. This technique is generally referred to as the flux method.
.Simil~rly, in a hydrotherm~l method, water or other polar solvent cor,~ ing a soluble inorganic salt is employed to dissolve the reactant components. The hydr~th~-rm~l method is usually carried out under~ress.llc and at a terl,l~r,.l~ ranging from about 100 C to about 400 C. Moreover, using the various synthetic routes of the present invention, the array of reactant components can be ~r~sc,-. ;7f~ or de~le~l. ;7P~ under an S inert atmosphere, oxygen or other gas. In addition, in the synthetic routes of the present invention, various regions on the substrate can be exposed to difr~len~ heat hictori~s using, for eY~mple, laser thermolysis, wherein bursts of energy of a predetermined dllr~tion and intensity are delivered to target regions on the substrate.
In fact, in another embodiment of the present invention, the predefine~
10 regions on a substrate can be subjected to different reaction tempeldLules byindepPndently heating the predefinPd regions using a thin-film resistive PlemPnt In this embo~limPnt, a resistive PlemPnt such as tungct~Pn, is deposited on a clean substrate using any one of the previously described thin-film deposition techniques. The resistive e1PmPnt is deposited, for example, in strips along the rows or columns of pre~efin~
15 regions. Each strip is connect~d to an electrical lead which is ~tt~-~h~1 to a power supply. The temperature of the predefined regions can be regulated by varying the power input to a given strip. In general, any conductive m~t~-ri~l having a melting point higher than the ~ dLule at which the reaction is to be carried out can be used as the resistive Plement Suitable m~t~ri~lc include, but are not limited to, metals, alloys, and 20 cPr~mics. Examples of such m~teri~lc include, but are not limited to, indium doped tin oxide (rrO), tlmgctpn~ molybdenum, t~nt~lllm, platinum, copper-nickel alloys, pl~timlm and rhodium alloys, aluminum-nickel alloys, etc.
In some instances, it may be nP~Ps~ry to coat the resistive element with a protective coating so as to prevent interdiffusion between the resistive elemPnt and the 25 array of colll~onents. The protective coating is applied in the form of a thin-film m~tt~ri~l using the previously described thin-film deposition techniques. The l,rotec~ive coating is made from a m~t~ri~l which effectively conducts heat and which is inert at the ~ >e~dL~re at which the reaction is to be carried out. Examples of suitable m~ttori~lc include, but are not limited to, MgO, SrTiO3, BaTiO3, Al2O3 and other semiconductor 30 and cPr~mi~ m~t~ri~l~ which are good conductors and inert.
Once the resistive elem~nt has been deposited, an array of co~ ents is generated using thin-film deposition techniques in combination with m~kin,~ techniques.
An eY~mrle of this approach is illustrated in FIG. 12. In this eY~mr!~, a library of , W O96111878 PCTrUS95/13278 49 cGln~unds was gPnPr~tP~3 subsequent to the deposition of thin-film resistive strips. As str~ted in FIG. 12, a resistive e1e~nent occupies an entire column of ~redelin~
regions on the substrate. It will be readily appa.ent to those of skill in the art, however, that the resistive elemPnt can be deposited in any pattern and, thus, deposition str~tP~jpls 5 can be deci~n~d so that the resistive elemçnt covers different pred~fin~ regions on the substrate.
Furth~rmore, using the synthetic routes of the present invention, the array of colllponents can be processed between the various delivery steps. For PY~mIlle, co~ ol~ent A can be delivered to a first region on a substrate and, thereafter, exposed to 10 oxygen at an elevated ~l"~?~ldture, for example. Subsequently, col,lponent B can be delivered to the first region on the substrate and, thereafter, co",ponents A and B can be reacted under a set of reaction conditions. Other manipulations and proc~in~ steps which can be carried out between the various delivery steps will be a~ t to those of skill in the art upon reading this ~ r,1Os11re.
As such, using the methods of the present invention, the following m~tPri~1~ can be ~ aLed: covalent network solids, ionic solids and molecular solids.
More particularly, the methods of the present invention can be used to prepa.c, for example, inorganic m~t~ri~1~, intermPt~11ic m~t~ , metal alloys, c~r~mic m~tt~ri~
organic m~tt~ri~1~, organom~t~llic m~teri~1~, non-biological organic polymers, csj"",osi~
20 m~t~ri~1~ (e.g., inorganic composites, organic composites, or combinations thereof~, etc.
Ceramics can be pl~c;d, for in~t~nce, by delivering reactant co,llponents to predefined regions on the substrate using, for example, solution based delivery techniques. Once the reactant cG"~onents of interest have been delivered to the substrate, the substrate is heated to the boiling point of the solvent to e~,~oldt~ off the solvent. ~lt~rn~tively, the 25 solvent can be removed by delivering the reactant co".ponenls to a heated substrate. The substrate is then o~ i7P~ to remove unwanted components (e.g., carbon, nilrogell, etc.) from the array. The substrate is then flash heated at a lelll~ldlul~i; of about 800 C to about 875 C for about two minutes Thereafter, the reaction is rapidly qut-nr~h~l and - the array is sc~nn~ for m~tPri~1~ having a particular prope"y, such as 111min~scen-e, 30 su~er~o,lductivity~ tric strength, etc. M~gnetic m~ttori~1~ can be pl~al~d using a similar process except that in the case of m~nPtiC m~t~ri~ the components are delivered to the substrate and simultaneously reacted thereon in the presence of a m~gnPtic field.
W O96/11878 PCTrUS95113278 Moreover, an array of zeolites, i.e., hydrated eili~tPs of al~minum and either sodium, r~lcil~m or both, can be ~l~ared using the m~th~s of the present invention. To ~r~UG an array of such m~tPri~le, the reactant col,l~nents are delivered to pre~lefinP~ regions on a substrate in the form of a slurry. Using a low t~ cl~lulk S (e.g., 60 C to about 70 C) hydrothPrm~l method, for ~Y~mp1P~ the zeolites will crystallize out of solution. In addition, organic polymers can be pre~dlGd by delivering a monomer (or monomers) of interest to predçfin~l regions on the s~ usually in theform of a solution. Once the monomer of interest has been delivered, an ;~ tor iS
added to each region on the substrate. The polymP-ri7~tion reaction is allowed to proceed until the i~ o~ is used up, or until the reaction is termin~tP~l in some other manner.
Upon completion of the polymPri7~ti~ n reaction, the solvent can be removed by, for example, evaporation in vacuo.
It will be readily a~arGmt to those of skill in the art that the foregoing synthetic routes are intendPd to illuctr~t~, and not restrict, the ways in which the rG~ct~nte can be sim~llt~n~Pously reacted to form at least two m~tto.ri~le on a single substrate. Other synthetic routes and other mo lifis~ti~ns known to and used by those of skill in the art can also be used.
VIII. Methods For Screening the Array of Materials Once ~ ued, the array of materials can be screened in parallel for m~tçri~lc having useful l,l~Gllies. Either the entire array or, ~ltPrn~tively, a section thereof (e.g., a row of predPfinod regions) can be screened in parallel for m~tPri~le having useful pl~pGlLies. Sc~nning detection systems are preferably utilized to screen an array of materials wherein the density of regions per unit area will be greater than .04 25 regions/cm2, more preferably greater than 0.1 regions/cm2, even more preferably greater than 1 region/cm2, even more preferably greater than 10 regions/cm2, and still more preferably greater than 100 regions/cm2. In most preferred embo~imPnte, sc~nningdetection systems are preferably utilized to screen an array of m~teri~l.e wherein ~e density of regions per unit area will be greater than 1,000 regions/cm2, more preferably 10,000 regions/cm2, even more preferably greater than 100,Q00 regions/cm2, and still more preferably 10,000,000 regions/cm2.
Accordingly, in a preferred embodiment, the array of m~tPri~1c is synthPei7P~ on a single substrate. By synthçci7ing the array of m~tPri~le on a single W O96/11878 PCT~US95/13278 ~ul~ e~ scloe.~ g the array for m7(~eri~1~ having useful ~,~,~.lies is more easily carried out. I~o~lLies which can be screened for in~ rle for PY~mr~lP, el~Pctri~ thermalmPich~ni~l, morphological, optical, ~ netic~ che-rnic~l, etc. More particularly, useful pç~ ,Lies which can be screened for are set forth in Table I, infra. Any m~tPri~1 found 5 to possess a useful propelLy can subsequently be plc~ ed on a large-scale.
The t)lu~.Lies listed in Table I can be screened for using conventit n~l mPth~e and devices known to and used by those of skill in the art. Sc~nnin~ systems which can be used to screen for the pl~cllies set forth in Table I incl~de, but are not limited ts~, the following: sç~nnin~ Raman spP~l-oscopy; sc~nnin~ NMR ~e ;l.oscoL~y;
10 sc~nnin~ probe s~eclloscol)y inc~ lin~, for e~mple, surface po~n~ialometry, tnnnpllin~
current, atomic force, acoustic microscopy, ehe~ring-stress microscopy, ultra fast photo eYcit~tion, electrostatic force microscope, t--nnelin~ in~luced photo emission microscope, m~gnPt1C force miclosco~e, microwa~e field-induced surface harmonic genP~tion micl~osco~e, nonlinP~r alt~".aLing-current t--nnPlling microscopy, near-field sc~nnin~
15 optical mi.l~,sc~, inPl~tic electron t~nnPling spectrometer, etc.; optical microscopy in different wavelPngth; sc~nning optical ellipsometly (for mP~cllring dielectric constant and multilayer film thicknt~); sc~nnin~ Eddy-current microscope; electron (~liffr~ction) microscope, etc.
More particularly, to screen for conductivity and/or superconductivity, one 20 of the following devices can be used: a Sr~nning RF Susceptibility Probe, a Sr~nning RF/Microw~ve Split-Ring Resonator Detector, or a Sc~nning Superconductors Quantull-Illt~lÇelellce Device (SQUID) Detection System. To screen for hardness, a nanoindentor (li~mon(l tip) can, for eY~mple, be used. To screen for m~gnptorpci~t~nre~ a Sc~nning RFtMicrowave Split-Ring RPSO~ O1 Detector or a SQUID Detection System can be 25 used. To screen for crys~llinity, infrared or Raman spe~ osco~y can be used. To screen for m~gnPtic strength and coercivity, a Sr~nning RF Susceptibility Probe, a Sc~nnin~ RF/Microwave Split-Ring Resonator Detector, a SQUID Detection System or a Hall probe can be used. To screen for fluorescence, a photo~letP~tor or a charged-- coupled device camera can be used. Other sc~nnin~ systems known to those of skill in 30 the art can also be used.
W O96/11878 PCTrUS9S113278 TABLEI. EX~PLES OFPROP~Kll~S WHICH CANBESCREENED FOR
ELECTRICAL: SUPERCONDUCTIVl~Y
CRITICAL CURRENT
CRITICAL MAGNETIC FIELD
CONDUCTIVlTY
RESISTIVITY FOR RESISTIVE FILMS
DIELECTRIC CONSTANT
DIELECTRIC STRENGTH
DIELECTRIC LOSS
STABILITY UNDER BIAS
POLARIZATION
PERMIl~VITY
PIEZOELECTRICITY
ELECTROMIGRATION
I~R~ 'A r.- COEFFICIENT OF EXPANSION
THERMAL CONDUCTIVITY
TEMPERATURE VARIATION
VOLATILlTY & VAPOR PRESSURE
MEC~INICAL: STRESS
ANISOTROPY
ADHESION
HARDNESS
DENSITY
DUCTILITY
ELASTICITY
POROSITY
MORPNOLOGY: CRYSTALLINE OR AMORPHOUS
MICROSTRUCTURE
SURFACE TOPOGRAPHY
CRYSTALLITE ORIENTATION
OPTICAL. REFRACTIVE INDEX
ABSORPTION
BIREFRINGENCE
SPECTRAL CHARACTERISTICS
DISPERSION
FREQUENCY MODULATION
EMISSION
MAGNETIC: SATURATION FLUX DENSITY
MAGNETORESISTANCE
MAGNETORESTRICTION
W O96tll878 PCTrUS95/13278 COERCIVE FORCE
MAGNETIC: PERMEABILITY
C~EMICAL: COMPOSlTION
COMPLEXATION
ACIDlTY-BASIClTY
CATALYSIS
lMPURlTIES
REACIIVlIY WlTH SUBSTRATE
CORROSION & EROSION RESISTANCE
The arrays of the present invention can be screened sequentially or, ely, they can be screened in parallel using a sc~nning system. For in~t~nce~ thearray of m~tt-.ri~le can be sequentially screened for superconductivity using, for eY~mp1e, m~gnPtic decoration (Bit~er pattern) and electron holography. ~1tPrn~tively, the array of 5 m~t~ri~l.e can be sc~nned for supereonductivity using, for example, a Hall-probe, m~gnPtic force mic,vscol~y, SQUID microscopy, a AC susceptibility miclusco~e, a microwave absorption microscope, an Eddy current microscope, etc.
In a presently plc;r~;lled embodiment, a sc~nnin~ detection system is employed. In one embo~1im~Pnt the substrate having an array of m~tPri~l~ thereon is 20 fixed and the det~P~tor has X-Y motion. In this embo~limpnt~ the substrate is placed inside a sealed chamber, close to the detector. The det~P,ctor (e.g., an RF Reson~or, a SQUID detector, etc.) is ~ttachPd to a rigid rod with low thermal conductivity coupled to an X-Y positioning table at room ~ eldture with a sc~nning range of up to l inch and a 2 ~m spatial reso1~-tinn The position of the detector is controlled using stepping 25 motors (or servomotors) connPctP~l ~o a computer-conkolled positioner. The ~II,~ldture of the detector and the substrate can be lowered via helium e~ch~nge gas by liquid helium reservoir located around the chamber. This sc~nning system can be operated at t~P~"~ ..ies r~nging from 600K down to 4.2K (when immersed in liquid helium).
In another embo-liment, the detector is fixed and the substrate having an 30 array of m~tPri~1~ thereon has R-~ motion. In this embo~limpnt~ the substrate is placed on a rotating stage (e.g., a spur gear) driven by a gear rack which is coupled to a micrometer and a stepping motor. This rotating stage is located on a cryogenic sliding table which is driven by a separate micrometer and stepping motor system. This system is capable of sc~nning an area having a l inch radius with a l ~m spatial reso1~-tion. The W O96/11878 PCTrUS95113278 sc~nnin~ and probing are controlled through the use of a col"~?u~el. As with the other embc~im~nt the Le~ lul~ of the dçtector and the ~ubsl~Le can be lowered via helium eY~ n~e gas using a liquid helium reservoir located around the chamber. This sc~nning system can be operated at tG~ tUlGS r~nging from 600K down to 4.2K (when 5 i,nl"Gl~ed in liquid helium).
Using either of the foregoing embodiments, a .Sc~nning RF Susceptibility Det~cti~ n System can, for example, be used to detect the superconductivity of a large array of m~tP-r~ (see, e.B., FIG. 13). Using photolithographic techniques, a micro (about 1 x 1 mm2) spiral coil can be fabricated to probe the conductivity of a sample 10 ~rlj~rPnt to the coil. The signals are picked up by a phase-sensitive detP~tion electronic circuit. Thereafter, the data is analyzed by a computer to obtain a correlation between the ~lu~Lies and stoiehinmetry of a given sample. If desired, analytical results can be fed back to the delivery system so that the system can "zoom in" on the most promising stoiclliometry in the next synthesis cycle.
Moreover, a ~erco-lducting microcircuit implemPnt~tion of a parallel LC
~so~ ce circuit can be used to scan the array of materials for those that are su~o~ ucting. A parallel LC circuit is simply an inductor in parallel with a c~p~itor.
The elPGtrie~l l,r~ lies of both circuit elements give the circuit a reson~nce frequency where a maximum amount of input voltage is transmitted through to the output. The 20 sharpness of the peak, convention~lly measured by its Q value, is determined by the m~t~ri~l$ used in the circuit, whereas the frequency of the lt;sonance is set by the c~p~eit~nce and the inrluct~nce It has been determined that manufacturing the circuit out of a ~uL~elcol--lucting m~teri~l, such as niobium, gives a very high Q value, i.e., a Q
value on the order of 10,000 or more. This is in contrast to commercially available, 25 non-su~ ol-d~lcting capacitors and inductors which generally give Q values on the order of hundreds. The steep peak of the niobium circuit gives rise to high sensitive detection.
In this system, actual dete~h-)n is done by the induction coil. The induct~nce of an inductor is a function of the m~gnetic field geometry through its coils.
In the presence of a nearby superconducting sample, the magnetic field through the 30 incluGtor is distorted by the expulsion of field by the m~teri~l (i.e., the Mei~ner effect).
This, in turn, changes the inductance and shifts the rçson~nce. By following the~esQ~ Ge, one can readily determine when a m~tPri~l is supe~ c~in~. _ W O96/11878 PCTrUS9r,113278 In this sc~nning device, the total circuit is ap~luAi~ tPly S mm x 2.5 mm, with an active area equal to applu,~ y one-fourth of that. The coil is a spiral coil having dimPn~ioî c of about 1.5 mm per side, and the c~r~itor is a two-plate niobium c~r~it~r with a SiO2~ PlPCtriC (i.e., iln.~nl~ting) layer. SQUID m~nPtQmeterS have 5 achieved spatial res~ tinns of 10 ~m, but their sensitivities have been limited by noise present in the Jos~Pph~on junction In the sc~nnin~ device of the present invention, however, the device is unencumbered by noise from the Josephson junction and, thus, a sensitivity for ~mple~ of 1 ~m or less can be achieved. In this embo-lim~nt sensitivity, rather than spatial resolution~ is a more critical crit~rion.
It will be readily a~ el~ to those of skill in the art that the fc,~cgoing ~letP~.t;on systems are intPn~led to i1ln~tr~te, and not restrict, the ways in which the array Of m~tPri~l can be screened for those m~tPri~l~ having useful prop~llies. Other ~lPtP~tinn systems known to and used by those of skill in the art can ~imil~rly be used.
5 LY. Alterna~ive Embo~iments In another embo~limPnt of the present invention, at least two dirrt;lGl-l arrays of m~tPri~l~ are p cpalcd by de1ivering subst~nti~lly the same reaction colll~onelll~
at subst~nti~lly id~nti~l concentr~tinns to predefined regions on both first and second substrates and, thereafter, subjecting the components on the first substrate to a first set of 20 reaction conditions and the colnpollen~s on the second substrate to a second set of reaction conditions in a wide array of compositions. If a first substrate has, for example, components A and B on a first region on the substrate and, in addition, components X
and Y on a second region on the substrate, the second substrate is ~ al~d in a manner such that it has subst~nti~lly the same components in pre~PfinP~ regions thereon. That is 25 to say, the second substrate is substantially identir~l to the first substrate in terms of the colll~ollents cont~in~A thereon. As such, in this example, the second substrate would also have components A and B on the first region on the substrate and, in addition, colll~nents X and Y on the second region on the substrate.
Once the components have been delivered to their a~pr~iate prP~dPfinPd 30 regions on the substrate, the colll~onents on the first substrate are reacted using a first set of reaction conditions, whereas the components on the second substrate are reacted using a second set of reaction ccnditions. It will be understood by those of skill in the art that the components on the first substrate can be reacted under a first set of reaction W O96/11878 PCTrUS9S/13278 c~ntliti~n~ at the same time as the co,.,~onents on the second substrate are reacted under a second set of reaction conditions or, ~ t..~t;.~ely, the components on the first substrate can be reacted under a first set of reaction conditions either before or after the colllpol~ents on the second substrate are reacted under a second set of reaction conditions.
S In this embodimPnt the effects of various reaction p~r~mPte S can be studied and, in turn, optimi7P.d Reaction p~r~mPters which can be varied include, for eY~mrlt~, reactant amounts, reactant solvents, reaction telll~ldtul~s, reaction times, the t;S~ureS at which the re~t tic-ns are carried out, the atmospheres in which the re~t tion~
are conducteA, the rates at which the reactions are quen~ PA, etc. Other reaction p~r~mPter~ which can be varied will be a~arellt to those of skill in the art.
Alte~ tively, the first set of reaction conditions can be the same as the second set of reaction con-lition~, but, in this embo-lim~nt the pr~cec~in~ steps after the components on the first and second substrates have been reacted would differ from the first substrate to the second substrate. For example, the first substrate can be exposed to oxygen at elevated ~Ill~ldlures~ while the second substr~tP is not processed at all.
.Al~P...~ ely, in another aspect of this emb~impnt~ the first substrate having component A on the first region of the substrate and component X on the second region of the substrate is exposed to a particular set of reaction conditions (e.g., exposed to oxygen at elevated lel.~eldLules), while the second substrate also having colllponent A
20 on the first region of the substrate and colllpollent X on the second region of the substrate is not exposed to such reaction conditions. Thereafter, component B isdelivered to the first region on both the first and second substrates, and component Y is delivered to the second region on both the first and second substrates. Once the desired components have been delivered to the first and second regions on the first and second 25 substrates, the co,llpol-ents are simultaneously reacted under subst~nti~lly i~Pnti~l reaction co~tlitions. This particular embodiment allows one to determine the effects interm~Ai~tP proces~ing steps have on a particular array of m~tP,ri~ls. As set forth above, any of a number of dirrelel~t reaction parameters can be varied.
In still another embodiment of the present invention, a method is provided 30 for producing an array of materials varying from one another in terms of chPmi~
composition and colll~onent stoichiom~trie~. In this method, a reactant component can be delivered to a particular predPfinP~I region(s) in a gradient of stoichiometri~s.
Mor~vel, multiple reactant components can be delivered to a particular predefined W O96/11878 PCTrUS95/13278 region(s) in a gradient of stoirhiomPt1ries. For example, a first component of a first m~t~qri~1 and a first colllp~llent of a second m~tPri~l are deposited on first and second reaction regions, respectively. Thereafter, a second component of the first m~t~ri~1 and a second component of the second m~teri~1 are deposited in a g~tlitont of stoichiometries S from top to bottom (or left to right) on the first and second reaction regions, respectively. Once the co,l,~vllents have been delivered to the st1bst~tP the co"l~onents are sim~11t~n~P~usly reacted to form m~teri~ varying from one another in terms of rhP-mi~l composition and çhPnnir~l sl~içhi~ mP.tri~s.
In yet another embodirnent of the present invention, a m~tPri~l having a 10 useful ~rv~ y is provided. The m~1Pri~1 is ~-c~arcd by a process com~ri.~ing the steps of: (a) forming an array of different m~tPri~l~ on a single substrate; (b) sclælling the array for a m~teri~1 having a useful ~lo~lly; and (c) making additional amounts of the m~t~.ri~1 having the useful l,rvp~l~y. Such m~t~ri~1.c inc1ude7 for example, interme.t~11ic m~t-~ri~1~, metal alloys, ceramic materials, organomPt~llic m~tP.ri~1~, organic polymers, 15 cv~ ?o~ile m~teri~ls (e.g., inorganic composites, organic co~ osi~es, or combinations thereof), etc. In addition~ useful properties include, for example, electrical, thermal, mf~rh~ni~-~1, morphological, optical, rn~gn~tic, ch~7nic~l, etc.
Using the Çvl~going method, a new family of giant m~gnelore~7Li~re (GMR) cobalt oxides has been discovered. Arrays of materials co~ in~ different compositions 20 and stojchiometries of Ln"MyCoO~, wherein Ln is, for ex~mr1e, Y and La, and M is, for example, Pb, Ca, Sr and Ba, were formed using thin film deposition techniques incombination with m~C~ing techniques (See, Example D, in~a, for the protocol used to generate the arrays of cobalt oxide thin-film materials). Once formed, the arrays of m~t~.ri~1~ were screened for those m~tPri~1~ among them having useful p,v~llies. More 25 particularly, the arrays of m~t.o.ri~1~ were screened for spe~ific m~t~ri~1~ having giant m~gnetoresistive (GMR) ~?rvpel~ies, among others. In doing so, m~teri~ having large m~netore.~i~t~nce (MR) were discovered. Once the m~teri~1.c having useful properties were ide.ntifiç.1, additional amounts of such m~t(~.ri~l~ were ~rei)~ed for further analysis.
- The colllpuunds in this new family of GMR cobalt oxides have the 30 following general formula: Ay~ )My~COOz~ wherein A is a metal sel~t~d from the group c-~n~i~ting of 1~nth~mlm (La), yttrium (Y), cerium (Ce), praseodylllilll" (Pr), neody""u"l (Nd), promethium (Pm), samarium (Sm), eulul~iulll (Eu), gadolinium (Gd), terbium Clb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), yllelbiulll ,, ,,, , , ,, , , ,, , . ,,,,,,, , , ,, ,,,, _ , . . .
CA 02202286 l997-04-l8 W O 96/11878 PCTrUS9S/13278 (Yp) and lllt~illm a~u); M is a metal se1ect~1 from the group con.ci.~tin~ of c~ m (Ca), strontium (Sr), barium (Ba), lead (Pb), th~11inm (Il) and bismuth (13i); y has a value ran~ing from about 1 to about 2; x has a value r~ngin~ from about 0. l to about 0.9; and z has a value r~nging from about 2 to about 4. The compounds in this new family of 5 GMR cobalt oxides generally have a layered, perovskite-related structure, i.e., a cubic perovskite structure with some slight distortion.
In a ~lcsently prcrellcd embo~1im~nt the compounds in this new farnily of GMR cobalt oxides have the following general formula: A~ CoOz, wherein A is a metal s~1~.ted from the group con~ ting of ]~nth~m-m (La), yttrium (Y), cerium (Ce), pr~ yll iulll (Pr), neodymium (Nd), promethium (Pm), ~111i11;11111 (Sm), el-n)piu.n (Eu), g~-lolinillm (Gd), terbium (Tb), dys~losium (Dy), holmium (Ho), erbium (Er), th111i11m (Tm), ytterbium (Yp) and lutecium (Lu); M is a metal se1e~tecl from the group con.~i~tin~ of c~1ei11m (Ca), ~Llol~Liulll (Sr), barium (Ba), lead (Pb) and ~flminn (Cd); x has a value ranging from about 0.1 to about 0.9; and z has a value r~nging from about 2 to about 4. Within the scope of this formula, certain embo~limPnt.~ are .L)lc;r~ d, namely those in which x has a value r~n~ing from about 0.2 to about 0.7 and, even more c;r~lc;d, are those in which x has a value ranging from 0.3 to about 0.5.
In a further ~ ere~.ed embodiment, the compounds in this new family of GMR cobalt oxides have the following general formula: Lal ~M,~CoOz, wherein M is a metal sP1eoted from the group con~ ting of barium, calcium and ~LIun~ l; x has a value r~nging from about O.l to about 0.9; and z has a value ranging from about 2 to about 4.
Within the scope of this formula, certain embodiments are ~r~relled, namely those in which x has a value ranging from about 0.2 to about 0.7 and, even more ~lefell~d, are those in which x has a value r~ngin from 0.3 to about 0.5. As mentioned, the compounds in this new family of GMR cobalt oxides generally have a layered, perovskite-related structure.
In yet another embodiment of the present invention, libraries of microdevices, such as thin-film c~r~l-itors or thin-film electro1-~mint~s~nt module.~" can be g~.n~ t~d using the method~ previously described for gP.nP.rating arrays of m~t~ri~
For eY~mr1e, a thin-film c~r~ritor consists of two electrode m~t~ri~l~ se~ted by an --inm1~tin~ or dielectric m~t~ri~l An array of thin-film c~r~eitc~rs can be formed by first dt;L,osiLi.lg an electrode material on each of the predefined regions on the substrate. An array of rlielp~tric m~teri~l~ can then be generated on top of the electrode surface using W O96/11878 PCTrUSgS113278 the meth~ previously described. On top of this layer, another electrode layer can be deposited, reos-llting in an array of thin-film c~r~ritors~ each r~r~ritl~r co~ h)g a dirrc;l~;nt ~iPl~-ct~ic m~teri~l By measuring the c~pa~it~nce at each of the predPfinP~
regions on the substrate, the ~elroll"allce of the various ~iPlPctric m~tPri~l~ for thin-film c~r~itors can be tested and optimi7~P~l~ It will be readily ~ cnl to those skilled in the art that this approach is fully applicable to other thin-film devices, such as thin-film electroll-minP,scPnt displays. In addition, it will be readily ~ Gnl to those skilled in the art that any one of the various layers in a thin-film device can be an array of dirre~"t m~tPri~l~ at the same or dirrel~l t stoichimPtrie~, or an array of the same m~teri~l at dirrclent stoichiometries. Moreover, the order of the various layers can be varied (e.g., the electrode m~teri~l in the thin-film ~p~itnrs can be deposited on either the top or bottom of the other layers. Thus, using the methods of the present invention, each of the layers in a given thin-film device can be optimi7P~.
It will be understood by those of skill in the art that the rOlcgoillg discussions directed to the various delivery techniques, synthetic routes, s~ileening methods, etc. are fully applicable to the above embo~iment~ of the present invention.
X. Exa~nples The following eY~mI)les are provided to illustr~tP the efficacy of the inventions herein.
A. Synthesis of An Arr~y of i!6 Copper Oxide T~zin-Film Ma~erials This example illustrates the synthesis and s~;,~ning of an array of copper oxide thin-film m~tPn~l~ The re~c~t~nt~ were delivered to a 1.25 cm x 1.25 cm MgO
substrate with a (100) polished surface. The substrate having 16 preAPfinPd regions thereon was contained in a reaction chamber in vacuo. The re~ct~nt~ were delivered to the substrate in the form of thin-films using a ~ul~e~ g system in combination with binary m~1ring techniques. The binary mask was made of st~inlP~ steel. A RF
m~gnPtron gun sputtPring system was used to deliver the reactant coll,~nents to the pre~efinPcl regions on the substrate. The RF m~gnPtron ~ P-~ g gun (Mini-mak m~mlf~tllred by US, Inc., Campbell~ CA) used was about 1.3 inches in ~ mPter. With RF input power (supplied by a Pl~mtherm-2000 with a m~t~hing network) of 50 to about 200 W, deposition rates ranged from about 0.3 A/s to about 2 A/s for the five _ _ O96/11878 PCTrUS95/13278 dirr~l~l reactant co..~pol-~nt~. The RF m~gn~tron sprayer was positioned about 3 to 4 inches above the subsll~te and the uniro~ ily of deposited film was about 5% over a 1 to
THE COMBINA7~0RLAL ,SYNTHESIS OF NOVEL MATERL~LS
This application is a c~ on-in-part of Serial No. 08/327,513, filed October 18, 1994, the tP~hinge of which are hereby incorporated by reference for all 10 yulyoses.
STATEMENT C)F GOVERNMENT INTEREST
This invention was made with Government ~UyyOll yul~ua~lt to Contract No. DE-AC03-76SF00098 awarded by the Department of Energy. The GovernmPnt has 15 certain rights in this invention.
FIELD OF l~lE INVENTION
The present invention generally relates to methods and apparatus for the parallel deposition, synthesis and screRning of an array of diverse m~tP.ri~le at known 20 locations on a single subs~rate surface. The invention can be applied, for example, to ylcy~ covalent network solids, ionic solids and molecular solids. More spel-ific~lly, the invention can be applied to prepare inorganic m~teri~le, intermetallic materials, metal alloys, cPr~mic m~tPri~le, organic m~tP.ri~le, organomP,t~llic m~t~.ri~l.e, non-biological organic yolymers~ composite m~t~.ri~l.e (e.g., inorganic composites, organic composites, 25 or combinations thereof), etc. Once yl~ d, these m~tPri~le can be screRned in parallel for useful ~lopellies inclllrling, for e~ample, electrical, thermal, mech~ni~
morphological, optical, magnetic, chemi~ ~l, and other yr~elLies.
o BACKGROUND OF THE INVENTION
., 30 The discov~ry of new m~tPri~l~ with novel chPmic~l and physical properties often leads to the development of new and useful technologies. Currently, there is a tremPn~lous amount of activity in the discovery and optimi7~tion of m~t~-.ri~l.e, such as ~upel~i~ductors, _eolites, m:lgnPtic m~tPri~ls, phosphors, nonlinear optical m~tPri~le, thermoelectric materials and high and low iiçlectric m~tPri~le Unfortunately, W O96/11878 PCTrUS95113278 even though the çhPmi.ctry of eYtrn-le~ solids has been extensively explored, few gene~
prinriplrs have emerged that allow one to predict with cG~ y the collll,osilion,structure and reaction paLllways for the synthesis of such solid state co-,-~u--ds.
Morwvel, it is difficult to predict a prion the physical pr~,Lies a particular three 5 rlimrncional structure will possess. Consider, for ey~mple~ the synthesis of the YBa2Cu307~ ~u~Glco~ ctor in 1987. Soon after the discovery of the La2 ,~Sr"CuO4 ~u~lconductor, which adopts the K2NiF4 structure (ReAnnr7, J.G. and K.A. Muller, Z.
Phy. B 64:189 (1986), it was observed that the application of ~les~ increased the tr~ncition t~ , (Chu, et al., Phys. Rev. Lett. 58:405 (1987)). As such, Chu, et 0 al. aUe~ ed to synthrci7~ a Y-Ba-Cu-O compound of the same stoichiometry in the hope that substitution of the smaller Pl,o.m-q.nt, i.e., yttrium, for lAntl.Anl- .. would have the same effect. Although they found su~Glcollductivity above 93K, no phase with K2NiF4 structure was observed (Wu, et al., Phys. Rev. Lett. 58:908 (1987)). Even for the relatively simple intermrt~llic compounds, such as the binary colllpounds of nickel and ~ir~olliulll (NisZr, Ni7Zr2, Ni3Zr, Ni2Zr8, NilOZr7, NillZrg, NiZr and NiZr2), it is not yet ndPrstood why only certain stoichiometries occur.
Clearly, the p,G~ Lion of new materials with novel c~lernir~l and physical ~ro~lLies is at best hapFenct~nce with our current level of underst~nding. Consequently, the discovery of new m~trri~l.c ciepen~1c largely on the ability to synth~oci7~ and analyze 20 new compounds. Given a~l.loAimately 100 elements in the periodic table which can be used to make C(Jlll~osiLions concisting of three, four, five, six or more elemPntc, the univG,~e of possible new col..pounds remains largely unexplored. As such, there exists a need in the art for a more efficient, economical and systematic approach for the synthesis of novel m~tf~ri~lc and for the screelling of such materials for useful ~ro~,Lies.
One of the processes whereby nature produces molecules having novel functions involves the gen~r~tion of large collections (libraries) of molecules and the sy.ct~.m~tic scl~ening of those collections for molecules having a desired p,~ ,Ly. An O
eY~mple of such a process is the humoral immune system which in a matter of weeks sorts through some 10l2 antibody moleculPs to find one which sperifir~lly binds a foreign pathogen (Nisonoff, et al., The Antibody Molecule (~ mic Press, New York, 1975)).
This notion of generating and screening large libraries of molecules has ,~cenLly been applied to the drug discovery process. The discovery of new drugs can be likened to the process of finding a key which fits a lock of unknown structure. One solution to the W O 96/11878 PCTrUS95/13278 problem is to simply produce and test a large number of different keys in the hope that one will fit the lock.
Using this logic, methods have been developed for the synthesis and S~.1Ge1~llg of large libldlics (up to 1014 molecules) of peptides, oligonucleotides and other 5 small mnl~~ .c. Geysen, et al., for example, have developed a method wherein peptide syntheses are carried out in parallel on several rods or pins (see, J. Immun.
Meth. 102:259-274 (1987), inco,~lnted herein by reference for all pul~oses).
~nPr~lly, the Geysen, e~ al. methocl involves function~li7.in~ the termini of polymeric rods and sequentially immer~ing the termini in solutions of individual amino acids. In 10 addition to the Geysen, e~ al. method, techniques have rGcel~lly been introduced for synthe.~i7in~ large arrays of different peptides and other polymers on solid surfaces.
Pirrung, et al., have developed a technique for generating arrays of peptides and other m~ cll1es using, for example, light-directed, spatially-addressable synthesis techniques (see, U.S. Patent No. 5,143,854 and PCT Publication No. WO 90/15070, inccl~ldted15 herein by referenoe for all purposes) In addition, Fodor, et al. have developed, among other things, a method of g~thP.ring fluoresce.nce intensity data, various photosen~itive pn~ling groups, m~c~ing techniques, and au~ ,lated techniques for p~ ning light-directed, spatially-addressable synthesis techniques (see, Fodor, et al., PCT
Publication No. WO 92/10092, the t.~çhing~ of which are incorporated herein by 20 reference for all p~ oses).
Using these various m,ethods, arrays cont~ining thousands or millions of dirrelG~ emPnt.~ can be formed (see, U.S. Patent Application No. 805,727, filed Deoe.mher 6, 1991, the te~rhing~ of which are incorporated herein by referenoe for all purposes). As a result of their relationship to semiconductor fabrication techniques, these metho~ls have come to be refer]red to as "Very Large Scale Immobilized Polymer Synth~si.~," or "VLSIPS~" te~.hnology. Such techniques have met with substantialsuccess in, for e ~mple, screening various ligands such as peptides and oligonucleotides to dete-rmine their relative binding affimity to a receptor such as an antibody.The solid phase synthesis techniques currently being used to ~1G~)~hG such 30 libraries involve the stepwise, i.e., sequential, coupling of building blocks to form the compounds of interest. In the Pirrung, et al. method, for example, polypeptide arrays are synth~ i7~d on a substrate by ~tt~ching photoremovable groups to the surface of the substrate, exposing sele~ted regions of the substrate to light to activate those regions, W O96/11878 PCTrUS95113278 u~ an amino acid ~ wi~ a ~hol~l_....... ov~ble group to ~e activdt d region, aI~d ",~5,t;.~, the st~ps of activa~on and ~ t~ .~1 until l oly~!;d~s of ~e desired length and ~u~ccs aD synth~s;7~ These solid phase synthesis lccl~ ucs, which ~e ~u~llial ~url;~p of b~ n~ blocks (e.g., amino acids) to form the 5 ~ l~u~ ~lc of ,nt~t, cannot readily be used to ~,p~, many lnOl`~;an~C and ~ ;C
CO...~ l.c From the above, it is seen that a m~thod and al.~K ~tl.c for syntheci~
and scl~ ~mg 1;1,.,~ ;P S of m~t~ri~l~, such as inolE;~ic m~tPn~ls~ at known ~ ;OnC on a ~bs~., t are ~Pci~A
SUMMARY OF THE INVENTION
The present i.~ iol~ provides .. ~-II.~s and al~ Js for the ~ ;nn and use of a ~ having an array of diverse m~tPri~lc in plc~r.i-~d regions thereon.
A s-~ te having an array of diverse m~t~Pri~ls thereon is p.~aLcd by ddi~ g 15 co~ of m~tPri~lc to ~ r~rd regions on the s..l,sl.,~le, and cimull;-n~u;,ly l~r.~;"g the ccl...~nf~ to form at least two m~tPn~lc M~tPn~lc which can be p using the ~-rll-~s and a~ Js of the present invention inc]u-l~P, for Py~mple~ covalent l~clw~ solids, ionic solids and ~le~ solids. More particularly, m~tPri~lc which can be pl~)alC~i include inorganic m~tPri~l~, ;ntf ~ ic m~t~.ri~lc, metal alloys, CP~mir, 20 m~t.-.ri~lc organic m~t~.ri~l~, ol~ o~ ic m~tPri~lc, non-biolo~ organic polymers, co...l~;t, m~tPri~lC (e.g., ihlOl~ iC cc,...l~s;t~ 5, organic ccsn~ f ~ or comhin~tinnc thercof), etc. Oncc ~ cd, these mate~i~1C can be scr~ned in parallel for useful es ;,,~1,l,1;ng, for ~ ~f e1p~ thprm~l"~f~ niç~ "ul~holngj~
optical, m~lptic~ chpmi~l and other plOpC~lifeS. As such, the present invention 2S provides ..I~ c and ~alus for the para~el ~ e~;s and analysis of novel m~t~.n~
having new and useful plop~.Lies. Any m~tPri~l found to possess a useful ~lU~ty can --be ~u_.~lly ~ d on a hrge-scale. ' --In one e."bo~ of the present invention, a first cc~ of a first m~tPri~l is de~ .vd to a first region on a ;~ sl.~.lr., and a first co~ P~I of a second 30 m~tPri~l is del;~. d to a second region on ~e same S.ll,s~.i.t~.. ThGI~, a second col..~n~ ~1 of the first m~tPn~1 is delivered to the first region on the ~vl~s~ , and a second co~ n~ of the second m~tPn~l is delivered to the second region on the ~ I,s~ le The p~ccss is ~ption~11y l~ d, with ?~litinn~1 cO...l~l-f ~l~, to form a vast W O96/11878 PCTnUS95/13278 s array of C~lllponents at ~ d, z.e., known, locations on the ~-,I,sl ~te. Thereafter, the coll,~l-ents are ciml~lt~nPously reacted to form at least two m~tPri~lc The co.~ enl~ can be sequentially or ~iml-lt~nPl!usly delivered to prPA~Pfin~P~ regions on the ,l.,.t~ in any str)ichiometly, inrl~ inp a gr~ nt of stoichiomPtriçs, using any of a 5 ~,1,1 e- of diLr~ei t delivery techniques.
In another embodiment of the present invention, a mPthod is provided for forming at least two dirrelel~t arrays of m~tPri~lc by delivering subst~nti~lly the same reaction colll~onents at ~,ubsl;~ lly ident~ conr~ntr~tions to reaction regions on both first and second substrates and, thereafter, subjecting the co.,.ponents on the first 0 SUbSildte to a first set of reaction conditions and the co~-ponents on the second substrate to a second set of reaction conditions. Using this method, the effects of the various reaction p~r~mp~tprs can be studied on many m~teri~lc simultaneously and, in turn, such reaction ~ can be optimi7~~ ction parameters which can be varied in~ de7 for PY~mpl~P, redctant amounts, reactant solvents, r_action ~-I~peldlù~es, reaction times, the ples.7~ at which the re~rti~ are carried out, the atmospheres in which the rP~rtionc are con-~uctP~l, the rates at which the reactions are quenrh-PIi, the order in which the re~ct~ntc are deposited, etc.
In the delivery systems of the present invention, a small, precisely metered amount of each reactant coll.~,nent is delivered into each reaction region. This may be accomplished using a variety of delivery techniques, either alone or in combination with a variet~ of m~cking techniques. For example, thin-film deposition techniques incombination with physical m~.cking or photolithographic techniques can be used to deliver various re~rt~nt~ to S-PlPCt-P~ regions on the substrate. ~e~ct~ntc can be delivered as amorphous films, e~i~ial films, or lafflce and superlattice structures. Moreover, using such techniques, re~t~t~nt~ can be delivered to each site in a unirollll distribution, or in a ~r~liPnt of stoichiomPtries. .Altern~lively, the various reactant components can be deposited into the reaction regions oiF interest from a ~licperlcPr in the form of droplets or powder. Suitable ~licpPn~Prs in~lud~P, for example, micn~pip~Ues, mP~h~nicmc adapted from inkjet printing technology and electrophoretic pumps.
Once the cGIIlponents of interest have been delivered to pre~efinP11 regions on the substrate, they can be reacted using a number of difrLrent synthetic routes to form an a~ay of m~tPri~l~ The components can be reacted using, for example, solution based sy~ esis techniques, photochP-mic~l techniques, polymerization techniques, template W O 96/11878 PCTrUS95/13278 directed synthesis techniques, epit~xi~1 growth techniques, by the sol-gel process, by tht-rm~1, inLd.t;d or microwave heating, by c~l~in~tion~ .cintf.ring or ~nn~linf~, by yd~ P-rm~1 mlothQ 1s, by flux methods, by cryst~lli7~tion through vaporization of solvent, etc. Th~;r~r~r, the array can be screened for m~tPri~l.c having useful S ~l~lies.
In another embodiment of the present invention, an array of inorganic m~tP.ri~l.c on a single substrate at pred.~.fin~ regions thereon is provided. Such an array can consists of more than l0, 102, 103, 104, l05 or l06 different ino~gallic cGI--~ui~ds.
In some embollimP-ntc, the density of regions per unit area will be greater than .04 l0 regions/cm2, more preferably greater than 0. l regions/cm2, even more preferably greater than 1 region/cm2, even more preferably greater than l0 regions/cm2, and still more preferably greater than l00 regions/cm2. In most ~rert;ll~d emb~1im~nt~, the density of regions per unit area will be greater than l,000 regions/cm2, more preferably l0,000 regions/cm2, çven more preferably greater than l00,000 regions/cm2, and still more preferably l0,000,000 regions/cm2.
In yet another aspect, the present invention provides a m~t~ri~1 having a useful plU~ y ~r~yar~d by: forming an array of materials on a single sul ~lldle;sc,ee~ g the array for a m~tP.ri~1 having a useful property; and making ~Ariihon~l amounts of the m~tt-ri~1 having the useful plo~lly. As such, the present invention 20 provides methods and apparatus for the parallel synthesis and analysis of novel m~t~ri~1 having new and useful prope,Lies.
Using the fc,regoing method, a new family of giant m~nelc~ Li~le (GMR) cobalt oxides has been discovered. Arrays of materials con~ dirrerent compositions and st~-ic~ metries of Lnl xMxCoOz, wherein Ln is, for example, Y and La, M is, for 25 example, Pb, Ca, Sr and Ba, x has a value ranging from about 0.l to about 0.9 and z has a value r~nging from about 2 to about 4, were formed using thin film deposition techniques in combination with m~.cking techniques. Once formed, the arrays of m~teri~ were screened for those m~teri~1~ among them having useful ~ro~llies. More particularly, the arrays of m~t~.ri~1~ were screened for specific m~t~ri~1~ having giant 30 m~gn~$Qresistive (GMR) pn~lLies, among others. In doing so, large m~gnto.torç~i~t~n~
(MR) was found in Lal x-(Ba, Sr, Ca)x-CoOz ~mples, wherein x has a value r~n~in~ ~
from about 0. l to about 0.9, and z has a value r~nging from about 2 to about 4. Once W O 96/11878 PCTnUS95/13278 the m~tt~ri~lc having useful ~lu~lLies were i~1~ntifiPA additional a--lou--l~ of such m~t~.ri~l~ were ~lcL)~ed.
In doing so, it has been determined that the co~ uullds in this new family of GMR cobalt oxides have the following general formula: Ay~ )M~ CoOz~ wherein A is S a metal ~l~tP~ from the group con~icting of l~ U-l~ (La), yttrium (Y), cerium (Ce), rrac~lyllliulll (Pr), neody...iu... (Ncl), prom~thi~m (Pm), ~ i ;~ . (Sm), ~ ;Ulll (Eu), ~ 1inillm (Gd), ~ iUlll (Tb)l, dy;!~JlU:iiUlll (Dy), h()lmillm (Ho), erbium (Er), th~ lm (Tm), yLLt;lbiulll (Yp) and l~ ; . (Lu); M is a metal sPl~ct~d from the group c~ ncicting of c~killm (Ca), ~Lr~nliu,ll (Sr), barium (Ba), lead (Pb), th~llium ~I1) and bicmuth (13i); y has a value r~n~ing from about 1 to about 2; x has a value r~ngin~ frûm about 0.1 to about 0.9; and z has a value ranging from about 2 to about 4. Moreover, it has been ~ettorrninPA that the compounds in this new family of GMR cobalt oxidesgenerally have a layered, perovskite--related structure.
A further lm~lPrst~nl1in~ of the nature and advantages of the inventions herein may be realized by reference to the ~ portions of the speçific~tion and the ~tt~rhPA drawings.
B~IEF DESCRIPIION OF THE DRAWINGS
FIG. 1 illllCtrAtPS m~ckin~ of a substrate at a first location; the S-lbSLldle is shown in cross-se~tion;
FIGS. 2A-2I illustrate the use of binary m~cking techniques to generate an array of re~t~ntC on a single substraLte;
FIGS. 3A-3I illllctr~tP the use of physical m~ling techniques to genPr~tP
an array of re~t~ntc on a single substrate;
FIGS. 4A-4M illustrale the use of physical m~ ing techniques to gPnPr~te an array of re~ct~ntc on a single substrate;
FIG. 5 displays the elPmPntC of a typical guided droplet dispenser that may be used to deliver the reactant solution(s) of the present invention;
FIG. 6 illnctr~tPs an example of a reaction system employing an eight RF
m~gnPtrûn sputt~ring gun and a carrousel;
FIG. 7 illustrates an example of a reaction system employing an eight RF
m~gnPtron i~ullr ;llg gun and a c~c~ett~P;
W O96/11878 PCTrUS9S/13278 FIG. 8 i1l~-$tr~tP~ an example of a reaction system a pulsed laser and a c~.sett~; -FIG. 9 illllctr~tes an eY~mple of a reaction system employing a pulsed laser and a sliding and shutter m~kin~ system;
FIGS. 10A-lOD illllstr~tPs various masks which can be used in carrying out the mPtho-l~ of the present invention. FIG. 10A ilhl~tr~tes an eY~mple of an X/Y
shutter mask; FIG. 10B illllstr~tP~s S m~king p~tt~rn~ which can be used to create S
se~ columns along a substrate for 5 dirrt;le t reaction co~ onents; FIG. 10C
rs an example of how the X/Y shutter mask can be used to create a thickn 10 ~ nt of one coll,~onent across the substrate; and FIG. 10D a mask which when ~n~l~t~ across the substrate, 5 different components are deposited in each half of the substrate.
FIG. 11 illustrates an examply of a flat sheet col,ti.ining thereon both binary masks and an X/Y shutter.
FIG. 12 illllstr~t~ an example of temperature control in a library through resistive heating;
FIG. 13 illll5tr~tes an example of a Sc~nning RF Susceptibility Detection System which can be used to detect the ~ulJelcollductivity of an array of m~tPri~
FIG. 14 is a map of the reactant components delivered to the 16 pre~lefinP~ regions on the MgO substrate;
FIG. 15 is a pho~ogM~h of an array of 16 different compounds on the 1.25 cm x 1.25 cm MgO substrate;
FIGS. 16A-16B illustrate the resi~t~nce of the two conducting materials as a function of Lelll~el~ture;
FIG. 17 illustrate the binary masks used to generate the library of m~tPri~l~; numbers in lower left hand and upper righthand comers in-lic~te position of each member in the library; M0 corresponds to no secondary mask;
FIG. 18 is a photograph of the 128 member binary library prior to ~intPring; the color of each site is the natural color of reflected light from a white light source;
FIGS. 19A-19B illustrate resistivity vs. temperature plots:
(A) 13iCuSrCaO; and (B) BiCuSrCaCuCaO and BiCuCuSrCaCaO;
FIG. 20 illustrates the masks used to generate the YBCO-BSCCO library.
W O96/11878 PCTrUS95/13278 FIGS. 21A-21C ill~ P.c resistivity vs. ~ `.f..AI~ plots: (A) BiCuSrCaO; (13) YBaCaO; and (C) YBa2Cu3O";
FIG. 22 illllctr~tPs the masks used to generate the libr~riPs of cobalt oxide (CoO) thin-film m~tPri~lc9 S FIG. 23 illustrates a map of compositions and stc ichiometries (Ln,~MyCoO3 ~b~ where Ln = La and Y, and M = Ba, Sr, Ca and Pb) of thin film ~m~le~ in lihrariP.s L2 and L3. .~mrlPs are labeled by index (row mlm~er, col~mn llu~ ) in the text and figure legend. The first number in each box in~ tP.~ x and the second y. Black, solid circles int1ir~tç the ~mrlPs that show ci~nificant MR effects (>5%);
FIGS. 24A and 24B illllctr~tP. MR ratios of .~.e~G~ ;ve samples in L2 (19A) and L3 (19B) as a function of m~netic field;
FIGS. 2~A and 2~B illustrate the resistance of sample L3(13, 2) under OT
and 10T and the MR ratio (H = 10T) as a function of temperature (20A), and MR ratios of the sample for different m~gnetic fields as a function of t~ dtUlc; (20B). The solid lines are guides to the eye;
FIGS. 26A, 26B and 26C illllctrat~o the X-ray diffraction p~tternc (in-l~
for cubic perovskite structure) for Ba~ Sr and Ca doped bulk samples, l~c~-Jely; ~e X-ray tliffr~ction p~tternC in~ te that the structure of this new class of cobalt oxides is cubic perovskite with some slight distortion; and FIG. 27 illllctr~t~.s the l~gn~.ti7~tic)n of the bulk sample La058Sr0.4lCoO~s under lT field as a function of ~~ eJ~dture. The solid line is a guide to the eye. The inset in FIG. 22 ilhl.ctr~t~q.s the MR ra~ios of the sample at different t~ pe~dLures as a function of m~gnetic field.
DETAILED DESCRIPTION OF THE lNVENTlON
AND PREFERRED EMBODIMENTS
CONTENTS
S I. Glossary II. General Overview m. ~ol~tion of Reaction Regions on The Substrate IV. MP.tho l~ For Delivery Of Pe~ct~nt Components A. Delivery Using Thin-Film Deposition Techniques B. Delivery Using A Dispenser V. Multi-Target, Thin-Film Deposition Systems VI. Moving The Dispenser With Respect To The Substrate VII. Synthetic Routes For RP~-.ting The Array Of Components VIII. Methods For Screening An Array Of Materials IX. , .~llr~ e Embodim~nt~
X. F.Y~mr11~S
A. Synthesis of An Array of 16 Copper Oxide Thin-Film ~teri~
B. Synthesis of An Array of 128 Copper Oxide Thin-Film M~tP.ri~l~
C. Synthesis of An Array of 128 Copper Oxide Thin-Film ~t~.ri~
Con~ .g BiSrCaCuO and YBaCuO Superconducting M~tP.ri~
D. Synthesis of Arrays of Cobalt Oxide Thin-film ~t~.ri~l~
E. Synthesis of An Array of 16 Different Organic Polymers F. Synthesis of An Array of Different Zeolites G. Synthesis of An Array of Copper Oxide Compounds Using Spraying Deposition Techniques H. Synthesis of An Array of 16 Different Zinc Silicate Phosphors I. Synthesis of An Array of Copper Oxide Thin-Film M~t~.ri~l~ Using Sputtering Techniques In Combination With Photolithography M~clrin~
Techniques XI. Conclusion W O 96/11878 PCT~US95/I3~78 1. Glossary The following terms are intPn~P~ to have the following general ....-~nil.
as they are used herein.
5 1. Sul,slldle: A m~tPri~l having a rigid or semi-rigid ~urf~e In many emb~imPntc, at least one suIface of the sL~ dle will be ~ubs~ 11y flat, although in some emb~limPntc it may be desirable to physically sep~dte synthesisregions for different m~tPri~ls with, for PY~mple, ~lim~hPs~ wells, raised regions, etched trenches, or the like. In some embo-iimPntc, the substrate itself contains wells, raised regions, etched trenches, etc. which form all or part of the synthesis regions. According to other emb~impnt~ small beads or pellets may be provided on the surface within dimples or on other regions of the surface or, ely, the small beads or pellets may thPmcelves be the substrate.
15 2. Predefined Region: A pre~ltqfin~cl region is a lO(`~li71y~ area on a substrate which is, was, or is intPnd~PCl to be used for formation of a srlP~t~d m~tPri~l and isotherwise r~r~ d to herein in the ~ltPrn~tive as "known" region, "reaction"
region, a "SPl~P~tP~1" region, or simply a "region." The prPAefinPcl region may have any convenient shape, e.g., linear, circular, rectangular, elliptical, wedge-shaped, etc. Additionally, the pre~lefined region, i.e., the reaction site, can be a bead or pellet which is coated with a reactant component(s) of interest.
In this embo-limPnt7 the bead or pellet can be identifi~d with a tag, such as anetched binary bar code that can be used to in~ tP the history of the bead or pellet, i.e., to identify which co-,-~nents were deposited thereon. In some emb~limPntc, a predefined region and, therefore, the area upon which each distinct m~tPri~l is synthPci7~ is smaller than about 25 cm2, preferably less than 10 cm2, more preferably less than S cm2, even more preferably less than 1 cm2, still more preferably less than 1 mm2, and even more preferably less than 0.5 mm2. In most pr~r~ d emb~im~ntc, the regions have an area less than about 10,000 ~m2, preferably less than 1,000 ~Lm2, more preferably less than 100 ~m2, and even more preferably less than 10 ~m2.
W O96/11878 PCTrUS95/13278 3. Radiation: Energy which may be selectively applied inclu-ling energy having a wavelength between 10-14 and 104 meters inclurling, for example, electron beam r~ tion, gamma r~ tion, x-ray radiation, ultraviolet r~i~tion, visible light, infrared r~ tion, microwave radiation and radio waves. "Trradi~tion" refers to S the appli~tion of r~ tion to a s~ re 4. ~o~ on~nt "Component" is used herein to refer to each of the individual chPrnir~l substances that act upon one another to produce a particular m~tPri~l and is otherwise lc;r~ d to herein in the ~lt~"-~ re as "reactant" or "reactant component." That is to say, the colllponents or, ~ltPrn~tively, react~nt~ are the m~ cul.os that act upon one another to produce a new molecule(s), i.e., product(s); for example, in the reaction HCl + NaOH NaCl + H2O, the HCl and the NaOH are the co,nponents or re~ct~nt~. -15 5. Material: The term "m~t~ri~l" is used herein to refer to solid-state co,llpounds, eYt~n~e~ solids, eYt~nded solutions, clusters of molecules or atoms, crystals, etc.
6. (~ovalent Network Solids: Solids that consist of atoms held together in a large network of chains by covalent bonds. Such covalent network solids inl.lude, but are not limited to, tli~mond, silicon nitride, graphite, b-lnkmi~terfullerene and --organic polymers which cannot be synth~i7Pd in a stepwise fashion.
7. Isnic Solids: Solids which can be modeled as cations and anions held together by el~ctri~l attraction of opposite charge. Such ionic solids in~ludç, but are not rçstrict~d to, CaF2, CdCl2, ZnCl2, NaCl2, AgF, AgCl, AgBr and spinels (e.g., ZnAl2O4, MgAl2O4, FrCr2O4, etc.).
-8. Molecular Solids: Solids con~isting of atoms or molecules held together by intermolecular forces. Molecular solids indude, but are not limited to, extendedsolids, soiid neon, organic compounds, synthetic or organic metals (e.g., tetrathiafulvalene-tetracyanoquinoneAim-oth~ne (I IF-TCNO)), liquid crystals (e.g., cyclic siloxanes) and protein crystals.
-W O96/11878 PCTrUS95tl3278 9. Inorganic ~te~ M~tP.ri.~l~ which do not contain carbon as a ~
el~mPnt The oxides and snlrhitlP-~ of carbon and the mPt~llic carbides are considered inorganic m~ten~ Examples of inorganic con.~llnds which can be synth~i7~d using the mPtho-ls of the present invention inclu~e, but are not S restricted to, the following:
(a) Tntprmpt~1lics (or TntPrmPAi~te Con~*tuPnt~ ntPrm~t~l1ie compounds cQ~ ule a unique class of m~t~llic m~t~ri~l~ that form long-range o~e~d crystal structures below a critical ~ u~,. Such m~tPri~l~ form when atoms of two metals combine in certain pro~Gllions to form crystals with a dirr~,clll structure from that of either of the two metals (e.g., NiAl, CrBe2, CuZn, etc.).
(b) Metal Alloys: A substance having met~llic ~r~llies and which is col-l~sed of a Illi~lUlc; of two or more chemical elemPnt~ of which at least one is a metal.
(c) M~nPtic Alloys: An alloy exhibiting Çellon~gn~ti~m such as silicon iron, butalso iron-nickel alloys, which may contain small amounts of any of a number of other el~m~onts (e.g., copper, aluminum, chromium, molybdenum, v~n~lium, etc.), and iron-cobalt alloys.
(d) ~Pr~mic~s Typically, a cPr~mic is a metal oxide, boride, carbide, nitride, or a llli~Ult~ of such m~tPri~l~. Ce~mics are inorganic, nonmPt~llic, nonmolecul~r solids, in~ lu-ling both amorphous and crystalline m~tPri~l~. Cer~mics are t~tive of m~teri~l~ that can be formed and screened for a particular ~ y using the present invention. Such m~t-ori~l~ include, for example, ~lnmin~, coniulll, silicon carbide, aluminum nitride, silicon nitride, the YBa2Cu307 8 ~u~ clllctor, the La2"Sr~CuO4 supe conductors, the Bi2CaSr2Cu208+"
sup~ ctors~ the Bal "K"B;03 superconductors, the ReBaCu ~u~ondllctors, ferrite (BaFe~20,9), Zeolite A (Nal2t(SiO2)~2(Al02)]-27H20), soft and perm~n~nt magnets, high dielectric constant materials (BaTiO3), piezoelectric m~tP.r~ (e.g., lead zirconate titanate (PZT), NaNbO3, and NaTaO3), electro-optic m~tPri~l~
- (e.g., lithium niobate (LiNbO3)), giant magnetoresistant m~t~ (GMR), etc. A
"giant m~gnPtoresistant" m~tPli~l, as used herein, refers to a m~tPli~l having achange in re~i~t~nre when exposed to a m~gnetic field that is greater than S
percent relative to the re~i~t~nce it had when no field was applied. That is to say, the absolute value of the percentage change in re~i~t~nce is greater than 5 percent, W O96111878 PCTrUS95/13278 i.e., ¦~R¦ > 5%. Thechangeinreci~t~nceisd~ "l,hedby:
~R z [Resist~nc6~ Mlen A Fiold I~ AppliedJ - [Resist~nCe ~en No Field I6 Appli~
R . [Resi~tance When No Field Is Appliedl 10. Or~anic Materia~s: Co~ uullds, which generally consist of carbon and hydrogen, with or without oxygen, nitrogen or other elPm~ntc, except those in which carbon does not play a critical role (e.g., carbonate salts).
F.Y~mplPs of organic m~tPri~l.c which can be synth~ci7~1 using the methods of the present invention inc.lllcle, but are not restricted to, the following:
(a) Non-biological, organic polymers: Nonmpt~ c m~tPri~lc c~ ncictin~ of large macromolecules composed of many repe~fing units. Such m~t.o.ri~l.c can be either natural or synthetic, cross-linked or non-crocclinkPrl, and they may be homopolymers, copolymers, or higher-ordered polymers (e.g., terpolymers, etc.). By "non-biological," a-amino acids and nucleotides are ~Y~ le l. More particularly, "non-biological, organic polymers" eyc~ p those polymers which are synthesized by a linear, stepwise coupling of building blocks. Examples of polymers which can be d using the methods of the present invention include, but are not limited to, the following: polyurethanes, polyesters, polycarbonates, polyethylPnPiminPs, poly~çet~tPs, polystyrenes, polyamides, poly~nilinPs, polyacetylenes, polypyrroles, etc.
11. Or~nometallic Materials: A class of compounds of the type R-M, wherein carbon atoms are linked directly with metal atoms (e.g., lead tetraethyl (Pb(C2Hs)4), sodium phenyl (C6H5-Na), zinc dimethyl (Zn(CH3)2), etc.).
12. Composite Materials: Any combination of two m~tPri~ liffPrin~ in form or composition on a macroscale. The con~tit~le-nt~ of composite m~t~ri~l~ retain their ~ o.nti~iP~s~ i:e., they do not dissolve or merge completely into one another although they act in concert. Such co~ osite materials may be inorganic, organicor a combination thereof. Included within this definition are, for example, doped m~tPri~l~, dispersed metal catalysts and other heterogeneous solids.
W O 96/11878 PCT~US95~I3278 II. General Overview The present invention provides methods and a~)~aldtus for the ~,r~p~ ;on and use of a ~ubsLIdlG having an array of m~tt~ri~l~ in predPfinP~1 regions thereon. The invention is ~IP~rihecl herein prim~rl ly with regard to the ~re~ ;on of inolE;~Iic S m~tP.ri~l~, but can readily be applied in the ~,lG~ ;on of other m~t-ori~l~ M~tPri~l~
which can be ~le~alc d in accord~ ce with the methods of the present invention in~ltlde, for eY~mple, covalent network solids, ionic solids and mnlPc~ r solids. More particularly, m~tPri~l.c which can be l~lGl~alGd in acco~ ce with the mPth~ls of the present invention inclu-lP, but are nol: limited to, il~Ol~ iC m~tPri~1~, intermPt~llic 10 m~tPri~, metal alloys, CP.r~miC m~t~ri~l.c, organic m~tPri~l~, organomPt~llic m~tPri~
non-biological organic polymers, composite materials (e.g., inorganic COIll~OSi~organic composites, or combin~tion~ thereof), or other m~tPri~lc which will be a~ t;nt to those of skill in the art upon review of this disclosure.
The resulting substrate having an array of m~tt-ri~l.c thereon will have a 15 variety of uses. For eY~mple, once ~lGpar~d, the substrate can be screened for m~tPri~l~
having useful pl.)~ies. Accordingly, the array of m~teri~l~ iS preferably synthP~i on a single substrate. By synthPsi7in~ the array of mateAals on a single ~ul~sL~screening the array for m~tPri~l~ having useful properties is more easily carried out.
Properties which can be screened for include, for example, elP~tric~l, thermal 20 mech~nic~l, morphological, optical, m~gnP,tic, chP.miç~l, etc. More particularly, properties which can be screened for inclllde, for example, conductivity, super-conductivity, resistivity, thermal conductivity, anisotropy, hardness, crystallinity, optical tr~n~r~renCy, m~netoresi~t~nce, permeability, frequency doubling, photoemi~ion, coercivity, ~ plp-ctric strength, or other useful properties which will be appalcllt to those 25 of skill in the art upon review of this disclosure. I~ ntly, the synthe~i7ing and screening of a diverse array of m~tPri~lc enables new compositif)n~ with new physical properties to be itiPntifiP~i Any material found to possess a useful ~r~lty can be subsequently ~r~a,cd on a large-scale. It will be a~a- nt to those of skill in the art that once useful m~tPri~l~ have been idPntifiPd using the methods of the present invention, a 30 variety of different methcl-ls can be used to ~lcpalc such useful m~teri~ on a large or bulk scale with es~nti~lly the same structure and ~lopel~ies.
~ PnPr~lly, the array of materials is yl~ucd by succes~ively delivering components of m~tPri~l~ to pre~e-finPA regions on a substrate, and siml-lt~n~usly reacting _ _ W O96/11878 PCTrUS95/13278 the co--,~nents to form at least two m~tPr~ In one emb~imP-nt, for example, a first component of a first m~tPri~l is delivered to a first prefGl.ed region on a substrate, and a first col--~onent of a second m~t~Pri~l is delivered to a second ~lGrGllGd region on the same substrate. Thereafter, a second component of the first m~tPri~l is delivered to the S first region on the substrate, and a second co--,~onent of the second m~tPri~l is delivered to the second region on the substrate. Each cor"ponent can be delivered in either a l...;r.,.... or gradient fashion to produce either a single stoichiometry or, alternatively, a large number of stoiçhiometries within a single preAçfinPA region. Moreover, re~rt~nt~
can be delivered as amorphous films, e~it~ial films, or lattice or su~ e structures.
10 The process is repe~tPA, with additional co",~nents, to form a vast array of components at predP-finP~i, i.e., known, locations on the substrate. Thereafter, the components are ~imlllt~nPously reacted to form at least two m~tPri~ As eYrl~inP11 hereinbelow, the co"~nents can be sequentially or simultaneously delivered to predefine~ regions on the substrate using any of a number of dirrelt;J~t delivery techniques.
In the mPtho-ls of the present invention, the components, after being delivered to pre~lPfine~ regions on the substrate, can be reacted using a number of different synthetic routes. For example, the components can be reacted using, for example, solution based synthesis techniques, photoch~mir~l techniques, polymPri7~tion techniques, tP-mpl~tP- directed synthesis techniques, epitaxial growth techniques, by the sol-gel process, by thermal, infrared or microwave heating, by c~lcin~tion, ~intrrin~ or ~nnP~linF~, by hy~ hermal methods, by flux methods, by cryst~lli7~tion through vaporization of solvent, etc. Other useful synthesis techniques that can be used to ~imlllt~nPously react the components of interest will be readily apl)a,c~"l to those of skill in the art.
Since the reactions are con~luctP~ in parallel, the ~u~ber of reaction steps can be minimi7Pcl. Moreover, the reaction con~iti()nS at dirr~,cl t reaction regions can be controlled intlepen-lently. As such, reactant amounts, reactant solvents, reaction le".pel~lult;s, reaction times, the rates at which the reactions are qllenched, deposition order of re~ct~nt~, etc. can be varied from reaction region to reaction region on the substrate. Thus, for example, the first co",ponent of the first m~tPri~l and the first co",~onent of the second m~teri~l can be the same or different. If the first component of the first m~tPri~l is the same as the first co",ponent of the second m~tPri~l~, this co",~nent can be offered to the first and second regions on the subst~te in either the W O 96/11878 PCT~USg~/13278 same or dir~c~l~ amounts. This is true as well for the second col,l~onent of the first m~t~.ri~l and the second component of the second m~ttq.ri~l, etC. As with the first cc,.-.l~ol~ent of the first and second m~t~ , the second co.~onent of the first m~t~
and the second component of the second m~t~ri~l can be the same or dirr~lci l and, if the S same, this co~ onent can be offered to the first and second regions on the sul,slldte in either the same or different amounts. Moreover, within a given preAefinPA region on the substrate, the cGl..~l~ent can be delivered in either a uniform or gr~rliPnt fashion. In hnn~ if the same co..,~onents are delivered to the first and second regions on the ~ul)slld~e at id~-ntic~l concentrations, then the reaction conditions (e.g., reaction 10 tem~ es, reaction times, etc.) under which the reactions are carried out can be varied from reaction region to reaction region.
Moreover, in one embodiment of the present invention, a method is provided for forming at least two different arrays of m~teri~l~ by delivering subst~nt~ y the same reactant co."ponents at subst~nti~lly identic~l con~ntr~tions to re~action regions on both first and second substrates and, thelc~~ , subjecting the col"~onents on the first ~ulJsLLdte to a first set of reaction con~litions and the co-"l~onents on the second substrate to a second set of reaction conditions in a wide array of co",~o~ on~. Using this method, the effects of the various reaction p~r~mPtPrs can be studied and, in turn, optimized. Reaction p~r~mPtPrs which can be varied include, for example, reactant amounts, reactant solvents, reaction le."~t;-dtures, reaction times, the pl~S .UlC;S at which the reactions are carried out, the atmospheres in which the re~tion~ are con-luct~P~, the rates at which the reactions are qu~Pn~hP~l, the order in which the re~ct~nt~ are deposited, etc. Other reaction p~r~mPtP~s which can be varied will be a~ t to those of skill in the art.
The reactant col"~nerlts in the individual reaction regions must often be prevented from moving to ~ e-nt reaction regions. Most simply, this can be ensured by leaving a sl-fficient amount of space between the reaction regions on the substrate so that the various components cannot interdiffuse between reaction regions. Moreover, this can be ensured by providing an al~pro~liale barrier between the various reaction regions on the ~UbsLldte. In one approach, a me~h~ni~l device or physical structure defines the various reaction regions on the substrate. A wall or other physical barrier, for example, can be used to prevent the reactant col~lponents in the individual reaction regions from moving to adjacent reaction regions. This wall or physical barrier can be removed after W O96/11878 PCTrUS9~113278 the synthesis is carried out. One of skill in the art will ap~rec;ate that, at times, it may be benPfici~l to remove the wall or physical barrier before scl~n-ng the array of m~tP.ri~
In another approach, a hydrophobic m~tPri~l, for example, can be used to S coat the region surrounding the individual reaction regions. Such m~tPn~1S prevent aqueous (and certain other polar) solutions from moving to ~ rPnt reaction regions on the substrate. Of course, when non-aqueous or nonpolar solvents are employed, different surface co~ting~ will be required. Moreover, by choosing ap~.u~liate m~tPri~1~ (e.g., substrate m~tPri~l, hydrophobic co~ting~ reactant solvents, etc.), one can control the 10 contact angle of the droplet with respect to the substrate surface. Large contact angles are desired because the area surrounding the reaction region remains un~velled by the sol~ltion within the reaction region.
In the delivery systems of the present invention, a small, precisely metered amount of each reactant col"pollent is delivered into each reaction region. This may be 15 ~complished using a variety of delivery techniques, either alone or in combination with a variety of m~ ing techniques. For example, thin-film deposition techniques in comhin~tion with physical m~clring or photolithographic techniques can be used to deliver the various reactant components to s~ ted regions on the substrate. More particularly, ~u~ g systems, spraying techniques, laser ablation techniques, electron beam or 20 th~rm~l evaporation, ion im~ nt~tion or doping techniques, t~h~mi~l vapor deposition (CVD), as well as other techniques used in the fabrication of integr~ted circuits and epitaxially grown m~tçri~l~ can be applied to deposit highly uniform layers of the various reactant components on selected regions on the substrate. ~ltPrn~tively, by varying the relative geometries of the mask, target and/or substrate, a gradient of reactant25 c~ ponents can be deposited within each predefined regions on the substrate or, ~lt~rn~tively, over all of the predefin~qA regions on the substrate. Such thin-film deposition techniques are generally used in combination with m~ing techniques toensure that the reactant co",pollents are being delivered only to the reaction regions of interest. ~ -Moreover, in addition to the foregoing, the various reactant components can be deposited on the reaction regions of interest from a dispenser in the form of droplets or powder. Conventional micr~il)ellillg apparatuses can, for eY~mple, be --adapted to dispense droplet volumes of 5 nanoliters or smaller from a capillary. Such W O 96/11878 PCTrUS95/13278 droplets can fit within a reaction region having a (1i~m~.ter of 300 ~m or less when a mask is employed. The ~iicpencp~r can also be of the type employed in convention~l ink-jet ~r;.~ . Such inkjet licp~n~Pr systems include, for example, the pulse pres~ule type ~licI~encpr system, the bubble jet type ~lisrPnc~r system and the slit jet type ~li.cp~n~.r 5 system. These inkjet tii~pen~r systems are able to deliver droplet volumes as small as S
picr-liters. Moreover, such llicp~n~l systems can be manual or, ~ ;vely, they can be ~ulollla~d using, for eY~mple, robotics techniques.
The ~li.cI-e.ncer of the present invention can be aligned with respect to the a~lupliate reaction regions by a variety of conventional systems. Such systems, which 10 are widely used in the microelectronic device fabrication and testing arts, can deliver droplets of reactant col-,ponents to individual reaction regions at rates of up to 5,000 drops per second. The tr~ne1~tional (X-Y) accuracy of such systems is well within 1 ~um.
The position of thLe dispenser stage of such systems can be calibrated with respect to thLe position of the substrate by a variety of methods known in the art. For example, with 15 only one or two reference points on the substrate surface, a "dead reckoning" method can be provided to locate each reaction region on the substrate. The reference marks in any such systems can be accur~t~oly idçntifi~1 by using capacitive, resistive or optical sensors.
vely~ a "vision" system employing a camera can be employed.
In another embodiment of the present invention, the dispenser can be 20 aligned with respect to the reaction region of interest by a system analogous to that employed in m~gnetic and optical storage media fields. For example, the reaction region in which the reactant co-llponent is to be deposited is jdentifilod by its track and sector location on the disk substrate. The di~peneer is then moved to the app-~liale track while the disk substrate rotates. When the applopriate reaction region is poeitiol-~d 25 below the dispenser, a droplet of reactant solution is rele~eed.
In some embo-lim~-nte, the reaction regions may be further defined by dimples in the substrate surface. This will be especially advantageous when a head or other sensing device must contact or glide along the substrate surface. The dimples can also act as id~ntific~tion marks direcl:ing the dispenser to the reaction region of interest.
W O96/11878 PCTrUS95/13278 III. Isolafion of R~n~fion Regions On A Substrate In a ~lGrG lGd emb~impnt~ the methods of the present invention are used to prG~e an array of diverse m~teri~l~ at known ~ tiOnC on a single substrate surf~ce.
F.~P.nti~1ly, any conceivable substrate can be employed in the invention. The substrate can be organic, inorganic, biological, nonbiological, or a combination of any of these, PYi.cting as particles, str~n-ls, preripit~tes, gels, sheets, tubing, spheres, cont~inPrs, c~pill~riPs, pads, slices, films, plates, slides, etc. The substrate can have any convenient shape, such a disc, square, sphere, circle, ~tc. The substrate is preferably flat, but may take on a variety of ~lt~rn~tive surface configur~tionc For example, the substrate may contain raised or dGprGssed regions on which the synthesis of diverse m~tPri~l.c takes place. The substrate and its surface preferably form a rigid support on which to carry out the re~rtinnc described herein. The substrate may be any of a wide variety of m~tPr~ in~ in,~, for e~mple, polymers, plastics, pyrex, quartz, resins, silicon, silica or silica-based m~tPri~ls, carbon, metals, inorganic ~1~CSeS, inorganic crystals, membranes, etc. Other substrate m~t~ri~l~ will be readily aL~ar. n~ to those of skill in the art upon review of this ~li.celosllre. Surfaces on the solid substrate can be composed of the same m~tPri~l~ as the substrate or, alternatively, they can be dirrGlc.lt, i.e., the substrates can be coated with a different m~tPri~l Moreover, the substrate surface can contain thereon an adsorbent (for example, cellulose) to which the components of interest are delivered. The most a~)r~liate substrate and substrate-surface m~tPri~l~ will depend on the class of m~tPri~l.c to be synthesi7çd and the selection in any given case will be readily a~a,enl to those of skill in the art.
In some embo limPnt~, a predçfinPd region on the substrate and, the,cfore, the area upon which each distinct material is synthP.si7Pd is smaller than about 25 cm2, preferably less than 10 cm2, more preferably less than 5 cm2, even more preferably 1 cm2, still more preferably less than 1 mm2, and still more preferably less than 0.5 mm2.
In most ~ref~lled embo-limPntc, the regions have an area less than about 10,000 ,um2, preferably less than 1,000 ,um2, more preferably less than 100 ~m2, and even more preferably less than 10 ~Lm2.
In plt;Ç~ d embo limPnt~, a single substrate has at least 10 different m~tPri~l~ and, more preferably, at least 100 different m~t~qri~l~ synthP~i7Pd thereon. In even more p~erc~ d embo-limçnt~, a single substrate has more than 103, 104, 105, 106, or more m~t-~ri~ synthesized thereon. In some embo~iimPnt~ the delivery process is W O96/11878 PCTnUS95113278 ed to provide m~t~ri71~ with as few as two ccjl-.~nents, although the process can be readily ~rl~rtP~ to form m~tPri~l~ having 3, 4, S, 6, 7, 8 or more co.llponents therein. The density of regions per unit area will be greater than .04 regions/cm2, more preferably greater than 0.1 regions/cm2, even more preferably greater than 1 region/cm2, 5 even more preferably greater than 10 regions/cm2, and still more preferably greater than 100 regions/cm2. In most pl~r~llcd embl!dim~nt~, the density of regions per unit area will be greater than 1,000 regions/cm2, more preferably 10,000 regions/cm2, even more preferably greater than 100,000 regions/cm2, and still more ylcÇ~l~bly 10,000,000 regions/cm2.
In other embo~lim~nts~ the substrate can be a series of small beads or pellets (hereinafter "beads"). The number of beads used will depend on the number of m~teri~l~ to be synthrsi7~d and can range anywhere from 2 to an infinite number of beads. In this emboclim~nt, each of the beads is uniformly coated with the reactant co~ onent(s) of interest and, thereafter, reacted. This is readily done, for eY~mple, b 15 using a series of vessels each of which contains a solution of a particular reactant component. The beads are equally divided into groups colle~ollding to the nllmber of ccslllponents used to generate the array of materials. Each group of beads is then added to one of the vessels wherein a coating of one of the cor.,ponents in solution forms on the surface of each bead. The beads are then pooled together into one group and heated to 20 produce a dry component layer on the surface of each of the beads. The process is repe~tPA several times to generate an array of different reaction col~L~nents on each of the beads. Once the components of interest have been deposited on the beads, the beads are reacted to form an array of m~te~ . All of the beads may or may not be reacted under the same reaction conditions. To determine the history of lthe components25 deposited on a particular bead, mass specLIuscopic techniques can be used.
ely, each bead can have a tag which intlir~tes the history of colllponents deposited thereon as well as their stc;chiometries. The tag can be, for eY~mple, a binary tag etched into the surface of the bead so that it can be read using spe.;lloscopic techniques. As with the single substrate having an array of m~tPri~1~ thereon, each of0 the individual beads or pellets can be screened for m~tPri~l~ having useful l~ro~lies.
More particularly, if an array of m~tP~ is to be g~nP~tPd based on Bi, Cu, Ca and Sr using a series of beads as the substrate, for example, four vessels co~ g aqueous solutions of Bi(NC)3)3, Cu(NO3)3, Ca(NO3)3 and Sr(NO3)3 would be W O96/11878 PCTnUS9S113278 employed. A portion of the beads are added to the vessel cont~ining the Bi(N03)3solution; a portion of the beads are added to the Cu(NO3)3 solution; a portion of the beads are added to the vessel co~ g the Ca(NO3)3 solution; and, finally, a portion of the beads are added to the vessel con~ -g the Sr(NO3)3 solution. Once the beads are 5 ul-iro~ ly coated with the reactant component con~ ed in the vessel, the beads are removed from the vessel, dried, etched, pooled together into one group and, th~l~f~l, ~ubse luently divided and added to the vessels cont~inin~ the for~going l~;L~u~Lco~ ~nents of interest. The process is optionally re~eated, with ~d~1ition~l reactant components, to form a vast array of coll-pollents on each of the beads. It will be readily 10 ~al~nt to those of skill in the art that a number of variations can be made to this technique to generate a vast array of beads cou~ -g a vast array of colll~nents thereon. For example, some of the beads can be coated with only two cGIllponents, others with more than two components. Additionally, some of the beads can be coated two or more times with the same con.ponent, whereas other beads are coated a single 15 time with a given component.
As previously e~q)l~inP~1, the substrate is preferably flat, but may take on a variety of ~ltern~tive surface configurations. Regardless of the configuration of the ~ubsLI~Le surface, it is imperative that the reactant components in the individual reaction regions be prevented from moving to ~ljac~nt reaction regions. Most simply, this can be 20 ensured by leaving a sufflcient amount of space between the regions on the substrate so that the various components cannot interdiffuse between reaction regions. Moreover, this can be ensured by providing an a~luyliate barrier between the various reaction regions on the ~ubsLI~te. A merh~ni~l device or physical structure can be used to define the various regions on the substrate. For example, a wall or other physical barrier can be 25 used to ~rt;vent the reactant col.lponents in the individual reaction regions from moving to ~dj~nt reaction regions. Alternatively, a dimple or other recess can be used to prevent the reactant components in the individual reaction regions from moving to çnt reaction regions.
If the substrate used in the present invention is to contain ~imrlPs or other 30 reces~P.s, the dimples must be suffici~pntly small to allow close p~king on the substrate.
Preferably, the dimples will be less than 1 mm in di~metPr~ preferably less than 0.5 mm in diameter, more preferably less than lO,OOO ~m in ~ m~tPr, even more preferably less than 100 ~m in ~ mPter, and still more preferably less than 25 ~m in rli~mPt~Pr.
W O96111878 PCTrUS95/13278 23 Dimples having these ~h~ teri~tirs can be produced by a variety of techniques inrlll-lin~ laser, pressing, or etching techniques. A suitable rlimpl~ substrate surfaoe can, for e~mrle, be provided by pressing the substrate with an i 1lll.. ;..1~
"master" such as those commonly used to ~lep~ compact optical disks. In addition, an 5 isotropic or anisotropic etching technique employing photolitho~ hy can be employed.
In such techniques, a mask is used to define the reaction regions on the substrate. After the ~sl-dLe is irra~ t~d through the mask, selPct~d regions of the ~)hoL~)lcsist are removed to define the arrangement of reaction regions on the substrate. The dimrlPs may be cut into the substrate with standard plasma or wet etching techniques. If the 10 ~ul,s~"dte is a glass or silicon m~teri~l, suitable wet etch m~tPri~l~ can include hydrogen fluoride, or other common wet etch~nt~ used in the field of semicon-luctnr device fabrication. Suitable plasma elc-~ commonly used in the semiconductor device fabrication field can also be employe~. Such plasma etchants include, for f Y~mp~, lu,Gs of halogen cont;~il-in~ gases and inert gases. Typically, a plasma etch will 15 produce ~limrlps having a depth of less than 10 ~Lm, although depths of up to 50 ~Lm may be obtained under some Con~ition~
Another method for p~ g a suitably dimpled surface employs photoçhPmic~lly etchable glass or polymer sheets. For example, a photoch~mic~llyetchable glass known as "FOTOFORM" is available from Corning Glass Company (New 20 York). Upon exposure to r~ tinn through a mask, the glass becomes soluble in aqueous sclution~. Thelear~r, the exposed glass is simply washed with the a~lu~liale soll-tinn to form the dimpled surface. With this material, well-defined iimrles can be made having aspect ratios of 10 to 1 (depth to ~ m~tt~r) or greater, and depths of up to 0.1 inches. Dimple ~ mPtt~rs can be made as small as 25 ~m in a 250 ~m thick glass 25 layer. Moreover, the rlimpl~ surface can contain thereon an adsorbent (for Py~mple, cellulose) to which the co---ponents of interest are delivered.
Even when a ~impled surface is employed, it is often illl~l~l to ensure that the substrate m~teri~l is not wetted beyond the reaction region parameters. Most simply, this can be ensured by leaving a sufficient amount of space between the regions 30 on the substrate so that the various components cannot interdiffuse between reaction regions. In addition, other techniques can be applied to control the physical interactions that affect wetting, thereby en~urinp~ that the solutions in the individual reaction regions do not wet the ~ull~unding surface and cont~min~t~o other reaction regions. Whether or CA 02202286 1997-04-lX
WO 96/11878 PCT/US9~113278 not a liquid droplet will wet a solid surface is governed by three tensions: the surface tension at the liquid-air intPrface, the intt-rf~ei~l tension at the solid-liquid int~o.rf~ and the surface tension at the solid-air interface. If the sum of the liquid-air and liquid-solid tensions is greater than the solid-air tension, the liquid drop will form a bead (a 5 phenomenon known as "lensing"). If, on the other hand, the sum of the liquid-air and liquid-solid tensions is less than the solid-air tPn~ion~ the drop will not be confinP~ to a given location, but will instead spread over the sl-rf~re. Even if the surface tensions are such that the drop will not spread over the surface, the contact or wetting angle (i.e., the angle between the edge of the drop and the solid substrate) may be sufficiently small 10 such that the drop will cover a relatively large area (possibly e~ctending beyond the confines of a given reaction region). Further, small wetting angles can lead to formation of a thin (appro~cim~trly 10 to 20 A) "precursor film" which spreads away from the liquid bead. Larger wetting angles provide "taller" beads that take up less surface area on the substrate and do not form precursor films. Speeific~lly, if the wetting angle is 15 greater than about 90, a pl~ul:.ur ~llm will not form.
M~.tho ls for controlling chPmic~l compositions and, in turn, the local surface free energy of a substrate surface include a variety of techniques a~aç~nt to those in the art. Chrmiç~l vapor deposition techniques as well as other techniques applied in the f~hrir~tion of i~-le~ ed circuits can be applied to deposit highly uniform 20 layers on stol~ted regions of the substrate surface. If, for eY~mple, an aqueous reactant solution is used, the area surface inside the reaction regions may be hydrophilic, while the surface surrounding the reaction regions may be hydrophobic. As such, the surface çherni.~try can be varied from position to position on the substrate to control the surface free energy and, in turn, the contact angle of the drops of reactant solution. In this 25 manner, an array of reaction regions can be defined on the substrate sl-rf~r~.
Moreover, as previously rYrl~ined, the reactant colll~nents in the individual reaction regions can be prevented from moving to adjaçent reaction regions by leaving a suffiçient amount of space between the regions on the substrate so that the various components çannot interdiffuse between reaction regions.
W O96/11878 PCTrUS95/13278 IV. Methods For Delive~ y Of i~n~t~t Components In the delivery systems of the present invention, a small, precisely metered amount of each reactant co~ onent is delivered to each reaction region. This may be accomr1i~hPfl using a variety of delivlo~ry techniques, either alone or in combination with S a variety of physical m~ing or phot~lithographic techniques. Delivery techniques which are suitable for use in the meth~s of the present invention can generally be broken down into those involving the use of thin-film deposition techniques and those ~nvolving the use of lisp~n~ers.
A. Delive1y Usin~ Thin-FSlm Deposition Technigues Thin-film deposition techniques in combination with physical m~lrinp techniques or photolithographic techniques can be used to deposit thin-films of the various re~ct~nt~ on predefin~d regions on the substrate. Such thin-film deposition techniques can generally be broken down into the following four categc,lies: t;vd~oldli~e 15 methods, glow-discharge processes, gas-phase chemi~l processes, and liquid-phase cilP~ techniques. Tnclll~Pd within these ~leg~j.ies are, for example, ,~u~
techniques, spraying techniques, laser ablation techniques, electron beam or thPrrn~l ~vd~uldlion techniques, ion implanta~;on or doping techniques, çhPmic~l vapor deposition techniques, as well as other techniques used in the fabrication of il~te~ p~d circuits. All 20 of these techniques can be applied to deposit highly u~ layers, i.e., thin-films, of the various re~ t~nt~ on selectçd regions on the substrate. Moreover, by adjusting the relative geometries of the masks, the delivery source and/or the substrate, such thin-film deposition techniques can be used to generate uniform gra~lient~ at each reaction region on the substrate or, ~lt~rn~tively, over all of the reaction regions on the substrate. For 25 an overview of the various thin-film deposition techniques which can be used in the m~th~ of the present invention, see, for example, Handbook of Thin-Film Deposition Processes and Techniques, Noyes Publication (1988), which is incollJol~ted herein by reference for all L,ul~oses.
Thin-films of the various r~ t~nt~ can be deposited on the substrate using 30 e~ e methods in combination with physical m~ ing techniques. Generally, in thermal evaporation or vacuum evaporation methods, the following sequential steps take place: (1) a vapor is gçnt-r~ted by boiling or subliming a target m~tPri~l; (2) the vapor is transported from the source to a substrate; and (3) the vapor is conden~ed to a solid film O96/11878 PCTrUS95/13~78 on the substrate surf~ce. E~d~)old~ i.e., target rn~tP-n~le, which can be used in the evaporative methods cover an extraoldin~y range of chP-mi~l reactivities and vapor ~ iSUlCS and, thus, a wide variety of sources can be used to vaporize the targetm~t.ori~lc. Such sources inçlude, for example, resict~nce-heated fil~m~ntc, electron beams; crucible heated by conducticn, r7di~tic)n or rf-inductions; and arcs, exploding wires and lasers. In ~r~rellcd embo-limPntc of the present invention, thin-film deposition using ~v~ldlive methods is carried out using lasers, fil~mPntc, electron beams or ion beams as the source. In further ~l~rt;llcd embo~limentc of the present invention, thin-film deposition using evd~ldLive methods is carried out using lasers as the source. In such laser ablation techniques, an eYçim~r or YAG laser, having snffici~nt power to cause evapnr~tinn, is directed through a viewport to a target m~t~ri~l held under vacuum.
The target m~t~ri~l is vaporized, the vapor is transported from the source to a substrate, and the vapor is con-l~need to a solid, thin-film on the substrate snrf~ e Successive rounds of deposition, through different physical masks, using the r~l~Oi~g e-vdp.,ldLiv-e methode can be used to gC;ne;ldle an array of reactants on a substrate or parallel synthPsie.
~ olec~ r Beam ~i~xy (MBE) is an e~,al)oldLi~e method that can be used to grow epit~ l thin-films. In this method, the films are formed on single-crystal substrates by slowly evaporating the elPmPnt~1 or molecular conetitu~nte of the ~llm from separate Knudsen effusion source cells (deep crucibles in furnaces with cooled shrouds) onto substrates held at ten.pe dtures a~.u~.iate for chemic~l reaction, epitaxy and re-evaporation of excess re~t~nte The Knudsen effusion source cells produce atomic or mnlPc~ r beams of relatively small ~ mPt~r which are directed at the heated substrate, usually silicon or g~ lm arsenide. Fast shutters are interposed between the source cells and the substrates. By controlling these shutters, one can grow supPrl~ttices with precisely controlled uniformity, lattice match, composition, dopant concentrations, hi~ nes~ and intPrf~eS down to the level of atomic layers.
In ~lrlition to e~/dl,u-a~ e methods, thin-films of the various re~ct~nt~ can be deposited on the substrate using glow-discharge processes in combination withphysical m~ inE techniques. The most basic and well known of these processes is S,L~ullP~ g, i.e., the ejection of surface atoms from an electrode surface by moment-.m transfer from bombarding ions to surface atoms. Sp~ l irlE or sputter-deposition is a tenn used by those of skill in the art to cover a variety of processes, all of which can be used in the methods of the present invention. One such process is RF/DC Glow O 96/11878 PCTrUS95/13278 Discl~ e Plasma Spul(P-~;n~. In thi~ process, a plasma of energized ions is created by applying a high RF or DC voltage between a c~th~le and an anode. The energized ions from the plasma bombard the target and eject atoms which are then deposited on asubsl-dle. Ion-Beam S~UIIP~;n~ is another eY~mrle of a ~ull~ cess which can be used to deposit thin-films of the various reactant co",~onents on a substrate. Ion-Beam Spu~ is similar to the for~going process except the ions are supplied by an ion source and not a pl~cm~ It will be app~llt to one of skill in the art that other~ull~ g techniques (e.g., diode ~ul~ g, reactive sputtPrinP~ etc.) and other glow-discharge processes can be used in the methods of the present invention to deposit thin-films on a substrate. Successive roun,ds of deposition, through different physical masks, using ~~ e~ g or other glow-discharge techniques can be used to generate an array of reactants on a substrate for parallel syntht-cic.
In addition to e~/dL~ldli~te methods and sputtPrin~ techniques, thin-films of the various re~rt~ntc can be depositecl on a substrate using Chernic~l Vapor Deposition (CVD) techniques in combination with physical m~cking techniques. CVD involves the form~tion of stable solids by decomposition of gaseous ch~-mic~lc using heat, pl~cm~
ultraviolet, or other energy source, or a combination of energy sources. Photo-Fnh~nr~d CVD, based on activation of the reactants in the gas or vapor phase by electrom~gnPtic tic)n, usually short-wave ultraviolet r~ tion, and Plasma-Assisted CVD, based onactivation of the re~rt~ntc in the gas or vapor phase using a plasma, are two particularly useful chP-mi~l vapor deposition techniques. Successive rounds of deposition, through diLr~lenl physical masks, using CVD technique can be used to generate an array of re~ct~ntc on a substrate for parallel synthPcic.
In addition to evaporative methods, sputtPring and CVD, thin-films of the various reactants can be deposited on a substrate using a number of different mP~h~nic~l techniques in combination with physical m~cking techniques. Such mPrh~nir~l techniques inrhlde, for Py~mple, spraying, spinning, dipping, draining, flow coating, roller coating, ~les~ule-curtain coating, brushing, etc. Of these, the spray-on and spin-on techniques are particularly useful. Sprayers which can be used to deposit thin-films inclnde, for example, ultr~conic nozzle sprayers, air atomizing nozzle ~ldyel~ and atomizing nozzle s~ldyel~. In ultrasonic sprayers, disc-shaped cP-r~mic piP7Oe1P~t-ic ~ncducPrs covert electrical energy into mech~nic~l energy. The tr~nc-iucers receive electrical input in the form of a high-frequency signal from a power supply that acts as a W O96/11878 PCTrUS95/13278 combination ose~ tQr/~mrlifiP-r. In air ~lo~ ing slJldyel~, the no771es inlclll~i~ air and liquid streams to produce a comrl~ptply atomized spray. In atomizing sprayers, the nozzles use the energy from a ~ræ~i",;7~d liquid to atomize the liquid and, in turn, produce a spray. Successive rounds of deposition, through different physical masks, 5 using mPrh~nir~l techniques, such as spraying, can be used to generate an array of re~ct~ntc on a substrate for parallel synthP~
In addition to the folcgoillg techniques, photolit~ rhic techniques of the type known in the semiconductor industry can be used. For an overview of such techniques, see, for exarnple, Sze, VLSI Technology, McGraw-Hill (1983) and Mead, et 0 al., Introdu~tion to VLSI ~ystems, Addison-Wesley (1980), which are incorporated herein by reference for all purposes. A number of different photolithographic techniques known to those of skill in the art can be used. In one embo-limPnt, for e~mple, a photoresist is deposited on the substrate snrf~re; the photoresist is selectively exposed, i.e., photolyzed; the photolyzed or exposed photoresist is removed; a reactant is deposited on 15 the PYposed region(s) on the substrate; and the rem~ining unphotolyzed photoresist is removed. ~llr. ~ rely, when a negative photoresist is used, the photoresist is deposited on the substr~tP s~ re; the photoresist is selectively exposed, i.e., photolyæd; the unphotolyzed photoresist is removed; a reactant is deposited on the exposed region(s) on the sllbstr~te; and the r~ g photoresist is removed. In another emb~limprlt~ a 20 reactant is deposited on the substrate using, for es~mrle, spin-on or spin-coating techniques; a photoresist is deposited on top of t~e re~rt~nt; the photoresist is selectively exposed, i.e., photolyzed; the photoresist is removed from the exposed region(s); the exposed region(s) are etched to remove the reactant from that region(s); and theining unphotolyzed photoresist is removed. As with the previous embo-limPnt a 25 negative photoresist can be used in place of the positive photoresist. Such photolithographic techniques can be repeated to produce an array of re~rt~ntc on a substrate for parallel synthesis.
It will be readily a~ar~nt to those of skill in the art that the foregoing deposition techniques are intPnded to illustrate, and not restrict, the ways in which the -30 re~rt~nt~ can be deposited on the substrate in the form of thin-films. Other deposition techniques known to and used by those of skill in the art can also be used.
FIG. 1 and FIG. 2 illustrate the use of the physical m~ckin~ techniques which can be used in conjunctions with the aforementioned thin-film deposition W O 96/11878 PCTrUS95/13278 techniques. More particularly, FIG. 1 illll~tr~tP~ one embodiment of the invention di~l( se~ herein in which a substrate 2 is shown in cross-section. The mask 8 can be any of a wide variety of different m~tPri~lc inclu-ling, for eY~mple, polymers, pl~.~ti~, resins, silicon, metals, inorganic g1~S~P~;, etc. Other suitable mask m~tPri~l~ will be S readily a~cllt to those of skill in tlle art. The mask is brought into close proximity with, im~gP~ on, or brought directly into contact with the ~sLIdtc surface as shown in FIG. 1. "OpPnin~" in the mask cc~ ~nd to regions on the substrate where it is desired to deliver a re~ct~nt The op~enings in the mask can take on a variety of dirrclcl.
sizes and shapes. Typically, the openings are circular, rectangular or square.
~ ely, however, they can be linear such that the co~ ents are delivered in a linear fashion from one end of the s~l~sLldLe to the other. This "linear" arrangement f~cilit~t~s screening or ~etPctic)n in certain in~t~nces, such as when thermoelPctric m~tPri~l~ are being discovered and optimi7p~ Conventional binary m~ekin~ techniques in which one-half of the Imask is exposed at a given time are illustrated hereinbelow. It will be readily ap~a,c,-t to those of s~kill in the art, however, that m~cking techniques other than col,~/elllional binary m~cking techniques can be used in the rnethods of the present invention.
As shown in FIG. 2A, the substrate 2 is provided with regions 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50 and S2. Regions 38, 40, 42, 44, 46, 48, 50 and 52 are m~ckPcl, as shown in FIG. 2B, and co",~ollent A is delivered to the exposed regions in the form of a thin-film using, for example, spraying or s~u~e~
techniques, with the res-llting structure shown in FIG. 2C. Thereafter, the mask is repositioned so that regions 26, 28, 34, 36, 42, 44, 50 and 52 are m~kP~i, as shown in FIG. 2D, and component B is delivered to the exposed regions in the form of a thin-film, with the reslllting structure shown in FIG. 2E.
As an ~ltPrn~tive to repositioning the first mask, a second mask can be used and, in fact, multiple masks are frequently required to generate the desired array of reactants. If multiple m~Ling steps are used, ~lignmPnt of the masks may be pelr~ led - using conventional ~lignment techniques in which ~lignmPnt marks (not shown) are used 30 to ~curAtP~y overly succes~ive masks with previous p~lle~ing steps, or more sophi~ticAtPA techniques can be used. Moreover, it may be desirable to provide separation between exposed areas to account for ~ nmPnt tolerances and to ensureseparation of reaction sites so as to prevent cross-cont~min~tinn. In addition, it will be W O 96/11878 PCTrUS95/13278 llnderstQod by those of skill in the art that the delivery techniques used to deliver the various re~t~nt~ to the regions of interest can be varied from reactant to re~ t~nt but, in most in~t~n~s~ it will be most pr~ ti~l to use the sarne deposition technique for each of the re~ct~nt.~.
After co,l,~,-ent B has been delivered to the substrate, regions 30, 32, 34, 36, 46, 48, S0 and 52 are m~.clr~l, as shown in FIG. 2F, using a mask different from that used in the delivery of co,ll~onents A and B. Component C is delivered to the exposed regions in the form of a thin-film, with the resl-ltinE structure shown in FIG.
2G. Th~;rearlel, regions 24, 28, 32, 36, 40, 44, 48 and S2 are m~cl~d, as shown in FIG. 2~I, and component D is delivered to the exposed regions in the form of a thin-film, with the reslllting structure shown in FIG. 2I. Once the c~lllponents of interest have been delivered to ap~r~-iate predefined regions on the substrate, they are ~imllltAn~ously reacted using any of a number of different synthetic routes to form an array of at least two m~t~ri~
lS As previously mentioned, m~.~king techniques other than conventional binary m~ckinE techniques can be employed with the aforementioned thin-film deposition techniques in the met~oll.e of the present invention. For example, FIG. 3 illust~tP.s a m~ckinE technique which can be employed to generate an array of m~t~o.ri~ , eachcon.~ tinE of a comhin~tion of three different col,-pollents, formed from a base group of four dirr~lc.~t colll~vllents. In non-binary techniques, a separate mask is employed for each of the different colllpollents. Thus, in this example, four different masks are employed. As shown in FIG. 3A, the substrate 2 is provided with regions 54, 56, 58 and 60. Region 56 is m~.~k~.d, as shown in FIG. 3B, and colllponent A is delivercd to the exposed regions in the form of a thin-film using, for P~mple, spraying or s~ul~r~ ;~'E --25 techniques, with the resultin.~ structure shown in FIG. 3C. Thereafter, a second mask is employed to mask region 54, as shown in FIG. 3D, and component B is delivered to the exposed regions in the form of a thin-film, with the resulting structure shown in FIG.
3E. Thereafter, region 58 is masked using a third mask, as shown in FIG. 3F, andcomponent C is delivered to the exposed regions in the form of a thin-film, with the resultin~ structure shown in FIG. 3G. Finally, a fourth mask is employed to maskregion 60, as shown in FIG. 3H, and component D is delivered to the exposed regions in -the form of a thin-film, with the re.~ulting structure shown in FlG. 3I. Once the components of interest have been delivered to a~lo~liate preclefined regions on the wo 96/11878 PcT/uss~Jl3278 substrate, they are sim~ nP~usly rea.cted using any of a number of different synthetic routes to form an array of four dirr~fen~ m~tPri~
FIG. 4 i~ sl~.t~s another m~kin~ technique which can be employed to ~.ner~t~ an array of m~tP.ri~l.c, each ~Qn~i.ctin~ of a combination of three dirrt;lc~lt S cG~ onents~ formed from a base group of SiA dirre~ t col--ponents. As shown in FIG.
4A, the substrate 2 is provided with regions 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98 and 100. Regions 64, 68, 72, 76, 80, 84, 88, 92, 96 and 100 are m~lrPd, as shown in FIG. 413, and cG---ponent A is delivered to the .A~osed regions in the form of a thin-film using, for example, spraying or s~ g techniques, 10 with the res-lltin~ structure shown in FIG. 4C. Thereafter, a second mask is employed to mask regions 62, 66, 7~, 74, 80, 82, 88, 90, 96 and 98, as shown in FIG. 4D, and component B is delivered to the exposed regions in the form of a thin-film, with the resultin~ structure shown in FIG. 4E. Thereafter, regions 64, 66, 70, 74, 78, 82, 86, 92, 96, and 100 are m~ P~l using a third mask, as shown in FIG. 4F, and co.l.pol~ent C
lS is delivered to the exposed regions in the form of a thin-film, with the resulting structure shown in FIG. 4G. Thereafter, a fourth mask is employed to mask regions 64, 66, 70, 76, 78, 84, 88, 90, 94 and 98, as shown in FIG. 4H, and co.-,ponent D is delivered to the exposed regions in the form of a thin-film, with the resultin~ structure shown in FIG.
4I. Thelc~rler, regions 62, 68, 70, 74, 80, 84, 86, 90, 94 and 100 are m~Pcl with a.
20 fifth mask, as shown in FIG. 4J, and co~pol-ent E is delivered to the exposed regions in the form of a thin-film, with the resnlting structure shown in FIG. 4K. Finally, a sixth mask is employed to mask regions 62, 68, 72, 76, 78, 82, 86, 92, 94 and 98, as shown in FIG. 4L, and co---ponent F is delivered to the exposed regions in the form of a thin-film, with the reslllting structure shown in FIG. 4M. Once the co...ponents of interest 25 have been delivered to a~liate pre~r.fin~ regions on the substrate, they are ~imlllt~neously reacted using any of a, number of different synthetic routes to form an array of 20 difrelGnt m~tPri~l~
It will be readily appal:ent to those of skill in the art that prior to reactingthe fol~going co---ponents, an additional reactant colll~nent can be delivered to the 30 pre~lefinP~ regions on the substrate in a gradient of stoichiomPtries. For example, once the six co-ll~onents have been delivered to app,opliate pre~efinP~ regions on the substrate, a seventh component can be delivered in a gradient fashion across the entire substrate or across portions of the substrate. The seventh co-llponent can, for ex~mr1e, W O96/11878 PCTrUS95113278 be de~osiled ll~u~h an ~ o~liate mask from left to right as a ~ pnt layer r~n~in~
from about 100 A to 1,000 A in thi~knP.ss Thereafter, the reactant co.,-pollents can be .cimlllt~ne~usly reacted using any of a number of different synthetic routes to form an array of dirrt;lc,~t m~tPri~lc.
In ~rl~1itinn, it will be readily ap~arent to those of skill in the art that ~ltPrn~tive m~Cl~in~ techniques can be employed to gentldle an array of m~tPri~lc, each cnnCistin~ of a combination of 3 or more co-"ponents, formed from a base group of four or more components. In fact, the present invention provides a general method which can be used to gP.nP.r~te coml-in~tc-i~l m~Clrin~ p~tternc for eYI-erimPntC involving the use of 10 distinct groups of reaction components, wherein the members of each group are related in such a way that it would not be desirable for them to interact with one another. In this mP.th~l, a vector is used to lei.lesellt each of the subgroups of col-lponents. For ~Y~mpl~o, a ~Ubg~vu~ of colllponents, such as the lanth~ni~1es, is l~ csented by a vector An~ = [Al, A2, A3, ... Aml = [La, Y, Ce, .... Lu], wherein m ranges from 1 to p, and p is the total number of members within the subgroup. It should be noted that the colll~onents can be placed in any order. Moreover, if a particular component of a subgroup is present at different stoichiometries, each of the dirrereilt stoichiometries would be .~r~ senled in the vector (e.g., Al 2 would correspond to a different stoit~hiometry than Al.,).
Once each of the subgroup of co.npollents is l~.es~ ed by a vector, a dyad of vectors is formed. For example, if there were two subgroups of co.nl,onents, e.g., subgroup A and subgroup B, the vector L~l~sentin~ the A subgroup of co..,pollents would be written Am = tA" A2, A3,.... Am]~ and the vector ~ es~l-tng the B subgroup of colllponents would be written Bn = [Bl, B2, B3,.... Bn]. A dyad of these two vectors 25 would be written A,nBn. This dyad is equal to the tensor of second order illll~t below.
Al Bl Al B2 ..... Al Bn A2 Bl A2 B2 ... - A2 Bn Am Bl A~n B2 .. - Am Bn --W O96/11878 PCTrUS95/13278 The dyad of vectors ADl and Bn results in producing all of the combin~tio~.
belweel~ ~e co~ P~ in subgroup A and the co,-l~ont~ in ~ubgç~u~) B. If the abovedyad is written in vector form, i.e., AmBn = [AlBl, AIB2,...AlBD, A2B" A2B2,...A2Bn, A~DBl, ~DB2~ AmB~ and another dyad is formed between this vector and a vector C~ =
S [Cl, C2, ...CJ, ~ g subgroupl C, then the following matrix cQn~ini~ every ternary combination be~ween subgroups A, B and C is formed.
Al Bl Cl Al Bl C2 .~- Al Bl Ck Al B2 Cl Al B2 C2 ~ Al B2 Ck Al Bn Cl Al Bn C2 ~ Al Bn Ck Am Bn Cl Am Bn C2 -- Am Bn Ck As such, given subgroups A~D~ BD~ C~C~ Dj, .. , all of the combinations using one coll,~onent from each group can be generated in an array format using the following method:
A. l[n the array, each subgroup will either be deposited along a row or along a column of the array. Therefore, the subgroups which co les~ond to the rows and the subgroups which collesl)ond to the columns must be sel~t~d The choice of subgroups will not alter the number of sites in the array, but it will affect the shape of the array. For example, either a 4 x 4 array or a 16 x 1 array can be created without ~ltPring the total number of sites in the array. Typically, the choice of geometry will depend on the configuration available for the library.
B. The rest of the method involves forming dyads within the Row cluster and C'olllmn cluster as illustrated above with subgroups A, B, and C. It should be noted that every dyad in array forrn is converted to a vector form before pr~ding to form the next dyad. There will be a point where only one vector will be present in each of the clusters. These vectors can be de~ign~t~1 the Row and Coll-mn vectors, re.,~ilively. When a dyad is formed between the Row and Column vectors, the res-llting array is the final format of the combin~tori~l library.
W O96111878 PCTrUS95/13278 34 C. The order of components within any of the vectors or arrays does not affect the result, but it does alter the m~ ing p~ttPrn~ needed to ~enPr~t~ the sarne result. If the final array of combinations is arranged as ill~sl.,.~ed in the above eY~mrle using subgroups A, B and C, then only masks with bars along columns or rows 5 will be needed to create a combinatorial library.
In non-m~thPm~t~ l terms, choosing :.Ul~gl'OU~)s ~ u~lCS that all of the rl~-n~ in a subgroup be deposited side by side across either the rows or the columns of the library. With a group of 4 el~mçntC, for example, the array would be subdivided into qu~ir~nt~ along either the rows or columns and then each col,-ponent would be 10 deposited in one of the quadrants. If the rows or columns were already subdivided into let us say thirds, then each of those thirds would be subdivided into qu~l1r~ntc and all 4 colll~nents would be deposited evenly across each of the three larger subdivisions.
It will be readily a~e.lt to those of skill in the art that the fol~oillg mPth~ can be used to generate combinatorial m~ing patterns for any ~ i...Pnt 15 given a set of predPfinP~ coll.~onents.
B. Delive~ Usin~ A Dz~penser In addition to the foregoing delivery techniques, AicrPncçrs can be utilized to g~nPr~t~P diverse combin~tions of reactant components in the form of droplets or 20 powder on a single substrate. As explained above, commercially available miclupi~ lg a~dtus can be adapted to dispense droplet volumes of S n~nolitPrs orsmaller from a capillary. Such droplets can fit within a reaction region having a meter of 300 ,um or less when a non-wetting mask is employed. In some embo iimpntc~ the mi~;l~ipeL~e is accurately and precisely positioned above the reaction, 25 as described below, before the reactant soll1tion is deposited.
In a dirr~re-~t ~,cr~lled embodiment, the present invention employs a solution de~osiling a~dlus that resembles devices commonly employed in the inkjet printing field. Such inkjet dispensers include, for example, the pulse ~r~s~ type, the bubble jet type and the slit jet type. In an inkjet dicpPncPr of the pulse pl~,S;~ll`e type, 30 the prinhng ink is jetted from a nozzle according to a change in plG~i~iUIG applied by a pi~7~P]çctrit~. device. In an inkjet ~icp~ncPr of the bubble jet type, bubbles are gPntr~tP~
with heat generated with a rçci.ct~nce device embedded in a nozzle, and printing ink is jetted by using the force due to the expansion of a bubble. In an inkjet riicpP,ncçr of the O 96/11878 PCTnUS9S/13278 slit jet type, printin~ ink is filled within a slit-like orifice wherein recording electrodes are aligned in coll~;s~~ Pnce to pixels, and a DC voltage pulse is applied bGlween a ~ r~ g electrode and a euu-l~el eleetrode arranged behind a lGcol.lillg paper. In this system, the printing ink around the to]p of the record electrode is charged el~ctric~lly so that the ink is ejected tuw~ds the recording paper with an electrostatic force to record a dot on the paper.
Such inkjet ~ tel~ can be used with minor mo ~ tion by simply substit ltin~ a reactant c~ g solution or reactant con~ ni~-g powder for the ink. For eY~mI~le, Wong, et al., Eul~ope~ Patent Application 260 965, incùll,vl~ted herein by reference for all purposes, describes t~e use of a pulse ~les~ure type inkjet printer to apply an antibody to a solid matri~c. In the process, a solution cont;,i~ the antibody is forced through a small bore no_zle that is vibrating in a manner that fr~mP-nt~ the solution into discrete droplets. The droplets are subsequently charged by passing through an electric field and then deflect~d on~o the matrix m?~teri~l For illustrative pul~oses, a convPntion~l ink drop printer of the pulse ~ssure type in~ des a reservoir in which ink is held under pr~s~iu~e. The ink reservoir feeds a pipe which is conn~cted to a nozzle. An electromPrh~ni~l t~n~d~lcer is employed to vibrate the no771e at some suitably high frequency. The actual structure of the nozzle may have a number of different constructions, incl~ in~ a drawn glass tube which is vibrated by an external tr~n~ducPr, or a metal tube vibrated by an eYt~-m~
~n~ducf~r (e.g., a pie7oPlP~tric crystal), or a m~gnPtostrictive metal tube which is m~gnPtostrictively vibrated. The ink accordingly is ejected from the nozzle in a stream which shortly thereafter breaks into individual drops. An electrode may be present near the nozzle to impart a charge to the d;roplets.
A sçhPm~tic drawing of an ink drop dispenser of the pulse ~ iUle type (such as is described in U.S. Patent Mos. 3,281,860 and 4,121,222, which are incol~ldled by reference herein for all purposes) which may be employed in the present invention is shown in FIG. 5. This a~aldtus comprises a reservoir 210 which contains a solution under pressure. Tubing 212 is connect~P~ to the reservoir 210 and termin~t~ in a metal nozzle 242. No_zle 242 is disposed within a hole provided in pie7~Pl~ctric crystal 240. The end of the metal tube and of the pie7oPlP~tric crystal are made to coincide. The tubing and the pie7OPlectric crystal are soldered together to form a perm~nPnt wa~elp~oof ~t~chmPnt. The coincident ends of the crystal and the tubing are W O96/11878 PCTrUS9S/13278 covered with a washer 244 which is termed an orifice washer. This washer has an opening 246 drilled thGlGlhrough through which the solution is emitted under P1~1rG.
A source of os~ tirn~ 218 is connPctP~l between the outside of the metal tubing 242 and the outside of the pie7oPlP~tric crystal 240. The construction is such that hPrmPti~
5 sealing can be employed which plO ~;~S against electror~lP-miç~l and atmosphPnc attack of the coll,~onents.
The piezoelectric crystal 240 is vibrated subst~nh~lly at the fr_quency of the source of oscill~hon~ c~ in~ the tubing and nozzle to vibrate whereby the solution stream breaks down into droplets 246. A signal source 224 which is syncLol~ized by the 10 source of os~ tions is connPcte~ between the nozzle and the charging cylinder 226. As a result, each of the drops, which should be subst~nti~lly the same mass, receives a charge, the amplitude of which is determined by the amplitude of the signal applied from the source 224 and the charging cylinder 226.
The charged drops, after passing through the charging cylinder, pass into an electric field which is established between two plates respectively 230 and 232 which are conn~t~1 to a field potential source 234. As a result of the action between the field and the charge of each drop, the drops are ~lefl~tçd from their center line path bGl~ce.
the plates in accol.lance with the charge which they carry. Thus, when they fall on an optionally moving writing medium 236, a deposition pattern occurs on the writing20 mt-Aillm l~l5;se~ tive of the information in the signals.
Although the inkjet printer of the pulse pressure type has been described in greater detail herein for purposes of illustration, it will be readily ap~alcnt to those of skill in the art that inkjet lJlinlGl~7 of the bubble jet type and the slit jet type can also be used, with only minor mo~lifi~tirns, to deliver reactant components to pre~efinP~
25 regions on the substrate. Moreover, although the ror~going rli~cu~ n refers to a single nozzle, in a ~lc;rGll~d emb~imt-nt inkjet ylintGl~ having multiple nozzles are used to deliver m~lltiple reactant components to a single preclPfin~ region on the substrate or, ~ltPm~tively, to multiple predefined regions on the substrate. In addition, as improvements are made in field of inkjet plil~ " such improvements can be used in the -30 methods of the present invention.
In other embodiment~, the reactant solutions can be delivered from areservoir to the substrate by an electrophoretic pump. In such a device, a thin capillary connects a reservoir of the reactant with the nozzle of the dispenser. At both ends of the capillary, electrodes are present to provide a potential dirrer~ -ce. As is known in the art, the speed at which a chPmir~l sl~ecies travels in a potential ~ lient of anelectrophoretic mPAillm is governed by a variety of physical pl~,Lies, inr.lurling the charge density, size, and shape of the species being transported, as well as the physical S and ~h~Pmic~l properties of the trans~ort mP~ lm itself. Under the proper conditions of potential gr~tliPnt capillary ~limpn~ and transport mPAillm rheology, a hydrodynamic flow will be set up within the capillary. Thus, bulk fluid Co~ the reactant of interest can be pumped fiom a lcis~ oir to the substrate. By adjusting the ~
position of the substrate with respect to the electrophoretic pump nozzle, the reactant 10 solution can be precisely delivered to pre~lefinPd reaction regions on the substrate.
Using the aforP~mPntinned dispenser systems, the reactants can be delivered to predPfinP~l regions on the substrate either sequentially or ~imlllt~n~usly. In a presently pief~.led emborlimPnt the re~rt~nt~ are simultaneously delivered to either a single pre~lefinP,d region on the substrate or, ~lle. ..~tively, to multiple pred~P-finPA regions 15 on the substrate. For eY~mrlç, using an inkjet ~ pçn~er having two noz71~os~ t~,vo dirr~ t reactants can be ~imlllt~nPously delivered to a single pre lPfin~ region on the substrate. ~ ely, using this same inkjet dispenser, a reactant can be .~imlllt~n~ously delivered to two dirr~ t predPfin~d regions on the ~ul s~l~te. In this in~t~n~e, the same reactant or, ~ltçrn~tively, two different react~nt~ can be delivered. If 20 the same reactant is delivered to both of the pre~lPfin~P~ regions, it can be delivered in either the same or dirrt;,~;nl amounts. Similarly, using an inkjet dispenser having eight nozzles, for example, eight different reactants can be ~imlllt~neously delivered to a single predefined region on the substrate or, ~l~ern~tively, eight re~t~n~.~ (either the same or dirî~l~nl) can be ~imlllt~nt-Qusly delivered to eight different predrfin~l regions on the 25 substrate.
VI. Multfi-Target, Thin-Film J:)eposifion Systems The reaction systems used in carrying out the previously desçrihe~ thin-- film deposition techniques can vary widely and will depe.nd, in large part, on which thin-30 film deposition technique is being employed. The present invention provides a number of different multi-target, thin-film deposition systems which can be used in carrying out the mf thofls of the present invention. Many embodiments and variations of the systems W O96/11878 PCTrUS95/13278 disclosed herein will become a~c;nt to those of skill in the art upon review of this ~li cr.l~,sllre.
A. A Sputtenng System Wi~h A Carrousel An eY~mple of an eight RF m~gnPtron s~u~lP~ g gun system which can be employed in the mPtho-~c of the present invention is illustrated in FIG. 6. This system compricP~c eight R~ m~gnPtron ~u(~ lg guns 110, each of which contains a reactant co",ponent of interest. The eight RF m~gnPtron sputtP-ring guns are located about 2 to about 5 inches above a disk 112 col.~inin~ thereon eight m~ng p~ttPrnc 114 as well as 10 eight film-thi~l~nPcc monitors 116. In this system, the eight RF m~gnPtron ~-"~e~ g guns as well as the disk are fixed. The substrate 118, however, is coupled to a substrate manipulator 120 which is capable of linear and rotational motion and which engages the substrate with the particular mask of interest so that the substrate is in contact with the mask when the s~u~leling begins. Combinations of the eight components are genPr~t~
15 on the sub~lldle by the sequential deposition of each component through its respective mask. This entire system is used in vacuo.
It is also possible to give the disk 112, which contains thereon the eight m~cking patters 114, rotational motion, thereby providing the flexibility needed to match any of the 8 reactant co~ ,onents with any of the eight m~Ckinf~ p~ttPrnC 114. With this 20 flPYihility, it would be advantageous to increase the capacity of the disk 112 to more than eight m~king p~ttt-rn~ 114 so that a reactant component can be deposited throughmultiple m~cking p~tt~rn.~ This is particularly useful when different film thicknPsses of a given reactant component are needed at different sites within the library. In addition, this system can be converted from a polar coordinate system to a X-Y coordina~ system 25 wberein the s~u~le~ g guns, tbe masks and the substrate are in a rectangular configuration.
B. A Sputtering System wi~h A C~ ette An alternative design for a combinatorial sputtt-nn~ system is illustrated in 30 FIG. 7. This system compri~es eight RF m~n~tron sputt~ring guns 110, each of which contains a react~nt component of interest, inserted from the side of the reaction chamber in a complete circle. The substrate is ~tt~rhPd to a shaft 130 having linear and rotational motion. As such, during deposition, the substrate can be tr~n~l~t-Pcl and rotated to face W O 96/11878 PCT~US95113278 any one of the eight RF m~n~tron ~u~ ;nP: guns 110. The subs~tP is locatRd within a ~ul)sll~le holder 132 which, in ~-i(1ition to hok~in~ the sl~bs~tP~ also locks one secondary m~1ring pattern 134 firmly above the substrate 118 (the pfilll~y mask is the grid which defines the size and density of the reactions sites on the substrate and which S is held fixed during the entire experimPnt). After deposition of a reactant co",~nc;lll, a manipulator 138 is used to remove the ~P~onr~ry mask, to place it in a Ç~c!~:Pttp 140, to remove the next desired secondary mask, and to place this mask above the substrate holder 132. The locking mP~h~ni~m on the substrate holder will assure the ~lignmtont of the mask preferably within 25 ~m. ~It will be readily ap~a~ent to those skilled in the art 10 that there are mnltirle schçmes and designs for locking me~h~ni.sm~ which will align a sul~sll~te to a mask with an ~ecur~cy better than 25 ~Lm.) In the configuration illll~tr~t in FIG. 7, the manipulator 138 has linear motion in the vertical direction, and the c~ettç 140 has linear motion in the horizontal direction. With this format, the manipulator 138 can be used to translLate any of the secondary masks in the c~ett~P 140.
15 This design applies preferably to the use of 2 masks, more preferably to the use of 8 masks, even more preferably to the use of 20 masks, and still more preferably to the use of more than 20 masks. Using this system, all of the reactant colllponents of interest can be deposiled through distinct m~ in~ patterns, thereby creating a combinatolial library of layered thin-film plt;~;Ul~iUl~i.
C A Pulsed L~zser Depositzon System With A Cns~ffe A system related to the one described above is that of the pulsed laser deposition system having a c~Ptte eYçh~nge mP~h~ni~m. This design is i1lustr~tP~d in FIG. 8. The reactant colll~nents are placed in a carrousel wheel which can hold at least 25 4 reactant col-.ponents and, more preferably, at least 8 reactant co,-l~onents. An ~ltPrn~tive approach is to place each reactant co--.ponent on a dirr~ t face of a polygon 142 (see, FIG. 8). If, for example, 1he polygon is a decagon, then ten reactant col,lponents can be mounted upon it. With either design, the goal is to be able to rapidly - move a reactant component in front of a laser beam 144 for a specific period of time, 30 and then change reactant colllponents almost in~t~nt~neously. In the carrousel embo limtont, the reactant col..ponents can be quickly rotated to int~l~e.;l the laser beam 144. In the polygon embodimPnt the reactant co...ponents can be interçh~ngP~l by.Spinning the desired polygon face to the front where the laser beam 144 is fixed.
W O 96/11878 PCTrUS9~13278 In co",p~. ;con to ~ h~g thin-film deposition techniques, pulsed laser thin-film de~o~;lioll techniques provide greater flexibility and speed in terms of in~lG~ ing the reactant co~lpol ents, but have reduced unirollllity over areas greater than 1 cm2. However, several techniques are cullclltly being used with lasers to yield S un;r~,s~ s of up to 100 cm2. The first and most common of such techniques is to move the substrate in a pl~nPt~ry motion during the deposition of a reactant component.
The ~lane~uy motion insures that the plume of material ejected by the reactant co",~onent is spread evenly throughout the substrate. The cost of moving the SUbSL,dle during deposition is a reduction in speed since, in effect, many 1 cm2 depositions are required to evenly cover a circle of, for example, 5 cm in ~ m~t~r.
Another approach to achieving uniformity over large areas during the deposition of thin-films is a technique that uses a rastered laser beam. In this design ctr~t~i in FIG. 8, a programmable mirror 146 allows the laser beam to be rastered over the entire ~ m~ter of the ablation target, i.e., the reactant cc,--,~onent. By varying the speed of the r~ct~ring laser beam as a function of position, the ablation plume can be g~n~or~t~ for longer periods of time near the outer edge of the substrate to yield uniform films. This technique also has the advantage of always producing a concictent plume as a function of time.
For the system illustrated in FIG. 8, the substrate is mounted on a shaft 130 which can be rotated and tr~ncl~t~1 vertically. Moreover, in addition to using a racttoring laser beam, each ablation target, i.e., reactant component, rotates so as to expose the entire surface of the target to the laser beam. This improves the uniformity of the deposition for areas greater than 1 square inch. As described above with respect to the system illustrated in FIG. 7, the substrate is placed within a sample holder 132, -and a secondary mask 134 is ~tt~rhe l to the substrate holder 132 above the substrate.
The secondary mask 134 is aligned correctly with the substrate through the use of a locking mto~h~nicm. The ~cur~y of the locking mPrh~ni~m should preferably be better than 25 ,um. In between deposition steps, a mask is interchanged, without breaking the vacuum, with one of the other secondary masks held in the c~cs~tte within the reaction chamber. The general procedure used to exchange the masks was described above.
W 096/11878 ~_1ru~3Srl3278 D. A Pulsed L~er D~, ~r~n System With A Sliding & Shu~ter ~ s~g System When lih~rie5 conl~in;~g more than 1,000 m~t~.ri~l.Q are ~huc~ul~;d to only - S contain ternary, ~''A~ 'y and q.. ;~ .y .. ~ , for e~mr'- the .~.-.. ke. Of dirr~.~n~ m~Q~ steps involved Call easily reach 30. Moreover, each library will likely require the use of some crigin~l m~ in~ p~ttPm~ Thus, it would be adv~nt~eouc to have a system which has the ability to create one of hundreds of dirr~ m~c~in~
p~ c in front of a s.ll~slr, ~e, each within a few sec~n~1~ Such a system is ill..~l. .t~d in FIG. 9.
In this design, the l~ co~ on~-nt targets and laser can be configured as il1--~ A in FIG. 9. The ;~ dle in a s~-bst-~t~- holder 132 is ~tt~h~A to a shaft 130 which has t~nsl~tiQn capabilities in the X, Y and Z directions as well as rotational c~r~biliff~-s The S~sL~ate iS placed below a fixed plate with an a~.lul~ 150 which will preferably be greater than 1 cm2, mlore ~l~f~l~bly greater than 6 cm2, and most f~dbly greater than 50 cm2. Above the a~.Lul~, plate 150 is a flat sheet 152 c~ h~ g thereon mllltir'~ masks. This sheet 152 is ~n~h~ to a manipulator or shaft 130 which can t~ncl~t~ any mask ~ cCLly over the a~.lu~ plate 150. Typically, there is little or no space ~et~ - the a~ ~Lul~ plate 150 and the sheet 152.
One of the masks on the sheet 152 will consist in its most general form of nine slu~s, each of which is a~l)f~;m~t~ly of the same lim~n~i~nC as the a~ u~e in the ap~Lur~ plate 150. Only the middle square is empty. This mask is shown in FIG.
10A. When ~tt~l-h~ to a flat sheel: which can be t~n~l~t~ in the X and Y directi~ns, this mask effectively be~o ~,FS an X/Y shutter mask. As such, it can create dirr~ t size s~lu~es, rect~ngl~s, 'L' shapes and bars in either the X or Y dil~l;nnc Given that the S~SLIdle can also t~ncl~t~ in the X and Y directinns, a two shutter ...,~ ni~m iS formed in this configuration It can readily be seen by those skilled in the art that there are other arrangements (such as an 'L' shaped mask instead of a square mask) which can create a two shutter sys~em that ~L~llllS as the one des~libed herein.
- 30 Using the X/Y shutter mask and svbs~ o comhin~ti~ n, hundreds of .lirr~ m~l ing configl~r~ti~n~ can be gæ~ t~l, each within a few se~ s. For eY~mrle the 5 m~lring p~tte~n~ set forth in FIG. 10B create 5 5~ lr Co]llmn~ along a s~lbs~ for 5 different reactant components. This id~ntit~l design can be eY~uted with the X/Y shutter mask by first slidhlg the mask to the right to form an opening 1/S the W O 96/11878 PCTrUS95/13278 size of the substrate, with the right side of the ~GlLule plate (as shown in the first mask in FIG. lOB), and then moving the substrate to the left after every deLo~it;ol . Ihus, in the same number of deposition steps, i.e., 5, an identir~l pattern is created without the need to eYrh~nge masks. Mo~eove, when a thirknPcc gr~liPnt of one component across S the library is desired, the X/Y shutter can, for eY~mI~le, be tr~ncl~tP~I at a constant speed from right to left as s4Own in FIG. 10C.
The ~o~Ggoing X/Y shutter system can adv~nt~geously be used in comhin~tion with more traditional binary m~cking techniques. For exarnple, when the mask set forth in FIG. 10D is tr~nQl~tP~d across the substrate, 5 different co"l~ollents are deposited in each half of the substrate. However, with the X/Y shutter system, twice the number of steps are nee~. Therefore, it is frequently adv~nt~geQus to incolpo binary masks in addition to the X/Y shutter on the flat sheet lS2 which sits directly above the ~ wt; plate 150. An eY~mpl~ of such a sheet configuration is ill--~t~te~ in FIG. 11. Notice that by rotating the substrate 90, it is possible to apply the m~clrin~;
15 p~ttPrn~ in both the X and Y directions which reduces the number of nece~.y masks by half. If the sheet is fixed in one-~imPncinn (e.g., the X direction), the ~ubsll~le must be given a ro~tion~l degree of freedom so that it can be roated 90.
In ~-ltlition to being used in combination with traditional binary m~cking techniques, the X/Y shutter system can be advantageously used in combination with other 20 m~cking techniques. In paticular, it can be used with the previously described method for genPr~ting m~king strategies for experiments involving the use of distinct groups of reaction co.,lpollents, wherein the members of each group are related in such a way that it would not be desirable for them to interact with one another. The following sets forth an eY~mple of how this can be carried out.
In this example, there are three groups of reactant co,ll~onents, i.e., group 8, group 5 and group 3, each of which contains 8, S, and 3 elempnt~
respectively. Moreover, group 8 has 5 settings per elemçnt, group S has 3 settings per elPment and group 3 has 1 setting per element. As such, the number of reaction sites on the array would be 1800 or (8 x 5) x ( 5 x 3) x (3 x 1). To plG~LlG an array having 1800 reaction sites, one could use a rectangular substrate having 40 rows running across the width of the substrate, and 45 columns running down the length of the substrate.
Group 8, having 8 elements and 5 settings per elçmP-nt7 would be deposited along the rows, whereas group S, having S elements and 3 settings per elemPnt, and group 3, W O96/11878 PCTnUS95/13278 having 3 el~mPnt~ and 1 seffing per elpment~ would be depo~i~d along the coll-mn~.
Using the laser system described in FIG. 9 and ~.~.c~lmin~ the deposition time is about 5 A/s for a 1" x 1" area and the deposition thichn~ for each layer is 2 A, the mlmher of m~ in~ steps required would be 34 fior a total deposition time of 23 ~ ..Y~s. This value S does not take into account the transfer time needed to eYch~n~e the 34 masks. Using the X/Y shutter system described above, 90 steps would be lc luircd for a total deposition time of 1 hour. However, using two masks in combination with the X/Y shutter system, the llulllb~ of m~Cl~ing steps required would be reduced to 50 and the deposition time would be reduced to 33 ..,i.u~es The folego;ng is an .oY~mple of the many different multi-target, thin-film deposition systems which can be used in carrying out the methods of the present invention. Such systems provide general st~t~gies and designs for the systems used to .nlo~r~te coml)inal~,ial libraries of layered thin-film m~t~ri~l~. It will be readily a~nl to those of skill in the art that the rc,lc;going systems can be modified and optimized in 15 minor ways to work with any of the different thin-film deposition techniques.
VII. Moving The Dispenser fi~th Respect To The Substrate To deposit reactant droplets conci~tPntly at precisely specified regions using a ~i~ren~r~ a frame of referenee common to the delivery instrument and the20 substrate is required. In other words, the reference coordinales of the instrument must be accurately mapped onto the reference coordinates of the substrate. Ideally, only two reference points on the substrate are required to completely map the array of reaction regions. The di~pen~rr instrument locates these reference points and then adjust its int.o.rn~l reference coordinales to provide the nece~.y mapping. After this, the25 ~ n~Pr can move a particular tli~t~nc~e in a particular direction and be positionrd dil~11y over a known region. Of course, the ~ )en~r instrument must provide precisely repeatable movemrnt~. Fulther, the individual regions of the array must not move with respect to the reference marks on the substrate after the reference marks have - been formed. Unfo,~u"ately, pressing or other mrrh~nic~l operations commonly 30 encoun~led during fabrication and use of a substrate may warp the substrate such that the correspordenre between the reference marks and the reaction regions is altered.
To allow for this possibility, a substrate CO,.~ both "global" and "local" reference marks is preferably employed. In l"cf~"cd emborlim~nt~, only two W O96111878 PCTrUS95/13278 44 global reference marks are conveniently located on the substrate to define the initial frame of reference. When these points are located, the ~ p~Pnser instrument has an a~r~ te map of the substrate and the predefinP~ regions therein. To assist in locating the exact position of the regions, the substrate is further subdivided into local S frames of reference. Thus, in an initial, "course" adju~tmtont the ~ pçn~Pr is po~itionecl within one of the local frames of lere ence. Once in the local region, the ~ pen~ing instrument looks for local reference marks to define further a local frame of reference.
From these, the 1ispen~lor moves exactly to the reaction region where the reactant is to be deposited. In this manner, the effects of warpage or other defoll"aLion can be 10 ...;ni...i,~xl. The number of local reference marks is determined by the amount of defol,nalion expected in the substrate. If the substrate is sllffiçi~ntly rigid so that little or no defull~laLion will occur, very few local reference marks are required. If substantial deformation is expected, however, more local reference marks are required.
Starting at a single reference point, the micruyi~LLe or other Iiy)çn~er is 15 ~n~l~t~ from one reaction region to another reaction region on the substrate by a correct tli~t~nre in the correct direction (this is the "dead reckoning" navigational technique). Thus, the di~ren~er can move from region to region, rli~rPncin~ correctly metered amounts of re~t~nts In order to initially locate the reference point and align the rli~ren~r directly over it, a vision or blind system can be employed. In a vision 20 system, a camera is rigidly mounted to the ~1icpçncer nozzle. When the camera locates the reference point(s), the di~pen~r is known to be a fixed ~ t~nce and direction away from the point, and a frame of reference is established. Blind systems locate the reference point(s) by capacitive, resistive, or optical techniques, for example. In one eY~mple of an optical technique, a laser beam is tr~n~mitted through or reflected from 25 the substrate. When the beam encounters a reference mark, a change in light intensity is det~ted by a sensor. C~r~citive and resistive techniques are simil~rly applied. A sensor registers a change in c~p~cit~nce or resistivity when a reference point is encountered.
For purposes of this invention, the spacing between the individual regions will vary in accord~ce with the size of the regions used. For PY~mple, if a 1 mm2 30 region is used, the sp~ring between the individual regions will preferably be on the order of 1 mm or less. If, for PY~mple, a 10 ~m2 region is used, the spacing between the individual regions will preferably be on the order of 10 ~m or less. Further, the angular relation between the cells is preferably con~i~te~lt, to within 0.1 degrees. Of course, the W O96/11878 PCTrUS95/13278 photolithn~r~rhic or other process used to define the ~rr~ngem~nt of cells will ~ccllr~tPly define the angle and sr~ein~. Howe~er, in subsequent processes (e.g., pressing pr~sses), the angle can be distorted. Thus, in some embo limPntc, it may be n~e~.y to employ "local" reference points throughout the array.
Tr~ncl~tional mPch~ni~m~ capable of moving with the desired precision are preferably equipped with position fe~lb~ mer,h~ni.cm.c (i.e., encoders) of the type used in devices for semicond~ctor device m~nuf~chlnn~ and testing. Such mP~h~nicmc will preferably be closed loop ~y~GIlls with inci~nifi~ ~nt bacl~l~ch and h~ sis. In lJlerellGd emb~lim~nt~, the tr~nCl~tion mPrh~nicm will have a high rescllltion, i.e., greater than five motor ticks per çnrod~r count. Further, the electro-mto~h~ni~lmP~h~nicm will preferably have a high repeatability relative to the region ~ mP~ter travel f~ict~nce (preferably, + 1-5 ~m).
To deposit a drop of reactant solution on the subslldte accurately, the dispenser nozzle must be placed a correct list~nce above the surface. The di.~pen~r tip preferably should be located about .1 cm to about 6 cm above the substrate surface when the drop is relP~Pd The degree of control neces~ry to achieve such accuracy can be ~tt~in~ with a repeatable high-resol~ltion translation mP~h~nicm of the type dPc~rihed above. In one emborlimPnt the height above the substrate is determined by moving the ~licpPncPr toward the substrate in small incremP~tc, until the dispenser tip touches the ~ dle. At this point, ~he ~iicrPn~r is moved away from the surface a fixed number of increments which coir~sl onds to a specific dict~nce~ From there, the drop is released to the cell below. Preferably, the increments in which the dispenser moves will vary in accordance with the size of the regions used.
In an ~lte. .~ e embor1imPnt the ~ pencçr nozzle is encircled by a sheath that rigidly extends a fixed rlict~nre beyond the licpenCPr tip. Preferably, this ii.ct~nce collG~nds to the rli~ct~n~ e at which the solution drop will fall when delivered to the sele~te~l reaction region. Thus, when the sheath contacts the substrate s~rf~ce, the movement of the licpencPr is halted and the drop is rP~ P~. It is not neces~,y in this - embodiment to move the ~licpPncer back, away from the substrate, after contact is made.
30 In this embodimPnt as well as the previous embodimPnt, the point of contact with the surface can be determined by a variety of techniques such as by monitoling the c~p~çit~nce or recict~nce between the tip of the dispenser (or sheath) and the ~L~sLI~dtG
W 096tll878 PCTtUS95/13278 below. A rapid change in either of these l,r~ellies is observed upon contact with the surf~ce To this point, the dispenser delivery system has been described only in terms of tr~nc1~tional movemPnt~ However, other systems may also be employed. In5 one emb~imPnt, the rli~pen~r is aligned with respect to the region of interest by a system analogous to that employed in m~gnPtic and optical storage media fields. For eY~m~1e, the region in which reactant is to be deposited is identified by a track and sector location on a disk substrate. The ~ ren~çr is then moved to the a~ro~iate track while the disk substrate rotates. When the a~l,l~liate cell is positioned below the 10 ~ pen.~tq.r (as referenced by the a~l~liate sector on the track), a droplet of reactant s~ tion is relP~ed.
Control of the droplet size may be accomplished by various techniques known to those of skill in the art. For example, in one embo~1imPnt, a convçnti~ n~1 mic~u~ g instrument is adapted to dispense droplets of five n~nolitPrs or smaller 15 from a capillary. Such droplets fit within regions having di~metPrs of 300 ,um or less when a non-wetting mask is employed.
Although the above embodiments have been directed to systems employing liquid droplets, minl1~cule aliquots of each test substance can also be delivered to the reaction region as powders or mini~tl1re pellets. Pellets can be formed, for example, 20 from the compound or component of interest and one or more kinds of inert binding m~tPri~1 The composition of such binders and methods for the plepal~tion of such"pellets" will be a~arent to those of skill in the art. Such "mini-pellets" will be co.. l.d~ible with a wide variety of test substances, stable for long periods of time and --suitable for easy withdrawal from the storage vessel and dispensing.
VI. Synthetic Routes For R~ fing The Array of Components Onçe the array of components has been delivered to pre~PfinPIi regions on the substrate, the components can be simultaneously reacted using a number of dirrelellt synthetic routes. The col"~nents can be reacted using, for example, solution based 30 synthesis techniques, photoçhtomi~1 teçhniques, polymeri7~tit)n teçhniques, temp1~tP
direçted synthesis techniques, epitaxial growth techniques, or by the sol-gel process, by thP,rm~l, infrared or microwave heating, by c~lcin~tion, sintPring or ~nnP~1ing, by hydlulllermal methods, by flux methods, by cryst~11i7~tion through v~oli~ion of W O 96tll878 PCTnUS95/13278 solvent, etc. Other useful synthesis techniques will be a~arc. t to those of skill in the art upon review of this disclosure. lMoreover, the most ap~ropliate synthetic route will depend on the class of m~tPri~lc to be synthPci7~p~ and the selection in any given case - will be readily a~ L to those of skill in the art. In addition, it will be readily 5 app~S;nt to those of skill in the art ~hat, if nto~Pc~ry~ the reactant components can be mixed prior to being reacted using, ~or eY~mple, ultr~cQnic techniques, mP~h~ni-~l techniques, etc. Such techniques Call be applied di~Lly to a given pred~.fin~d region on the substrate or, ~llr~ ely, to all of the predefined regions on the subslldte in a cimlllt~nP~us fashion (e.g., the substr~tP can be merh~nic~lly moved in a manner such 10 that the co~ onents are effectively mixed).
Traditional routes to solid-state synthesis involve the ~intPring of solid re~t~nt~. The standard method used to synth~i7P superconductors, for example, is to grind several metal-oxide powders together, co~ ess the Illi~LUie and, thereafter, bake at a te~ r~nging from 800 C to about 1000 C. The el~mPnt~ in the powder 15 llli~LUlC sinter, i.e., they react chPrnic~lly to form new compounds and fuse into a solid, without passing through the liquid or gaseous phase. Gaseous elemPnt~, such as oxygen, can be taken up during ~intPrin~ or, ~ltPrn~tively, in a subsequent step, and the ~it;S:iUl'~
of the system can be varied during ~e synthesis process. Unfortunately, using t~liti~n~l ~intPrin~ techniques, reac~ion rates are limited by the slow diffusion of atoms 20 or ions through solid re~t~nt~, intermPAi~tP~ and products. Moreover, high l~lll~ldLu~es are frequently required to accelerate diffusion and to thermodyn~mi~lly drive the formation of a stable phase.
In contrast to such traditional routes, in the present invention, new routes to solid-synthesis focus on the synthesis of compounds at lower l~ eldtures. It has 25 been found that reaction ~ates can be increased at lower ~lll~t;ldLures by drastically shortening the ~i~t~nce required for Idiffusion of the re~t~nt~ and by increasing the surface to volume ratio. This can be achieve,d by depositing the re~t~nt~ on thesubstrate in the form of very thin-films or, alternatively, by using solution based synthesis techniques wherein the re~t~nt~ are delivered to the substrate in the form of a 30 solution. Moreover, when the synthesis reaction is to be carried out at a temperature r~ngin~ from about 200 C to about 600 C, a molten salt can be employed to dissolve the reactant components. This technique is generally referred to as the flux method.
.Simil~rly, in a hydrotherm~l method, water or other polar solvent cor,~ ing a soluble inorganic salt is employed to dissolve the reactant components. The hydr~th~-rm~l method is usually carried out under~ress.llc and at a terl,l~r,.l~ ranging from about 100 C to about 400 C. Moreover, using the various synthetic routes of the present invention, the array of reactant components can be ~r~sc,-. ;7f~ or de~le~l. ;7P~ under an S inert atmosphere, oxygen or other gas. In addition, in the synthetic routes of the present invention, various regions on the substrate can be exposed to difr~len~ heat hictori~s using, for eY~mple, laser thermolysis, wherein bursts of energy of a predetermined dllr~tion and intensity are delivered to target regions on the substrate.
In fact, in another embodiment of the present invention, the predefine~
10 regions on a substrate can be subjected to different reaction tempeldLules byindepPndently heating the predefinPd regions using a thin-film resistive PlemPnt In this embo~limPnt, a resistive PlemPnt such as tungct~Pn, is deposited on a clean substrate using any one of the previously described thin-film deposition techniques. The resistive e1PmPnt is deposited, for example, in strips along the rows or columns of pre~efin~
15 regions. Each strip is connect~d to an electrical lead which is ~tt~-~h~1 to a power supply. The temperature of the predefined regions can be regulated by varying the power input to a given strip. In general, any conductive m~t~-ri~l having a melting point higher than the ~ dLule at which the reaction is to be carried out can be used as the resistive Plement Suitable m~t~ri~lc include, but are not limited to, metals, alloys, and 20 cPr~mics. Examples of such m~teri~lc include, but are not limited to, indium doped tin oxide (rrO), tlmgctpn~ molybdenum, t~nt~lllm, platinum, copper-nickel alloys, pl~timlm and rhodium alloys, aluminum-nickel alloys, etc.
In some instances, it may be nP~Ps~ry to coat the resistive element with a protective coating so as to prevent interdiffusion between the resistive elemPnt and the 25 array of colll~onents. The protective coating is applied in the form of a thin-film m~tt~ri~l using the previously described thin-film deposition techniques. The l,rotec~ive coating is made from a m~t~ri~l which effectively conducts heat and which is inert at the ~ >e~dL~re at which the reaction is to be carried out. Examples of suitable m~ttori~lc include, but are not limited to, MgO, SrTiO3, BaTiO3, Al2O3 and other semiconductor 30 and cPr~mi~ m~t~ri~l~ which are good conductors and inert.
Once the resistive elem~nt has been deposited, an array of co~ ents is generated using thin-film deposition techniques in combination with m~kin,~ techniques.
An eY~mrle of this approach is illustrated in FIG. 12. In this eY~mr!~, a library of , W O96111878 PCTrUS95/13278 49 cGln~unds was gPnPr~tP~3 subsequent to the deposition of thin-film resistive strips. As str~ted in FIG. 12, a resistive e1e~nent occupies an entire column of ~redelin~
regions on the substrate. It will be readily appa.ent to those of skill in the art, however, that the resistive elemPnt can be deposited in any pattern and, thus, deposition str~tP~jpls 5 can be deci~n~d so that the resistive elemçnt covers different pred~fin~ regions on the substrate.
Furth~rmore, using the synthetic routes of the present invention, the array of colllponents can be processed between the various delivery steps. For PY~mIlle, co~ ol~ent A can be delivered to a first region on a substrate and, thereafter, exposed to 10 oxygen at an elevated ~l"~?~ldture, for example. Subsequently, col,lponent B can be delivered to the first region on the substrate and, thereafter, co",ponents A and B can be reacted under a set of reaction conditions. Other manipulations and proc~in~ steps which can be carried out between the various delivery steps will be a~ t to those of skill in the art upon reading this ~ r,1Os11re.
As such, using the methods of the present invention, the following m~tPri~1~ can be ~ aLed: covalent network solids, ionic solids and molecular solids.
More particularly, the methods of the present invention can be used to prepa.c, for example, inorganic m~t~ri~1~, intermPt~11ic m~t~ , metal alloys, c~r~mic m~tt~ri~
organic m~tt~ri~1~, organom~t~llic m~teri~1~, non-biological organic polymers, csj"",osi~
20 m~t~ri~1~ (e.g., inorganic composites, organic composites, or combinations thereof~, etc.
Ceramics can be pl~c;d, for in~t~nce, by delivering reactant co,llponents to predefined regions on the substrate using, for example, solution based delivery techniques. Once the reactant cG"~onents of interest have been delivered to the substrate, the substrate is heated to the boiling point of the solvent to e~,~oldt~ off the solvent. ~lt~rn~tively, the 25 solvent can be removed by delivering the reactant co".ponenls to a heated substrate. The substrate is then o~ i7P~ to remove unwanted components (e.g., carbon, nilrogell, etc.) from the array. The substrate is then flash heated at a lelll~ldlul~i; of about 800 C to about 875 C for about two minutes Thereafter, the reaction is rapidly qut-nr~h~l and - the array is sc~nn~ for m~tPri~1~ having a particular prope"y, such as 111min~scen-e, 30 su~er~o,lductivity~ tric strength, etc. M~gnetic m~ttori~1~ can be pl~al~d using a similar process except that in the case of m~nPtiC m~t~ri~ the components are delivered to the substrate and simultaneously reacted thereon in the presence of a m~gnPtic field.
W O96/11878 PCTrUS95113278 Moreover, an array of zeolites, i.e., hydrated eili~tPs of al~minum and either sodium, r~lcil~m or both, can be ~l~ared using the m~th~s of the present invention. To ~r~UG an array of such m~tPri~le, the reactant col,l~nents are delivered to pre~lefinP~ regions on a substrate in the form of a slurry. Using a low t~ cl~lulk S (e.g., 60 C to about 70 C) hydrothPrm~l method, for ~Y~mp1P~ the zeolites will crystallize out of solution. In addition, organic polymers can be pre~dlGd by delivering a monomer (or monomers) of interest to predçfin~l regions on the s~ usually in theform of a solution. Once the monomer of interest has been delivered, an ;~ tor iS
added to each region on the substrate. The polymP-ri7~tion reaction is allowed to proceed until the i~ o~ is used up, or until the reaction is termin~tP~l in some other manner.
Upon completion of the polymPri7~ti~ n reaction, the solvent can be removed by, for example, evaporation in vacuo.
It will be readily a~arGmt to those of skill in the art that the foregoing synthetic routes are intendPd to illuctr~t~, and not restrict, the ways in which the rG~ct~nte can be sim~llt~n~Pously reacted to form at least two m~tto.ri~le on a single substrate. Other synthetic routes and other mo lifis~ti~ns known to and used by those of skill in the art can also be used.
VIII. Methods For Screening the Array of Materials Once ~ ued, the array of materials can be screened in parallel for m~tçri~lc having useful l,l~Gllies. Either the entire array or, ~ltPrn~tively, a section thereof (e.g., a row of predPfinod regions) can be screened in parallel for m~tPri~le having useful pl~pGlLies. Sc~nning detection systems are preferably utilized to screen an array of materials wherein the density of regions per unit area will be greater than .04 25 regions/cm2, more preferably greater than 0.1 regions/cm2, even more preferably greater than 1 region/cm2, even more preferably greater than 10 regions/cm2, and still more preferably greater than 100 regions/cm2. In most preferred embo~imPnte, sc~nningdetection systems are preferably utilized to screen an array of m~teri~l.e wherein ~e density of regions per unit area will be greater than 1,000 regions/cm2, more preferably 10,000 regions/cm2, even more preferably greater than 100,Q00 regions/cm2, and still more preferably 10,000,000 regions/cm2.
Accordingly, in a preferred embodiment, the array of m~tPri~1c is synthPei7P~ on a single substrate. By synthçci7ing the array of m~tPri~le on a single W O96/11878 PCT~US95/13278 ~ul~ e~ scloe.~ g the array for m7(~eri~1~ having useful ~,~,~.lies is more easily carried out. I~o~lLies which can be screened for in~ rle for PY~mr~lP, el~Pctri~ thermalmPich~ni~l, morphological, optical, ~ netic~ che-rnic~l, etc. More particularly, useful pç~ ,Lies which can be screened for are set forth in Table I, infra. Any m~tPri~1 found 5 to possess a useful propelLy can subsequently be plc~ ed on a large-scale.
The t)lu~.Lies listed in Table I can be screened for using conventit n~l mPth~e and devices known to and used by those of skill in the art. Sc~nnin~ systems which can be used to screen for the pl~cllies set forth in Table I incl~de, but are not limited ts~, the following: sç~nnin~ Raman spP~l-oscopy; sc~nnin~ NMR ~e ;l.oscoL~y;
10 sc~nnin~ probe s~eclloscol)y inc~ lin~, for e~mple, surface po~n~ialometry, tnnnpllin~
current, atomic force, acoustic microscopy, ehe~ring-stress microscopy, ultra fast photo eYcit~tion, electrostatic force microscope, t--nnelin~ in~luced photo emission microscope, m~gnPt1C force miclosco~e, microwa~e field-induced surface harmonic genP~tion micl~osco~e, nonlinP~r alt~".aLing-current t--nnPlling microscopy, near-field sc~nnin~
15 optical mi.l~,sc~, inPl~tic electron t~nnPling spectrometer, etc.; optical microscopy in different wavelPngth; sc~nning optical ellipsometly (for mP~cllring dielectric constant and multilayer film thicknt~); sc~nnin~ Eddy-current microscope; electron (~liffr~ction) microscope, etc.
More particularly, to screen for conductivity and/or superconductivity, one 20 of the following devices can be used: a Sr~nning RF Susceptibility Probe, a Sr~nning RF/Microw~ve Split-Ring Resonator Detector, or a Sc~nning Superconductors Quantull-Illt~lÇelellce Device (SQUID) Detection System. To screen for hardness, a nanoindentor (li~mon(l tip) can, for eY~mple, be used. To screen for m~gnptorpci~t~nre~ a Sc~nning RFtMicrowave Split-Ring RPSO~ O1 Detector or a SQUID Detection System can be 25 used. To screen for crys~llinity, infrared or Raman spe~ osco~y can be used. To screen for m~gnPtic strength and coercivity, a Sr~nning RF Susceptibility Probe, a Sc~nnin~ RF/Microwave Split-Ring Resonator Detector, a SQUID Detection System or a Hall probe can be used. To screen for fluorescence, a photo~letP~tor or a charged-- coupled device camera can be used. Other sc~nnin~ systems known to those of skill in 30 the art can also be used.
W O96/11878 PCTrUS9S113278 TABLEI. EX~PLES OFPROP~Kll~S WHICH CANBESCREENED FOR
ELECTRICAL: SUPERCONDUCTIVl~Y
CRITICAL CURRENT
CRITICAL MAGNETIC FIELD
CONDUCTIVlTY
RESISTIVITY FOR RESISTIVE FILMS
DIELECTRIC CONSTANT
DIELECTRIC STRENGTH
DIELECTRIC LOSS
STABILITY UNDER BIAS
POLARIZATION
PERMIl~VITY
PIEZOELECTRICITY
ELECTROMIGRATION
I~R~ 'A r.- COEFFICIENT OF EXPANSION
THERMAL CONDUCTIVITY
TEMPERATURE VARIATION
VOLATILlTY & VAPOR PRESSURE
MEC~INICAL: STRESS
ANISOTROPY
ADHESION
HARDNESS
DENSITY
DUCTILITY
ELASTICITY
POROSITY
MORPNOLOGY: CRYSTALLINE OR AMORPHOUS
MICROSTRUCTURE
SURFACE TOPOGRAPHY
CRYSTALLITE ORIENTATION
OPTICAL. REFRACTIVE INDEX
ABSORPTION
BIREFRINGENCE
SPECTRAL CHARACTERISTICS
DISPERSION
FREQUENCY MODULATION
EMISSION
MAGNETIC: SATURATION FLUX DENSITY
MAGNETORESISTANCE
MAGNETORESTRICTION
W O96tll878 PCTrUS95/13278 COERCIVE FORCE
MAGNETIC: PERMEABILITY
C~EMICAL: COMPOSlTION
COMPLEXATION
ACIDlTY-BASIClTY
CATALYSIS
lMPURlTIES
REACIIVlIY WlTH SUBSTRATE
CORROSION & EROSION RESISTANCE
The arrays of the present invention can be screened sequentially or, ely, they can be screened in parallel using a sc~nning system. For in~t~nce~ thearray of m~tt-.ri~le can be sequentially screened for superconductivity using, for eY~mp1e, m~gnPtic decoration (Bit~er pattern) and electron holography. ~1tPrn~tively, the array of 5 m~t~ri~l.e can be sc~nned for supereonductivity using, for example, a Hall-probe, m~gnPtic force mic,vscol~y, SQUID microscopy, a AC susceptibility miclusco~e, a microwave absorption microscope, an Eddy current microscope, etc.
In a presently plc;r~;lled embodiment, a sc~nnin~ detection system is employed. In one embo~1im~Pnt the substrate having an array of m~tPri~l~ thereon is 20 fixed and the det~P~tor has X-Y motion. In this embo~limpnt~ the substrate is placed inside a sealed chamber, close to the detector. The det~P,ctor (e.g., an RF Reson~or, a SQUID detector, etc.) is ~ttachPd to a rigid rod with low thermal conductivity coupled to an X-Y positioning table at room ~ eldture with a sc~nning range of up to l inch and a 2 ~m spatial reso1~-tinn The position of the detector is controlled using stepping 25 motors (or servomotors) connPctP~l ~o a computer-conkolled positioner. The ~II,~ldture of the detector and the substrate can be lowered via helium e~ch~nge gas by liquid helium reservoir located around the chamber. This sc~nning system can be operated at t~P~"~ ..ies r~nging from 600K down to 4.2K (when immersed in liquid helium).
In another embo-liment, the detector is fixed and the substrate having an 30 array of m~tPri~1~ thereon has R-~ motion. In this embo~limpnt~ the substrate is placed on a rotating stage (e.g., a spur gear) driven by a gear rack which is coupled to a micrometer and a stepping motor. This rotating stage is located on a cryogenic sliding table which is driven by a separate micrometer and stepping motor system. This system is capable of sc~nning an area having a l inch radius with a l ~m spatial reso1~-tion. The W O96/11878 PCTrUS95113278 sc~nnin~ and probing are controlled through the use of a col"~?u~el. As with the other embc~im~nt the Le~ lul~ of the dçtector and the ~ubsl~Le can be lowered via helium eY~ n~e gas using a liquid helium reservoir located around the chamber. This sc~nning system can be operated at tG~ tUlGS r~nging from 600K down to 4.2K (when 5 i,nl"Gl~ed in liquid helium).
Using either of the foregoing embodiments, a .Sc~nning RF Susceptibility Det~cti~ n System can, for example, be used to detect the superconductivity of a large array of m~tP-r~ (see, e.B., FIG. 13). Using photolithographic techniques, a micro (about 1 x 1 mm2) spiral coil can be fabricated to probe the conductivity of a sample 10 ~rlj~rPnt to the coil. The signals are picked up by a phase-sensitive detP~tion electronic circuit. Thereafter, the data is analyzed by a computer to obtain a correlation between the ~lu~Lies and stoiehinmetry of a given sample. If desired, analytical results can be fed back to the delivery system so that the system can "zoom in" on the most promising stoiclliometry in the next synthesis cycle.
Moreover, a ~erco-lducting microcircuit implemPnt~tion of a parallel LC
~so~ ce circuit can be used to scan the array of materials for those that are su~o~ ucting. A parallel LC circuit is simply an inductor in parallel with a c~p~itor.
The elPGtrie~l l,r~ lies of both circuit elements give the circuit a reson~nce frequency where a maximum amount of input voltage is transmitted through to the output. The 20 sharpness of the peak, convention~lly measured by its Q value, is determined by the m~t~ri~l$ used in the circuit, whereas the frequency of the lt;sonance is set by the c~p~eit~nce and the inrluct~nce It has been determined that manufacturing the circuit out of a ~uL~elcol--lucting m~teri~l, such as niobium, gives a very high Q value, i.e., a Q
value on the order of 10,000 or more. This is in contrast to commercially available, 25 non-su~ ol-d~lcting capacitors and inductors which generally give Q values on the order of hundreds. The steep peak of the niobium circuit gives rise to high sensitive detection.
In this system, actual dete~h-)n is done by the induction coil. The induct~nce of an inductor is a function of the m~gnetic field geometry through its coils.
In the presence of a nearby superconducting sample, the magnetic field through the 30 incluGtor is distorted by the expulsion of field by the m~teri~l (i.e., the Mei~ner effect).
This, in turn, changes the inductance and shifts the rçson~nce. By following the~esQ~ Ge, one can readily determine when a m~tPri~l is supe~ c~in~. _ W O96/11878 PCTrUS9r,113278 In this sc~nning device, the total circuit is ap~luAi~ tPly S mm x 2.5 mm, with an active area equal to applu,~ y one-fourth of that. The coil is a spiral coil having dimPn~ioî c of about 1.5 mm per side, and the c~r~itor is a two-plate niobium c~r~it~r with a SiO2~ PlPCtriC (i.e., iln.~nl~ting) layer. SQUID m~nPtQmeterS have 5 achieved spatial res~ tinns of 10 ~m, but their sensitivities have been limited by noise present in the Jos~Pph~on junction In the sc~nnin~ device of the present invention, however, the device is unencumbered by noise from the Josephson junction and, thus, a sensitivity for ~mple~ of 1 ~m or less can be achieved. In this embo-lim~nt sensitivity, rather than spatial resolution~ is a more critical crit~rion.
It will be readily a~ el~ to those of skill in the art that the fc,~cgoing ~letP~.t;on systems are intPn~led to i1ln~tr~te, and not restrict, the ways in which the array Of m~tPri~l can be screened for those m~tPri~l~ having useful prop~llies. Other ~lPtP~tinn systems known to and used by those of skill in the art can ~imil~rly be used.
5 LY. Alterna~ive Embo~iments In another embo~limPnt of the present invention, at least two dirrt;lGl-l arrays of m~tPri~l~ are p cpalcd by de1ivering subst~nti~lly the same reaction colll~onelll~
at subst~nti~lly id~nti~l concentr~tinns to predefined regions on both first and second substrates and, thereafter, subjecting the components on the first substrate to a first set of 20 reaction conditions and the colnpollen~s on the second substrate to a second set of reaction conditions in a wide array of compositions. If a first substrate has, for example, components A and B on a first region on the substrate and, in addition, components X
and Y on a second region on the substrate, the second substrate is ~ al~d in a manner such that it has subst~nti~lly the same components in pre~PfinP~ regions thereon. That is 25 to say, the second substrate is substantially identir~l to the first substrate in terms of the colll~ollents cont~in~A thereon. As such, in this example, the second substrate would also have components A and B on the first region on the substrate and, in addition, colll~nents X and Y on the second region on the substrate.
Once the components have been delivered to their a~pr~iate prP~dPfinPd 30 regions on the substrate, the colll~onents on the first substrate are reacted using a first set of reaction conditions, whereas the components on the second substrate are reacted using a second set of reaction ccnditions. It will be understood by those of skill in the art that the components on the first substrate can be reacted under a first set of reaction W O96/11878 PCTrUS9S/13278 c~ntliti~n~ at the same time as the co,.,~onents on the second substrate are reacted under a second set of reaction conditions or, ~ t..~t;.~ely, the components on the first substrate can be reacted under a first set of reaction conditions either before or after the colllpol~ents on the second substrate are reacted under a second set of reaction conditions.
S In this embodimPnt the effects of various reaction p~r~mPte S can be studied and, in turn, optimi7P.d Reaction p~r~mPters which can be varied include, for eY~mrlt~, reactant amounts, reactant solvents, reaction telll~ldtul~s, reaction times, the t;S~ureS at which the re~t tic-ns are carried out, the atmospheres in which the re~t tion~
are conducteA, the rates at which the reactions are quen~ PA, etc. Other reaction p~r~mPter~ which can be varied will be a~arellt to those of skill in the art.
Alte~ tively, the first set of reaction conditions can be the same as the second set of reaction con-lition~, but, in this embo-lim~nt the pr~cec~in~ steps after the components on the first and second substrates have been reacted would differ from the first substrate to the second substrate. For example, the first substrate can be exposed to oxygen at elevated ~Ill~ldlures~ while the second substr~tP is not processed at all.
.Al~P...~ ely, in another aspect of this emb~impnt~ the first substrate having component A on the first region of the substrate and component X on the second region of the substrate is exposed to a particular set of reaction conditions (e.g., exposed to oxygen at elevated lel.~eldLules), while the second substrate also having colllponent A
20 on the first region of the substrate and colllpollent X on the second region of the substrate is not exposed to such reaction conditions. Thereafter, component B isdelivered to the first region on both the first and second substrates, and component Y is delivered to the second region on both the first and second substrates. Once the desired components have been delivered to the first and second regions on the first and second 25 substrates, the co,llpol-ents are simultaneously reacted under subst~nti~lly i~Pnti~l reaction co~tlitions. This particular embodiment allows one to determine the effects interm~Ai~tP proces~ing steps have on a particular array of m~tP,ri~ls. As set forth above, any of a number of dirrelel~t reaction parameters can be varied.
In still another embodiment of the present invention, a method is provided 30 for producing an array of materials varying from one another in terms of chPmi~
composition and colll~onent stoichiom~trie~. In this method, a reactant component can be delivered to a particular predPfinP~I region(s) in a gradient of stoichiometri~s.
Mor~vel, multiple reactant components can be delivered to a particular predefined W O96/11878 PCTrUS95/13278 region(s) in a gradient of stoirhiomPt1ries. For example, a first component of a first m~t~qri~1 and a first colllp~llent of a second m~tPri~l are deposited on first and second reaction regions, respectively. Thereafter, a second component of the first m~t~ri~1 and a second component of the second m~teri~1 are deposited in a g~tlitont of stoichiometries S from top to bottom (or left to right) on the first and second reaction regions, respectively. Once the co,l,~vllents have been delivered to the st1bst~tP the co"l~onents are sim~11t~n~P~usly reacted to form m~teri~ varying from one another in terms of rhP-mi~l composition and çhPnnir~l sl~içhi~ mP.tri~s.
In yet another embodirnent of the present invention, a m~tPri~l having a 10 useful ~rv~ y is provided. The m~1Pri~1 is ~-c~arcd by a process com~ri.~ing the steps of: (a) forming an array of different m~tPri~l~ on a single substrate; (b) sclælling the array for a m~teri~1 having a useful ~lo~lly; and (c) making additional amounts of the m~t~.ri~1 having the useful l,rvp~l~y. Such m~t~ri~1.c inc1ude7 for example, interme.t~11ic m~t-~ri~1~, metal alloys, ceramic materials, organomPt~llic m~tP.ri~1~, organic polymers, 15 cv~ ?o~ile m~teri~ls (e.g., inorganic composites, organic co~ osi~es, or combinations thereof), etc. In addition~ useful properties include, for example, electrical, thermal, mf~rh~ni~-~1, morphological, optical, rn~gn~tic, ch~7nic~l, etc.
Using the Çvl~going method, a new family of giant m~gnelore~7Li~re (GMR) cobalt oxides has been discovered. Arrays of materials co~ in~ different compositions 20 and stojchiometries of Ln"MyCoO~, wherein Ln is, for ex~mr1e, Y and La, and M is, for example, Pb, Ca, Sr and Ba, were formed using thin film deposition techniques incombination with m~C~ing techniques (See, Example D, in~a, for the protocol used to generate the arrays of cobalt oxide thin-film materials). Once formed, the arrays of m~t~.ri~1~ were screened for those m~tPri~1~ among them having useful p,v~llies. More 25 particularly, the arrays of m~t.o.ri~1~ were screened for spe~ific m~t~ri~1~ having giant m~gnetoresistive (GMR) ~?rvpel~ies, among others. In doing so, m~teri~ having large m~netore.~i~t~nce (MR) were discovered. Once the m~teri~1.c having useful properties were ide.ntifiç.1, additional amounts of such m~t(~.ri~l~ were ~rei)~ed for further analysis.
- The colllpuunds in this new family of GMR cobalt oxides have the 30 following general formula: Ay~ )My~COOz~ wherein A is a metal sel~t~d from the group c-~n~i~ting of 1~nth~mlm (La), yttrium (Y), cerium (Ce), praseodylllilll" (Pr), neody""u"l (Nd), promethium (Pm), samarium (Sm), eulul~iulll (Eu), gadolinium (Gd), terbium Clb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), yllelbiulll ,, ,,, , , ,, , , ,, , . ,,,,,,, , , ,, ,,,, _ , . . .
CA 02202286 l997-04-l8 W O 96/11878 PCTrUS9S/13278 (Yp) and lllt~illm a~u); M is a metal se1ect~1 from the group con.ci.~tin~ of c~ m (Ca), strontium (Sr), barium (Ba), lead (Pb), th~11inm (Il) and bismuth (13i); y has a value ran~ing from about 1 to about 2; x has a value r~ngin~ from about 0. l to about 0.9; and z has a value r~nging from about 2 to about 4. The compounds in this new family of 5 GMR cobalt oxides generally have a layered, perovskite-related structure, i.e., a cubic perovskite structure with some slight distortion.
In a ~lcsently prcrellcd embo~1im~nt the compounds in this new farnily of GMR cobalt oxides have the following general formula: A~ CoOz, wherein A is a metal s~1~.ted from the group con~ ting of ]~nth~m-m (La), yttrium (Y), cerium (Ce), pr~ yll iulll (Pr), neodymium (Nd), promethium (Pm), ~111i11;11111 (Sm), el-n)piu.n (Eu), g~-lolinillm (Gd), terbium (Tb), dys~losium (Dy), holmium (Ho), erbium (Er), th111i11m (Tm), ytterbium (Yp) and lutecium (Lu); M is a metal se1e~tecl from the group con.~i~tin~ of c~1ei11m (Ca), ~Llol~Liulll (Sr), barium (Ba), lead (Pb) and ~flminn (Cd); x has a value ranging from about 0.1 to about 0.9; and z has a value r~nging from about 2 to about 4. Within the scope of this formula, certain embo~limPnt.~ are .L)lc;r~ d, namely those in which x has a value r~n~ing from about 0.2 to about 0.7 and, even more c;r~lc;d, are those in which x has a value ranging from 0.3 to about 0.5.
In a further ~ ere~.ed embodiment, the compounds in this new family of GMR cobalt oxides have the following general formula: Lal ~M,~CoOz, wherein M is a metal sP1eoted from the group con~ ting of barium, calcium and ~LIun~ l; x has a value r~nging from about O.l to about 0.9; and z has a value ranging from about 2 to about 4.
Within the scope of this formula, certain embodiments are ~r~relled, namely those in which x has a value ranging from about 0.2 to about 0.7 and, even more ~lefell~d, are those in which x has a value r~ngin from 0.3 to about 0.5. As mentioned, the compounds in this new family of GMR cobalt oxides generally have a layered, perovskite-related structure.
In yet another embodiment of the present invention, libraries of microdevices, such as thin-film c~r~l-itors or thin-film electro1-~mint~s~nt module.~" can be g~.n~ t~d using the method~ previously described for gP.nP.rating arrays of m~t~ri~
For eY~mr1e, a thin-film c~r~ritor consists of two electrode m~t~ri~l~ se~ted by an --inm1~tin~ or dielectric m~t~ri~l An array of thin-film c~r~eitc~rs can be formed by first dt;L,osiLi.lg an electrode material on each of the predefined regions on the substrate. An array of rlielp~tric m~teri~l~ can then be generated on top of the electrode surface using W O96/11878 PCTrUSgS113278 the meth~ previously described. On top of this layer, another electrode layer can be deposited, reos-llting in an array of thin-film c~r~ritors~ each r~r~ritl~r co~ h)g a dirrc;l~;nt ~iPl~-ct~ic m~teri~l By measuring the c~pa~it~nce at each of the predPfinP~
regions on the substrate, the ~elroll"allce of the various ~iPlPctric m~tPri~l~ for thin-film c~r~itors can be tested and optimi7~P~l~ It will be readily ~ cnl to those skilled in the art that this approach is fully applicable to other thin-film devices, such as thin-film electroll-minP,scPnt displays. In addition, it will be readily ~ Gnl to those skilled in the art that any one of the various layers in a thin-film device can be an array of dirre~"t m~tPri~l~ at the same or dirrel~l t stoichimPtrie~, or an array of the same m~teri~l at dirrclent stoichiometries. Moreover, the order of the various layers can be varied (e.g., the electrode m~teri~l in the thin-film ~p~itnrs can be deposited on either the top or bottom of the other layers. Thus, using the methods of the present invention, each of the layers in a given thin-film device can be optimi7P~.
It will be understood by those of skill in the art that the rOlcgoillg discussions directed to the various delivery techniques, synthetic routes, s~ileening methods, etc. are fully applicable to the above embo~iment~ of the present invention.
X. Exa~nples The following eY~mI)les are provided to illustr~tP the efficacy of the inventions herein.
A. Synthesis of An Arr~y of i!6 Copper Oxide T~zin-Film Ma~erials This example illustrates the synthesis and s~;,~ning of an array of copper oxide thin-film m~tPn~l~ The re~c~t~nt~ were delivered to a 1.25 cm x 1.25 cm MgO
substrate with a (100) polished surface. The substrate having 16 preAPfinPd regions thereon was contained in a reaction chamber in vacuo. The re~ct~nt~ were delivered to the substrate in the form of thin-films using a ~ul~e~ g system in combination with binary m~1ring techniques. The binary mask was made of st~inlP~ steel. A RF
m~gnPtron gun sputtPring system was used to deliver the reactant coll,~nents to the pre~efinPcl regions on the substrate. The RF m~gnPtron ~ P-~ g gun (Mini-mak m~mlf~tllred by US, Inc., Campbell~ CA) used was about 1.3 inches in ~ mPter. With RF input power (supplied by a Pl~mtherm-2000 with a m~t~hing network) of 50 to about 200 W, deposition rates ranged from about 0.3 A/s to about 2 A/s for the five _ _ O96/11878 PCTrUS95/13278 dirr~l~l reactant co..~pol-~nt~. The RF m~gn~tron sprayer was positioned about 3 to 4 inches above the subsll~te and the uniro~ ily of deposited film was about 5% over a 1 to
2 inch rli~m~.tPr area. The ~ g gas flow (Ar or Ar and O2) was controlled bymPtprin~ valves and dirr~ ial l~ul-~ping through a manual gate valve. To achieve a high de~os;iLion rate, it was deterrnined that the best gas ~ Si~lrt range was about 5 to 15 mTorr. The partial L~rt;ssule of each gas component in the chamber was monitored using a residual gas analyzer (Micropole Sensor by Ferran Scientific, San Diego, CA) directly up to 15 mTorr without dirrt;le ~tial pUIIIpillg.
The reactant co"~onents used to generate the array of copper oxide m~tçri~1~ were as follows: CuO, Bi2O3, CaO, PbO and SrCO3. CuO was used as the base elem~nt in an effort to discover new copper oxide m~t~ri~ and, thus, this component was delivered to each of the 16 predefine~ regions on the substrate. Prior to delivering the cGIl~L)onent of interest to the preclefined regions on the substrate, the base air pressure of the reaction chamber was lowered, within 10 to 15 minutes, to about 10-5 to 10~ Torr by a 250 l/s turbo pump and, if n~e~.~ry, it was furthered lowered to 10-8 Torr using eYt~n~ ulllping time in combination with heating the reaction chamber to about 100C to about 150C. Since only a single R~ m~gnetron gun ~ul~ g system was employed, the vacuum was broken and re-established each time the colllpollent was ch~n~.od. The film deposition thickness was monitored using a crystal micro-balance (STM-100 by Sycon InstrumPnt~, Syracuse, NY). Since the position of crystal micro-b~l~nce was not located at exactly the same position as the substrate, it was nP~.~.y to c~lihr~tç the thickn~ monitor reading for each coll-~onent with a profilometer.
The reactant components were delivered to the MgO substrate in the following order: Bi203, PbO, CuO, CaO and SrC03. The stoichiometry was d~-ci~n~dso that each of the five co.n~ollents was present in equal molar amounts, i.e., lBi:lPb:lCu:lSr:lCa as deposited film. The total thickness of the film was about 0.5 ,um for a five layered site. The thicknes.~ of each of the individual films as well as the sputtering rates at which each of the components were deposited are set forth in Table II, supra.
W O96/11878 PCTrUS9~/13278 TAI~ 11. DEPOSITION TNICKNESS AND ~'~Ul -l ~ING RATE FOR THE
COMPONENTS USED TO GENERATE AN ARRAY OF COPPER
5 OX~DES
Component Deposition Thic~nPs~ Sp"~lr~ Rate Bi2o3 1200 A 2 A/Sec PbO 970 A 1.6A/sec Cuo s40 A 1 A/Sec SrCO3 1650 A 3 A/Sec CaO 720 A 3 A/sec Once the co~ onents of interest were delivered to the 16 pre~lefined regions on the ~ul ~lldle as illll~tr~tP~d in FIG. 14, the substrate was placed in a furnace, and the coll,~nents were subsequently reacted. FIG. 15 is a photograph of the array of 16 dirrGlGI-t co~ uullds Oîl the 1.25 cm x 1.25 cm MgO substrate. The color of each site is the natural color of reflP~tP~l light from a white light source at an angle. The co",po-lents were ~imult~nPQusly reac~ed using the following heating and coolingprocedure: 50 C to 725 C in 2 hr., 725 C to 820 C in 1 hr., 820 C to 840 C in 0.5 hr. and 840 C to 750 C in 0.5 hr. Once the substrate cooled to a te",~ldLu.~ of about 750 C, the power was turned off. The heating and cooling procedure was ~elror",ed in ambient atmosphere. No ayyarGnt evaporation or meltin~ was observed.
Once reacted, each of the 16 predefined reaction regions was screened for re~i~t~nce. In doing so, it was found that two of the predçfined regions cont~inPd m~tPri~1~ which are conductinE. Contacts were put on these two sites in in-line 4-probe configuration, and it was determined that the contact resistances are less than hundred ohms (S2). Thereafter, the samples were cooled down to 4.2K in a liquid helium ~;l.y~7ldl to measure resistivity as a function of IG",peldl~lre. Factory calibrated Cernoxnl rç~i~t~nce Ik.~ A~ sensor (LakeShore) was used to measure lGIllpGldlulG. FIGS. 16A
and 16B shows the re~i~t~nce of the two conducting m~tPri~l~ as a function of le,,lpeldlule. The BiPbCuSrCa material has a met~llic conductivity (re~i~t~nce decrease with IGlllpGld~Ule) from room temperature down to about 100K, whereas the BiCuSrCa m~tPri~l has a rather flat and slightly upward ~e~llpeldture depçndPnce re~ist~nce W O96/11878 PCTrUS95/13278 Su~l~;onductinp critical lell,~ldtures ~c) for both Mm~1os are about 100K. Evidence of two su~l~n~ ctin~ phases in the resistivity measurement was not observed.
B. Svnthesis of An Array of 128 Copper Oxide Thin-Film Ma~e~ial S This eY~mple illnstr~t~s the synthesis and s.;læning of a 128 m~mher library con~i~tin~ of different combinations, st~ichiometries and deposition sequences of Bi, Ca, Cu, Pb and Sr. The library was gen~r~t~ by *~ target m~t.ori~1~ through physical masks using an RF m~gnçtron S~U~ g gun. S~ult ~ was carried out at 10-5to 104 torr with Ar as the S~ Çl;I-g gas; deposition rates were 0.1 to 1 A s~'. Film deposition thickn~ was monitored with a crystal microbalance and calibrated indepçndçntly with a profilometer. The unif<, ,-lily of the deposited films varied a~r~xi,,,~Ply 5% over a 2-inch diameter area. MgO single crystals with a (100) polished surface were used as substrates and CuO, Bi2O3, CaO, PbO and SrCO3 wereused as ;!~llllrl;~g targets. The library was generated using a binary m~ ing ~lldle~y by o~/ell~ing a primary physical mask cont~ining 128 (l x 2 mm) holes with a series of sçcon~ry masks (FIG. 17). (See, Fodor, S.P.A., et al., Science 251, 767 (1991)).Precursors were spu~ cd through the ap~lu~/iate binary mask in a stepwise fashion. Up to six i~enti~l 128 mPmber libraries could be synthçsi7~d simultaneously and processed under dirrelcnt conditions. In a binary synthesis, 2m compounds are formed for a given nllmber of m~ ing steps (m). The array contains all combinations that can be formed by dPleting one or more steps from the entire deposition/m~cking sequence. Additional m~kin~ schem~o~ can be used to generate other libraries, e.g., a library cûn~i~tin~ of all q~ tPrn~ry compounds derived from a group of ten precursors.
As mentioned, a 128-member library was gen~r~t~d to eY~min~ the effects of stoichiometry and deposition sequence on the ~lol~elLies of the BiSrCaCuO films. I~e library was generated as follows: 1, Bi, M0; 2, Bi, Ml; 3, Cu, M0; 4, Cu, M2; 5, Cu, M3; 6, Sr, M0; 7, Sr, M5; 8, Ca, M6; 9, Cu, M4; 10, Ca, M7, where the first entry lç~i~n~tçs the deposition step, the second dçcign~tes the çlem~nt and the third ~çsi~n~tes the mask (see, FIG. 18). The molar stoichiometry for each layer was 1: 1 relative to Bi (which was deposited as a 300 A layer), with the exception of steps 3 and 5 in which the Cu:Bi ratio was 0.5:1. The library was then sintered at 840C in air. The heating and cooling procedures were: 50C to 725C in 2 hr., 725C to 820C in 1 hr., 820C to 840C in 0.5 hr., 840C to 750C in 0.5 hr. The entire heating procedure was W O96/11878 PCTnUS95113278 perforTnP~ in air. No a~t;;nt evaporation or melting was observed. The re~i~t~n~e of each SitR was measured us;ng a 4-point contact probe.
Films with low resistivities such as the BiCuSrCaO film shown in FIG.
19A showed mPt~llic behavior with onset Tc's of 80K and 90K. This is in contrast to S the behavior of the BiCuCaSrO film found in the sixteen mçmher library. Other films were also found in the 128 member library, having iAPntir~l stoi~hiometries and different deposition sequences, that had distinct resistivity versus l~ P~ profiles, e.g.,BiCuSrCaCuCaO and BiCuCuSrCaCaO (FIG. 19B). This result su~gPst~ that different phases may be ~ ihle by controlling the deposition sequence. Films with excess Ca and Cu, e.g., BiSrCaCuO ratios of 2D2,4,4 and 2,2,4,5, showed a 110K phase, con~ictent with the formation of Bi2Sr2Ca2Cu3OI0.
C. Synthesis of an Arrav of 128 Copper Oxide 7~in-Film Materials Containinp BiSrCaCuO and YBaCuO Superconductin~ Matenals This ~Y~mple illustrates the synthesis and screening of a 128 member library con~ictin~ of dirrtr~i t combinations, stci~hiometries and deposition sequences of Ba, Y, Bi, Ca, Sr and Cu. The library was generated by s~u~ target m~t~ri~
through physical masks using an RF rn~nPtron sputtering gun. S~ul Ikl .i-g was carried out at 10-5 to 10~ torr with Ar as the s~ul(e~ ;ng gas; deposition rates were 0.1 to 1 A s-'.
Film deposition thic~nP~s was monitored with a crystal microbalance (STM-100 by Sycon InstrumPnts, Syracuse, NY) and calibrated indepen~iently with a profilometer. The unifc,l",ily of the dt;po~iled films varied approximately 5% over a 1 to 2 inch ~ mPtPr area. MgO single crystals with a (lal0) polished surface were used as substrates and BaCO3, Y203, Bi203, CaCD, SrC03 and CuO were used as s~ g targets. The library was genPr~tPA using a non-binary m~kin~ strategy as described below.
The 128-member library was generated to examine the effects of st~ ichiometry and deposition sequence on the ~,~elLies of the BiSrCaCuO and YBaCuO
thin-film m~tPri~ls. The library was generated as follows: 1, Bi, Ml; 2, Cu, M2; 3, La, M3; 4, Y3, M4; 5, Ba, M5; 6, Sr, M6; 7, Ca, M7, where the first entry desi~n~tes the deposition step, the second de~i~rl~tPs the elemPnt and the third dç~ign~tPs the mask employed (see, FIG. 20). The thic~nes~ of each of the individual films was as follows:
Bi2o3, looo A; cuo, 716 A; La2o3~ 956 A; Y203, 432 A; Baco3~ 1702 A; srco3~ 1524 A; CaO, 635 A. Following low temperature diffusion (--200-300C), the library was W O96/11878 PCTrUS95/13278 sintered at 840C in ambient atmosphere. The heating and cooling procedure used was as follows: 200C to 300C in 12 hr., 300C to 700C in 1 hr., 700C to 750C in 2 hr., 750C to 840C in 0.4 hr., 840C to 840C for 1 hr., 840C to 560C in 1 hr., 560C to 250C in 6 hr. After 6 hours at 250C, the power was turned off. The entire S heating procedure was performed in air. No a~rellt evaporation or m~lting was observed.
Once reacted, each of the 128 predPfined regions was screened for re~ist~n-e. The re~i~tanA~ of each site was measured using a 4-point contact probe.
Films with low resistivities, such as the BiCuSrCaO film and the YBaCuO film shown in FIG. 21, showed m.-t~llic behavior with onset Tc s of about 80K and 60K, respectively (see, FIG. 21).
D. Svnthesis of Arr~vs of Cobalt Oxide Thin-film Matenals This example illustrates the synthesis and screening of arrays of cobalt 15 oxide (CoO) thin-film m~t~ri~l~. The reactants were delivered to 2.5 cm x 2.5 cm LaAl03 ~ub~Llal~s with (100) polished surfaces. The substrates having 128 predt~-fined regions thereon were contained in a reaction chamber in vacuo. The re~t~nt~ weredelivered to the substrates in the form of thin-films using a ~u~P ;-lg system in combination with non-binary m~king techniques. The masks employed were made of 20 st~inl~s~ steel. A RF m~gnetron gun ~u~ g system was used to deliver the reactant conlponents to the predefined regions on the substrates. The l?F m~gnetron sy~ r~ g gun ~Mini-mak m~nllfa ~tllred by US, Inc., Campbell, CA) used was about 1.3 inches in rli~mPter. With RF input power (supplied by a Pl~mtherm-2000 with a m~t~ing network) of 50 to about 200 W, deposition rates ranged from about 0.3 A/s to about 2 25 A/s for the various reactant conlponents. The RF m~gnPtron sprayer was positioned about 3 to 4 inches above the substrates and the uniformity of de~osited film was about 5% over a 1 to 2 inch li~meter area. The ~u~ g gas flow (Ar or Ar and O2) was controlled by met~ring valves and differential pumping through a manual gate valve. To achieve a high deposition rate, it was determined that the best ples~u~e range was about 5 30 to 15 mTorr. The partial pressure of each gas component in the chamber was monitored using a residual gas analyzer (Micropole Sensor by Ferran Scientific, San Diego, CA) directly up to 15 mlbrr without differential pumping.
-W O 96/11878 PCTnUS9S/13278 The reactant co~ onents used to generate the arrays of cobalt oxide m~tPri~lc were as follows: Y2O3, La2O3, Co, BaCO3, SrCO3, CaO, PbO, Co, Co, La2OLa2O3, Y2O3, and Y2O3. The libraries were generated as follows: 1, Y, Ml; 2, La, M2;
The reactant co"~onents used to generate the array of copper oxide m~tçri~1~ were as follows: CuO, Bi2O3, CaO, PbO and SrCO3. CuO was used as the base elem~nt in an effort to discover new copper oxide m~t~ri~ and, thus, this component was delivered to each of the 16 predefine~ regions on the substrate. Prior to delivering the cGIl~L)onent of interest to the preclefined regions on the substrate, the base air pressure of the reaction chamber was lowered, within 10 to 15 minutes, to about 10-5 to 10~ Torr by a 250 l/s turbo pump and, if n~e~.~ry, it was furthered lowered to 10-8 Torr using eYt~n~ ulllping time in combination with heating the reaction chamber to about 100C to about 150C. Since only a single R~ m~gnetron gun ~ul~ g system was employed, the vacuum was broken and re-established each time the colllpollent was ch~n~.od. The film deposition thickness was monitored using a crystal micro-balance (STM-100 by Sycon InstrumPnt~, Syracuse, NY). Since the position of crystal micro-b~l~nce was not located at exactly the same position as the substrate, it was nP~.~.y to c~lihr~tç the thickn~ monitor reading for each coll-~onent with a profilometer.
The reactant components were delivered to the MgO substrate in the following order: Bi203, PbO, CuO, CaO and SrC03. The stoichiometry was d~-ci~n~dso that each of the five co.n~ollents was present in equal molar amounts, i.e., lBi:lPb:lCu:lSr:lCa as deposited film. The total thickness of the film was about 0.5 ,um for a five layered site. The thicknes.~ of each of the individual films as well as the sputtering rates at which each of the components were deposited are set forth in Table II, supra.
W O96/11878 PCTrUS9~/13278 TAI~ 11. DEPOSITION TNICKNESS AND ~'~Ul -l ~ING RATE FOR THE
COMPONENTS USED TO GENERATE AN ARRAY OF COPPER
5 OX~DES
Component Deposition Thic~nPs~ Sp"~lr~ Rate Bi2o3 1200 A 2 A/Sec PbO 970 A 1.6A/sec Cuo s40 A 1 A/Sec SrCO3 1650 A 3 A/Sec CaO 720 A 3 A/sec Once the co~ onents of interest were delivered to the 16 pre~lefined regions on the ~ul ~lldle as illll~tr~tP~d in FIG. 14, the substrate was placed in a furnace, and the coll,~nents were subsequently reacted. FIG. 15 is a photograph of the array of 16 dirrGlGI-t co~ uullds Oîl the 1.25 cm x 1.25 cm MgO substrate. The color of each site is the natural color of reflP~tP~l light from a white light source at an angle. The co",po-lents were ~imult~nPQusly reac~ed using the following heating and coolingprocedure: 50 C to 725 C in 2 hr., 725 C to 820 C in 1 hr., 820 C to 840 C in 0.5 hr. and 840 C to 750 C in 0.5 hr. Once the substrate cooled to a te",~ldLu.~ of about 750 C, the power was turned off. The heating and cooling procedure was ~elror",ed in ambient atmosphere. No ayyarGnt evaporation or meltin~ was observed.
Once reacted, each of the 16 predefined reaction regions was screened for re~i~t~nce. In doing so, it was found that two of the predçfined regions cont~inPd m~tPri~1~ which are conductinE. Contacts were put on these two sites in in-line 4-probe configuration, and it was determined that the contact resistances are less than hundred ohms (S2). Thereafter, the samples were cooled down to 4.2K in a liquid helium ~;l.y~7ldl to measure resistivity as a function of IG",peldl~lre. Factory calibrated Cernoxnl rç~i~t~nce Ik.~ A~ sensor (LakeShore) was used to measure lGIllpGldlulG. FIGS. 16A
and 16B shows the re~i~t~nce of the two conducting m~tPri~l~ as a function of le,,lpeldlule. The BiPbCuSrCa material has a met~llic conductivity (re~i~t~nce decrease with IGlllpGld~Ule) from room temperature down to about 100K, whereas the BiCuSrCa m~tPri~l has a rather flat and slightly upward ~e~llpeldture depçndPnce re~ist~nce W O96/11878 PCTrUS95/13278 Su~l~;onductinp critical lell,~ldtures ~c) for both Mm~1os are about 100K. Evidence of two su~l~n~ ctin~ phases in the resistivity measurement was not observed.
B. Svnthesis of An Array of 128 Copper Oxide Thin-Film Ma~e~ial S This eY~mple illnstr~t~s the synthesis and s.;læning of a 128 m~mher library con~i~tin~ of different combinations, st~ichiometries and deposition sequences of Bi, Ca, Cu, Pb and Sr. The library was gen~r~t~ by *~ target m~t.ori~1~ through physical masks using an RF m~gnçtron S~U~ g gun. S~ult ~ was carried out at 10-5to 104 torr with Ar as the S~ Çl;I-g gas; deposition rates were 0.1 to 1 A s~'. Film deposition thickn~ was monitored with a crystal microbalance and calibrated indepçndçntly with a profilometer. The unif<, ,-lily of the deposited films varied a~r~xi,,,~Ply 5% over a 2-inch diameter area. MgO single crystals with a (100) polished surface were used as substrates and CuO, Bi2O3, CaO, PbO and SrCO3 wereused as ;!~llllrl;~g targets. The library was generated using a binary m~ ing ~lldle~y by o~/ell~ing a primary physical mask cont~ining 128 (l x 2 mm) holes with a series of sçcon~ry masks (FIG. 17). (See, Fodor, S.P.A., et al., Science 251, 767 (1991)).Precursors were spu~ cd through the ap~lu~/iate binary mask in a stepwise fashion. Up to six i~enti~l 128 mPmber libraries could be synthçsi7~d simultaneously and processed under dirrelcnt conditions. In a binary synthesis, 2m compounds are formed for a given nllmber of m~ ing steps (m). The array contains all combinations that can be formed by dPleting one or more steps from the entire deposition/m~cking sequence. Additional m~kin~ schem~o~ can be used to generate other libraries, e.g., a library cûn~i~tin~ of all q~ tPrn~ry compounds derived from a group of ten precursors.
As mentioned, a 128-member library was gen~r~t~d to eY~min~ the effects of stoichiometry and deposition sequence on the ~lol~elLies of the BiSrCaCuO films. I~e library was generated as follows: 1, Bi, M0; 2, Bi, Ml; 3, Cu, M0; 4, Cu, M2; 5, Cu, M3; 6, Sr, M0; 7, Sr, M5; 8, Ca, M6; 9, Cu, M4; 10, Ca, M7, where the first entry lç~i~n~tçs the deposition step, the second dçcign~tes the çlem~nt and the third ~çsi~n~tes the mask (see, FIG. 18). The molar stoichiometry for each layer was 1: 1 relative to Bi (which was deposited as a 300 A layer), with the exception of steps 3 and 5 in which the Cu:Bi ratio was 0.5:1. The library was then sintered at 840C in air. The heating and cooling procedures were: 50C to 725C in 2 hr., 725C to 820C in 1 hr., 820C to 840C in 0.5 hr., 840C to 750C in 0.5 hr. The entire heating procedure was W O96/11878 PCTnUS95113278 perforTnP~ in air. No a~t;;nt evaporation or melting was observed. The re~i~t~n~e of each SitR was measured us;ng a 4-point contact probe.
Films with low resistivities such as the BiCuSrCaO film shown in FIG.
19A showed mPt~llic behavior with onset Tc's of 80K and 90K. This is in contrast to S the behavior of the BiCuCaSrO film found in the sixteen mçmher library. Other films were also found in the 128 member library, having iAPntir~l stoi~hiometries and different deposition sequences, that had distinct resistivity versus l~ P~ profiles, e.g.,BiCuSrCaCuCaO and BiCuCuSrCaCaO (FIG. 19B). This result su~gPst~ that different phases may be ~ ihle by controlling the deposition sequence. Films with excess Ca and Cu, e.g., BiSrCaCuO ratios of 2D2,4,4 and 2,2,4,5, showed a 110K phase, con~ictent with the formation of Bi2Sr2Ca2Cu3OI0.
C. Synthesis of an Arrav of 128 Copper Oxide 7~in-Film Materials Containinp BiSrCaCuO and YBaCuO Superconductin~ Matenals This ~Y~mple illustrates the synthesis and screening of a 128 member library con~ictin~ of dirrtr~i t combinations, stci~hiometries and deposition sequences of Ba, Y, Bi, Ca, Sr and Cu. The library was generated by s~u~ target m~t~ri~
through physical masks using an RF rn~nPtron sputtering gun. S~ul Ikl .i-g was carried out at 10-5 to 10~ torr with Ar as the s~ul(e~ ;ng gas; deposition rates were 0.1 to 1 A s-'.
Film deposition thic~nP~s was monitored with a crystal microbalance (STM-100 by Sycon InstrumPnts, Syracuse, NY) and calibrated indepen~iently with a profilometer. The unifc,l",ily of the dt;po~iled films varied approximately 5% over a 1 to 2 inch ~ mPtPr area. MgO single crystals with a (lal0) polished surface were used as substrates and BaCO3, Y203, Bi203, CaCD, SrC03 and CuO were used as s~ g targets. The library was genPr~tPA using a non-binary m~kin~ strategy as described below.
The 128-member library was generated to examine the effects of st~ ichiometry and deposition sequence on the ~,~elLies of the BiSrCaCuO and YBaCuO
thin-film m~tPri~ls. The library was generated as follows: 1, Bi, Ml; 2, Cu, M2; 3, La, M3; 4, Y3, M4; 5, Ba, M5; 6, Sr, M6; 7, Ca, M7, where the first entry desi~n~tes the deposition step, the second de~i~rl~tPs the elemPnt and the third dç~ign~tPs the mask employed (see, FIG. 20). The thic~nes~ of each of the individual films was as follows:
Bi2o3, looo A; cuo, 716 A; La2o3~ 956 A; Y203, 432 A; Baco3~ 1702 A; srco3~ 1524 A; CaO, 635 A. Following low temperature diffusion (--200-300C), the library was W O96/11878 PCTrUS95/13278 sintered at 840C in ambient atmosphere. The heating and cooling procedure used was as follows: 200C to 300C in 12 hr., 300C to 700C in 1 hr., 700C to 750C in 2 hr., 750C to 840C in 0.4 hr., 840C to 840C for 1 hr., 840C to 560C in 1 hr., 560C to 250C in 6 hr. After 6 hours at 250C, the power was turned off. The entire S heating procedure was performed in air. No a~rellt evaporation or m~lting was observed.
Once reacted, each of the 128 predPfined regions was screened for re~ist~n-e. The re~i~tanA~ of each site was measured using a 4-point contact probe.
Films with low resistivities, such as the BiCuSrCaO film and the YBaCuO film shown in FIG. 21, showed m.-t~llic behavior with onset Tc s of about 80K and 60K, respectively (see, FIG. 21).
D. Svnthesis of Arr~vs of Cobalt Oxide Thin-film Matenals This example illustrates the synthesis and screening of arrays of cobalt 15 oxide (CoO) thin-film m~t~ri~l~. The reactants were delivered to 2.5 cm x 2.5 cm LaAl03 ~ub~Llal~s with (100) polished surfaces. The substrates having 128 predt~-fined regions thereon were contained in a reaction chamber in vacuo. The re~t~nt~ weredelivered to the substrates in the form of thin-films using a ~u~P ;-lg system in combination with non-binary m~king techniques. The masks employed were made of 20 st~inl~s~ steel. A RF m~gnetron gun ~u~ g system was used to deliver the reactant conlponents to the predefined regions on the substrates. The l?F m~gnetron sy~ r~ g gun ~Mini-mak m~nllfa ~tllred by US, Inc., Campbell, CA) used was about 1.3 inches in rli~mPter. With RF input power (supplied by a Pl~mtherm-2000 with a m~t~ing network) of 50 to about 200 W, deposition rates ranged from about 0.3 A/s to about 2 25 A/s for the various reactant conlponents. The RF m~gnPtron sprayer was positioned about 3 to 4 inches above the substrates and the uniformity of de~osited film was about 5% over a 1 to 2 inch li~meter area. The ~u~ g gas flow (Ar or Ar and O2) was controlled by met~ring valves and differential pumping through a manual gate valve. To achieve a high deposition rate, it was determined that the best ples~u~e range was about 5 30 to 15 mTorr. The partial pressure of each gas component in the chamber was monitored using a residual gas analyzer (Micropole Sensor by Ferran Scientific, San Diego, CA) directly up to 15 mlbrr without differential pumping.
-W O 96/11878 PCTnUS9S/13278 The reactant co~ onents used to generate the arrays of cobalt oxide m~tPri~lc were as follows: Y2O3, La2O3, Co, BaCO3, SrCO3, CaO, PbO, Co, Co, La2OLa2O3, Y2O3, and Y2O3. The libraries were generated as follows: 1, Y, Ml; 2, La, M2;
3, Co, M3; 4, Ba, M4; 5, Sr, M5; 6, Ca, M6; 7, Pb, M7; 8, Co, M8; 9, Co, M9; 10,La, M10; 11, La, Mll; 12, Y, M12; and 13, Y, M13, where the first entry ~e~ign~tPc the deposition step, the second desi~n~t-p~s the elPm~-nt and the third de~ n~tPs the mask employed (see, FIG. 22). Co was used as the base e1PmP-nt in an effort to discover new cobalt oxide thin-film m~t~ri~lc having giant m~netorecict~nt ~ropellies and, thus, this co,ll~nent was delivered to each of the 128 pre~efinP~ regions on the ~ubsLldles. Prior to delivering the co~ onent of interest to the pre~Pfin~d regions on the substrates, the base air ~)leSi:iUl~; of the reaction chamber was lowered, within 10 to 15 ...i~ s, to about lo-5 to 10~ Torr by a 250 l/s turbo pump and, thereafter, it was furthered lowered to 10-8 Torr using eYtPnrle~ ~ulllping time in combination with heating the reaction chamber to about 100C to about 150C. Since only a single RF m~nPtron gun ~u~.;.-g 15 system was employed, the vacuum was broken and re-established each time the co.llponent was changed. The film de;position thicknPss was monitored using a crystal microb~l~nr~ (STM-100 by Sycon Instnlm~nt~, Syracuse, NY).
The reactant co-ll~nents were delivered to the LaAlO3 substrates in the following order: Y203, La203, Co, BaLCO3, SrC03, CaO, PbO, Co, Co, La203, La203,20 Y2O3, and Y2O3. The total thicknPss of the films was about 0.4 ~m for a five layered site. The thicknP~ of each of the individual films is set forth in Table III, supra.
W O96111878 PCTrUS95/13278 66 TABLE III. DEPOSI~ION THICKNESS AND SPUl -l ~ING RATE FOR THE
COMPONENTS USED TO GENERATE AN ARRAY OF COBALT
OXIDES
Component Deposition Thickne~
Y2O3 24s A
La2o3 350 A
co 145 A
BaCO3 600 A
SrCO3 538 A
CaO 24s A
PbO 316A
Co 128 A
1S co s5 A
La2o3 245 A
La2o3 245 A
Once the components of interest were delivered to the 128 preclefin~d -regions on the substrates, the substrates were placed separately in a furnace, and the components were subsequently reacted. The components in Library 2 (L2) were 25~imlllt~neously reacted using the following heating and cooling procedure: 200 C to 300 c in 12 hr., 300c to 650 C in 1 hr., 650 C to 850 C in 3 hr., 850 C to 900 C in 3 hr., and 900 C to 400 C in 2 hr. Once the substrate cooled to a temperature of about 400 C, the power was turned off. The heating and cooling procedures were performed in ambient atmosphere. No ap~arenl evaporation or melting was observed.
The components in Library 3 (L3) were simultaneously reacted using the following heating and cooling procedure: Room Temperature (RT) to 200 C in 1 hr., 200 C to 350 C in lS hr., 3so C to RT (system shut down and the substrate allowed to cool to RT), RT to 650 C in 2 hr., 650 C to 740 C in 13 hr., 740 C to 850 C in --lhr., 850 C to 900 C in 3 hr., 900 C to 650 C in 0.5 C hr, and 650 C to 250C
W O 96/11878 PCTrUS95/13278 in 2 hr. Once the substrate cooled to a lel"~lalurc of about 400 C, the power was turned off. The heating and cooling l.rûcedures were ~elrulllled in ~mhient atmosphere.
No a~l~wl~ cv~.dLion or mr-1tinp was observed.
Once reacted, each of the 128 pre~efinP~ reaction regions in the L2 and S L3 lihr~ri~5 was screened for giant m~gn~ot~resistant (GMR) m~tf-ri~l~. The resistivity of each sample as a function of m~netic field, perpendicular to the probing current, and ~ G was measured using the 4-probe contact method with a CO~ Ulcl controlled multi-ch;mn~ wilclling system. A liqLuid helium c; yogenic system with a ~uycl~ductin~ 12 Tesla (T) magnet l~mAmlfActllred by Janis Research Co., Inc., 10 Willmington, MA) was used to pelru-~l. variable Lelll~ U1C and field measuremPnt~.
FIG. 23 shows a map of the libraries and the stoichiometry of each sample. In addition, the black, solid circles in FIG. 23 in~lic~tr~i those samples which exhibited a signific~nt GMR ( ~ 5 %) effect.
From FIG. 23, it is a~alcllt that a new family of GMR mstf.ri~1~ based on 15 cobalt oxide has been discovered. The compounds in this new family of GMR cobalt oxides have the following general strueture: Ay.(l X)My~xcoo~ wherein A is a metal sf-1r-cted from the group cor~ ting of lanthanum (La), yttrium (Y), cerium (Ce),pr~f-~lyllliu~ll (Pr), neodymium (Nd), promPthi~lm (Pm), ~~ h~lll (Sm), euluyiulll (Eu), ~tlolini~lm (Gd), telbiulll(Tb), dysprosium (Dy), holmium (Ho), erbium (Er), 20 th~ m crm), yLL~ iulll (Yp) and luleciulll (Lu); M is a metal SPl~ct~ from the group con~i~tin~ of e~lcillm (Ca), ~ill`OllliUIII ~Sr), barium (Ba), lead (Pb), th~llil-m (Tl) and bismuth (Bi); y has a value r~n~ing from about 1 to about 2; x has a value ranging from about 0.1 to about 0.9; and z has a value r~nginp from about 2 to about 4. The col~ounds in this new family of GMR cobalt oxides generally have a layered 25 perovskite-related structure.
In a presently ~lcfe~led embodiment, the compounds in this new family of GMR cobalt oxides have the following general formula: Al "M,~CoO7, wherein A is a metal s,Dlr-cted from the group con~i~ting of lanthanum (La), yttrium (Y), cerium (Ce), - praseodymiu.. (Pr), neodymium (Nd)~ promethium (Pm), samarium (Sm), e~lu~iu---30 (Eu), ~ olinil-m (Gd), ~llLiulll (Ib), dysprosium (Dy), holmium (Ho), erbium (Er), thl~ m crm), ytterbium (Yp) and lulecium (Lu); M is a metal selected from the group con.~i~tin~ of c~lcil-m (Ca)~ strontium (Sr), barium (Ba), lead (Pb) and cil-lmil-n (Cd); x W O 96/11878 PCTrUS9S/13278 has a value r~n~in~ from about 0.1 to about 0.9, more preferably, 0.2 to 0.7 and, even more preferably, 0.3 to 0.5; and z has a value ran~in~ from about 2 to about 4.
Moreover, from FIG. 23, it is ap~ l that some of these cobalt oxide compounds have the form~ Lal xM~CoOz, wherein M is a member selPctP~ from the 5 group con~i~tin~ of Ca, Sr and Ba; x has a value r~n~in~ from about 0.1 to about 0.9;
and z has a value ranging from about 2 to about 4. With respect to these particular cobalt oxide compounds, it was determined that the plere,l~d molar fraction, i.e., x, is about 0.2 to about 0.7 and, even more preferably, about 0.3 to about 0.5. The n~rm~li7Pd m~f~nPtnreci~t~n~çs of representative ~mpl~Ps as a function of m~gnPtic field at fixed Le~ dLule (60 K) are shown in FIGS. 24A and 24B. The ~el~-~ldlure depPndP-nrx of the resi~t~nce and norm~li7P~ MR of a represent~tive sample L3 (13, 2) under different fields are shown in FIGS. 25A and 25B. In contrast to the behavior of m~ng~nP.se (Mn) oxide m~pnstt resistant (MR) m~teri~l~ (Jin, S., et al., Appl. Phys. Lett.
66:382 (1995)), it has been found that the MR effect increases as the size of the ~lk~line earth ion increases (see, FIGS. 24A and 24B).
The MR effects of the samples in L2 are larger than those of L3, p~su~l~ably due to dirrt;r~.lces in oxi-l~tion resl-lting from slightly different thP!rm~l tre~tment~ The largest MR ratio measured in this library was 72%, obtained for sample L2 (15,2) at T=7K and H=lOT. This value is co,-,pa,dble to those measured for films g~on~or~tP~ in a similar fashion in a Mn based library. As with the m~n~n~ co~ ,inin~
m~tPri~l~, optimi7~ti~n of composition, stoichiometry, substrate and synthetic conditions may lead to increases in the MR ratio. The corresponding Y(Ba, Sr, Ca)Co compounds show, however, much smaller (<5~) MR effects.
Three bulk samples with the stoichi~ metry LaO67(Ba,Sr,Ca)0.33CoOz, wherein z has a value of about 2 to about 4, were then synthP~i7P~d (sintered at 1400C
in air) for further structural study. X-ray diffraction patterns (FIGS. 26A-C) show that the crystal structure is basically cubic perovskite with lattice constant, a, equal to 3.846 A, 3.836 A, and 3.810 A for the Ba, Sr, and Ca compounds, respectively. The minor ~plittin~ of the intensity peaks are attlibuted to rhombohedral distortion from the perfect cubic perovskite structure (see, ~kh~m, F., et al., J. Amer. Chem. Soc. 72:3799 (1950)).
In addition, a bulk sample of stoichiometry IdOs8SrO4lcooz~ wherein z has a value of about 2 to about 4, was synthesi7~d and its magncti7~tion was measured with W O96/11878 PCTrUS95/13278 a SQUID m~nPt~meter (Quantum Design). The sample MR as a function of m~nPtic field and the sample m~g.~ n under lT m~gnPtic field as a function of tt;
were measured and are shown in FIG 27. A gradual r~ ""~nPti~ ~n~itinn starts at -200 K and ~ es below 50 K. The MR ratio of this bulk sample (60%) is 5 ~ignifif~ntly higher than that of the coll~onding thin film sample L2 (30%). The X-ray analysis of this sample confirrned the cubic perovskite structure with a = 3.82 A.
E. Svnthesis of An Array of 16 Different Or~anic Polymers This example illustrates the possible synthesis of an array of 16 dirr~l~nt 10 organic polymers formed by the polynnPri7~ti-)n of styrene with acrylonitrile. A 3 cm x 3 cm pyrex substrate having 16 predefine~ regions thereon is used in this example. Each of the pre~lefinP~l regions is 3 mm x 3 mm x 5 mm and, thus, the volume of each prede.fined region is about 45 ~L. To ensure that the reactants in a given region do not move to ~ cent regions, 35 ~L reaction volumes will be used.
A 2 M solution of the styrene monomer in toluene and a 2 M solution of acrylonitrile in toluene are used. The initi~t-)r used to initiate the polymP-ri7~tion reaction is benzoyl peroxide. A 70 mM solution of benzoyl peroxide in toluene is used. The initi~tor is present in each of the reactions at a 10 mM concentr~tion. The styrene, acrylonitrile and benzoyl peroxide solutions are delivered to each of the 16 predefinPd 20 regions on the substrate using an inkjet dispenser having three noz71e~ The first no7zles is connP~t~ to a reservoir cont~ining the 2 M solution of styrene in toluene, the second nozzle is conne~ted to a reservoir cont~ining the 2 M solution of acrylonitrile in t lllene, and the third nozzle is connP~tP~l to a reservoir c(mt~ining the 70 mM solution of benzoyl peroxide in tol~ene The initiator is delivered to each of the 16 predefined 25 regions only after the monomers have been delivered.
To generate an array of 16 different polymers of styrene and acrylonitrile, the reactant amounts set forth in Table IV, infra, are delivered to the 16 pre~lefin~i regions on the substrate. Once the monomers have been delivered to the 16 predPfinY1 regions on the substrate, 5 ~L of the 70 mM initiator solution is added. The 30 polymPri7~tion reaction is carried out at a temperature of about 60C and at ~mhient plt;s~ul~. The re~tion~ are allowed to proceed until the ~l",in~ol is used up. Upon completion of the polyme"7~tion reac~ion, the organic solvent is removed by evaporation W O 96/11878 . PCTrUS9S/13278 in vacuo (100 Torr). The re.,sulting polymers can be screened for hardness using, for çY~mrl.o, a n~nnin~lentnr (sharp tip).
TAl~LEIV. VARIOUS REACTANT COMPONENTS USED TO GENERATEAN
S ARR4Y OP 16 DIFF'ERENT POLYMERS
ti~n Region Amount of 2 M Solution Amount of 2 M Solution of Styrene (~L) of Acrylonitnle ~uL) 2 28.5 l.S
The reactant co-ll~nents were delivered to the LaAlO3 substrates in the following order: Y203, La203, Co, BaLCO3, SrC03, CaO, PbO, Co, Co, La203, La203,20 Y2O3, and Y2O3. The total thicknPss of the films was about 0.4 ~m for a five layered site. The thicknP~ of each of the individual films is set forth in Table III, supra.
W O96111878 PCTrUS95/13278 66 TABLE III. DEPOSI~ION THICKNESS AND SPUl -l ~ING RATE FOR THE
COMPONENTS USED TO GENERATE AN ARRAY OF COBALT
OXIDES
Component Deposition Thickne~
Y2O3 24s A
La2o3 350 A
co 145 A
BaCO3 600 A
SrCO3 538 A
CaO 24s A
PbO 316A
Co 128 A
1S co s5 A
La2o3 245 A
La2o3 245 A
Once the components of interest were delivered to the 128 preclefin~d -regions on the substrates, the substrates were placed separately in a furnace, and the components were subsequently reacted. The components in Library 2 (L2) were 25~imlllt~neously reacted using the following heating and cooling procedure: 200 C to 300 c in 12 hr., 300c to 650 C in 1 hr., 650 C to 850 C in 3 hr., 850 C to 900 C in 3 hr., and 900 C to 400 C in 2 hr. Once the substrate cooled to a temperature of about 400 C, the power was turned off. The heating and cooling procedures were performed in ambient atmosphere. No ap~arenl evaporation or melting was observed.
The components in Library 3 (L3) were simultaneously reacted using the following heating and cooling procedure: Room Temperature (RT) to 200 C in 1 hr., 200 C to 350 C in lS hr., 3so C to RT (system shut down and the substrate allowed to cool to RT), RT to 650 C in 2 hr., 650 C to 740 C in 13 hr., 740 C to 850 C in --lhr., 850 C to 900 C in 3 hr., 900 C to 650 C in 0.5 C hr, and 650 C to 250C
W O 96/11878 PCTrUS95/13278 in 2 hr. Once the substrate cooled to a lel"~lalurc of about 400 C, the power was turned off. The heating and cooling l.rûcedures were ~elrulllled in ~mhient atmosphere.
No a~l~wl~ cv~.dLion or mr-1tinp was observed.
Once reacted, each of the 128 pre~efinP~ reaction regions in the L2 and S L3 lihr~ri~5 was screened for giant m~gn~ot~resistant (GMR) m~tf-ri~l~. The resistivity of each sample as a function of m~netic field, perpendicular to the probing current, and ~ G was measured using the 4-probe contact method with a CO~ Ulcl controlled multi-ch;mn~ wilclling system. A liqLuid helium c; yogenic system with a ~uycl~ductin~ 12 Tesla (T) magnet l~mAmlfActllred by Janis Research Co., Inc., 10 Willmington, MA) was used to pelru-~l. variable Lelll~ U1C and field measuremPnt~.
FIG. 23 shows a map of the libraries and the stoichiometry of each sample. In addition, the black, solid circles in FIG. 23 in~lic~tr~i those samples which exhibited a signific~nt GMR ( ~ 5 %) effect.
From FIG. 23, it is a~alcllt that a new family of GMR mstf.ri~1~ based on 15 cobalt oxide has been discovered. The compounds in this new family of GMR cobalt oxides have the following general strueture: Ay.(l X)My~xcoo~ wherein A is a metal sf-1r-cted from the group cor~ ting of lanthanum (La), yttrium (Y), cerium (Ce),pr~f-~lyllliu~ll (Pr), neodymium (Nd), promPthi~lm (Pm), ~~ h~lll (Sm), euluyiulll (Eu), ~tlolini~lm (Gd), telbiulll(Tb), dysprosium (Dy), holmium (Ho), erbium (Er), 20 th~ m crm), yLL~ iulll (Yp) and luleciulll (Lu); M is a metal SPl~ct~ from the group con~i~tin~ of e~lcillm (Ca), ~ill`OllliUIII ~Sr), barium (Ba), lead (Pb), th~llil-m (Tl) and bismuth (Bi); y has a value r~n~ing from about 1 to about 2; x has a value ranging from about 0.1 to about 0.9; and z has a value r~nginp from about 2 to about 4. The col~ounds in this new family of GMR cobalt oxides generally have a layered 25 perovskite-related structure.
In a presently ~lcfe~led embodiment, the compounds in this new family of GMR cobalt oxides have the following general formula: Al "M,~CoO7, wherein A is a metal s,Dlr-cted from the group con~i~ting of lanthanum (La), yttrium (Y), cerium (Ce), - praseodymiu.. (Pr), neodymium (Nd)~ promethium (Pm), samarium (Sm), e~lu~iu---30 (Eu), ~ olinil-m (Gd), ~llLiulll (Ib), dysprosium (Dy), holmium (Ho), erbium (Er), thl~ m crm), ytterbium (Yp) and lulecium (Lu); M is a metal selected from the group con.~i~tin~ of c~lcil-m (Ca)~ strontium (Sr), barium (Ba), lead (Pb) and cil-lmil-n (Cd); x W O 96/11878 PCTrUS9S/13278 has a value r~n~in~ from about 0.1 to about 0.9, more preferably, 0.2 to 0.7 and, even more preferably, 0.3 to 0.5; and z has a value ran~in~ from about 2 to about 4.
Moreover, from FIG. 23, it is ap~ l that some of these cobalt oxide compounds have the form~ Lal xM~CoOz, wherein M is a member selPctP~ from the 5 group con~i~tin~ of Ca, Sr and Ba; x has a value r~n~in~ from about 0.1 to about 0.9;
and z has a value ranging from about 2 to about 4. With respect to these particular cobalt oxide compounds, it was determined that the plere,l~d molar fraction, i.e., x, is about 0.2 to about 0.7 and, even more preferably, about 0.3 to about 0.5. The n~rm~li7Pd m~f~nPtnreci~t~n~çs of representative ~mpl~Ps as a function of m~gnPtic field at fixed Le~ dLule (60 K) are shown in FIGS. 24A and 24B. The ~el~-~ldlure depPndP-nrx of the resi~t~nce and norm~li7P~ MR of a represent~tive sample L3 (13, 2) under different fields are shown in FIGS. 25A and 25B. In contrast to the behavior of m~ng~nP.se (Mn) oxide m~pnstt resistant (MR) m~teri~l~ (Jin, S., et al., Appl. Phys. Lett.
66:382 (1995)), it has been found that the MR effect increases as the size of the ~lk~line earth ion increases (see, FIGS. 24A and 24B).
The MR effects of the samples in L2 are larger than those of L3, p~su~l~ably due to dirrt;r~.lces in oxi-l~tion resl-lting from slightly different thP!rm~l tre~tment~ The largest MR ratio measured in this library was 72%, obtained for sample L2 (15,2) at T=7K and H=lOT. This value is co,-,pa,dble to those measured for films g~on~or~tP~ in a similar fashion in a Mn based library. As with the m~n~n~ co~ ,inin~
m~tPri~l~, optimi7~ti~n of composition, stoichiometry, substrate and synthetic conditions may lead to increases in the MR ratio. The corresponding Y(Ba, Sr, Ca)Co compounds show, however, much smaller (<5~) MR effects.
Three bulk samples with the stoichi~ metry LaO67(Ba,Sr,Ca)0.33CoOz, wherein z has a value of about 2 to about 4, were then synthP~i7P~d (sintered at 1400C
in air) for further structural study. X-ray diffraction patterns (FIGS. 26A-C) show that the crystal structure is basically cubic perovskite with lattice constant, a, equal to 3.846 A, 3.836 A, and 3.810 A for the Ba, Sr, and Ca compounds, respectively. The minor ~plittin~ of the intensity peaks are attlibuted to rhombohedral distortion from the perfect cubic perovskite structure (see, ~kh~m, F., et al., J. Amer. Chem. Soc. 72:3799 (1950)).
In addition, a bulk sample of stoichiometry IdOs8SrO4lcooz~ wherein z has a value of about 2 to about 4, was synthesi7~d and its magncti7~tion was measured with W O96/11878 PCTrUS95/13278 a SQUID m~nPt~meter (Quantum Design). The sample MR as a function of m~nPtic field and the sample m~g.~ n under lT m~gnPtic field as a function of tt;
were measured and are shown in FIG 27. A gradual r~ ""~nPti~ ~n~itinn starts at -200 K and ~ es below 50 K. The MR ratio of this bulk sample (60%) is 5 ~ignifif~ntly higher than that of the coll~onding thin film sample L2 (30%). The X-ray analysis of this sample confirrned the cubic perovskite structure with a = 3.82 A.
E. Svnthesis of An Array of 16 Different Or~anic Polymers This example illustrates the possible synthesis of an array of 16 dirr~l~nt 10 organic polymers formed by the polynnPri7~ti-)n of styrene with acrylonitrile. A 3 cm x 3 cm pyrex substrate having 16 predefine~ regions thereon is used in this example. Each of the pre~lefinP~l regions is 3 mm x 3 mm x 5 mm and, thus, the volume of each prede.fined region is about 45 ~L. To ensure that the reactants in a given region do not move to ~ cent regions, 35 ~L reaction volumes will be used.
A 2 M solution of the styrene monomer in toluene and a 2 M solution of acrylonitrile in toluene are used. The initi~t-)r used to initiate the polymP-ri7~tion reaction is benzoyl peroxide. A 70 mM solution of benzoyl peroxide in toluene is used. The initi~tor is present in each of the reactions at a 10 mM concentr~tion. The styrene, acrylonitrile and benzoyl peroxide solutions are delivered to each of the 16 predefinPd 20 regions on the substrate using an inkjet dispenser having three noz71e~ The first no7zles is connP~t~ to a reservoir cont~ining the 2 M solution of styrene in toluene, the second nozzle is conne~ted to a reservoir cont~ining the 2 M solution of acrylonitrile in t lllene, and the third nozzle is connP~tP~l to a reservoir c(mt~ining the 70 mM solution of benzoyl peroxide in tol~ene The initiator is delivered to each of the 16 predefined 25 regions only after the monomers have been delivered.
To generate an array of 16 different polymers of styrene and acrylonitrile, the reactant amounts set forth in Table IV, infra, are delivered to the 16 pre~lefin~i regions on the substrate. Once the monomers have been delivered to the 16 predPfinY1 regions on the substrate, 5 ~L of the 70 mM initiator solution is added. The 30 polymPri7~tion reaction is carried out at a temperature of about 60C and at ~mhient plt;s~ul~. The re~tion~ are allowed to proceed until the ~l",in~ol is used up. Upon completion of the polyme"7~tion reac~ion, the organic solvent is removed by evaporation W O 96/11878 . PCTrUS9S/13278 in vacuo (100 Torr). The re.,sulting polymers can be screened for hardness using, for çY~mrl.o, a n~nnin~lentnr (sharp tip).
TAl~LEIV. VARIOUS REACTANT COMPONENTS USED TO GENERATEAN
S ARR4Y OP 16 DIFF'ERENT POLYMERS
ti~n Region Amount of 2 M Solution Amount of 2 M Solution of Styrene (~L) of Acrylonitnle ~uL) 2 28.5 l.S
4 25.5 4.5 S ~ 24 6 6 22.5 7.5 S 8 l9.S l0.S
0 16.5 13.5 lS
12 13.5 16.5 14 lO.S l9.S
16 7.5 22.5 F. SYnthesis of An Arrrzy of Zeolites This example ill~lstr~t~s a possible method for the synthesis of an array of dirr~lei~t 7lo~1itPs. The re~ct~nt~ are delivered to a 9 cm x 9 cm Teflon substrate having 16 pre~lefined regions thereon. The substrate is placed in a sealed container having a le.. ~l~L~ure of about 100 C. Each of the 16 pre~efinecl regions on the substrate is a 1 , =
cm x 1 cm x 2 cm well. The re~ t~nt.~ are delivered to the substrate using a aulol~lated pipet,te.
W O 96/11878 PCTnUS95/13278 The five components used to ~en~r~t~ the array of 7~1it~.s are as follows:
Na20-Al203-5H20, KOH, Na20-2SiO2-5H20, NaOH and H20. The first four col"ponents are dissolved in water to con~ntr~tion~ of 2.22 M, 2.22 M, 8.88 M and 11.1 M? ~c~ Jely. In delivering the coll-ponents to the predefin~ regions on the~ul)s~lte, it is im ~ll~ulL that the Na20-2SiO2-5H20 solution is added last. The five reactant co,llL,onents are delivered to 1:he pre~iefined regions on the substrate in the al..uuli~ set forth in Table V, infra.
Once the rolc;going col-,~onents have been delivered to the ap~rù~?liale predefined regions on the substrate and allowed to react, the array can be sc~nn~d for l0 microstructure using a Raman Light Scattering System. Sc~nning of the array can begin 2 to 3 hours after the components have been delivered to the substrate and can continue for anywhere from S to l0 days. In ~:his example, Zeolite A will initially be formed at reaction region l. With time, however, Zeolite A will be converted to Zeolite P.Zeolite X will be formed at reaction region 3. Sodalite will be formed at reaction region 6. Zeolite L will be formed at reaction region 12. In addition, other 7~1ites may be formed at other reaction regions on the sul,s~ldle.
W O 96/11878 PCTrUS9S/13278 TA}~LE V. VARIOUS REACTANT COMPONENTS USED TO GENERATE AN
ARRAY OF ZEOLITES
~P~rtic)n Amount of Amount of Amount of Amount of Amount of S Region 2.2 M 8.88M 2.2M ll.lM H20(~L) Solution of Solution of Solution of Solution of Na20-Al203 KOH (~L) Na20-2SiO2 NaOH (~L) ., SH2O (~L) SH20 (~L) G. Synthesis of An Array of Copper Oxide Compounds Usin~ Spravin~
DeDosl~on Techniques This eY~mple illustrates the synthesis of an array of copper oxide compounds using spraying deposition techniques. The rP~ct~nt~ are delivered to a 1.25 cm x 1.25 cm MgO substrate having 16 pre~lPfinP11 regions thereon. The re~t~nt~ -are delivered in the form of thin-films using a sprayer in combination with physical m~.~lring techniques. The sprayer used in this example is a Sinitek 8700-120MS
ultrasonic sprayer. At a water flow rate of 0.26 GPM and a frequency of 120 KHz, this W O96111878 PCTrUS95/13278 y~r can ~enPr~tP. a cone-line sprayi~ng pattern of 2 inches and a droplet ~ met~Pr of 18 microns.
The four conll)c nents used in this example to generate the array of inorganic m~tPri~l.c are Bi(N03)3, Cu(NO3)3, Ca(NO3)3 and Si(NO3h. These colll~nents
0 16.5 13.5 lS
12 13.5 16.5 14 lO.S l9.S
16 7.5 22.5 F. SYnthesis of An Arrrzy of Zeolites This example ill~lstr~t~s a possible method for the synthesis of an array of dirr~lei~t 7lo~1itPs. The re~ct~nt~ are delivered to a 9 cm x 9 cm Teflon substrate having 16 pre~lefined regions thereon. The substrate is placed in a sealed container having a le.. ~l~L~ure of about 100 C. Each of the 16 pre~efinecl regions on the substrate is a 1 , =
cm x 1 cm x 2 cm well. The re~ t~nt.~ are delivered to the substrate using a aulol~lated pipet,te.
W O 96/11878 PCTnUS95/13278 The five components used to ~en~r~t~ the array of 7~1it~.s are as follows:
Na20-Al203-5H20, KOH, Na20-2SiO2-5H20, NaOH and H20. The first four col"ponents are dissolved in water to con~ntr~tion~ of 2.22 M, 2.22 M, 8.88 M and 11.1 M? ~c~ Jely. In delivering the coll-ponents to the predefin~ regions on the~ul)s~lte, it is im ~ll~ulL that the Na20-2SiO2-5H20 solution is added last. The five reactant co,llL,onents are delivered to 1:he pre~iefined regions on the substrate in the al..uuli~ set forth in Table V, infra.
Once the rolc;going col-,~onents have been delivered to the ap~rù~?liale predefined regions on the substrate and allowed to react, the array can be sc~nn~d for l0 microstructure using a Raman Light Scattering System. Sc~nning of the array can begin 2 to 3 hours after the components have been delivered to the substrate and can continue for anywhere from S to l0 days. In ~:his example, Zeolite A will initially be formed at reaction region l. With time, however, Zeolite A will be converted to Zeolite P.Zeolite X will be formed at reaction region 3. Sodalite will be formed at reaction region 6. Zeolite L will be formed at reaction region 12. In addition, other 7~1ites may be formed at other reaction regions on the sul,s~ldle.
W O 96/11878 PCTrUS9S/13278 TA}~LE V. VARIOUS REACTANT COMPONENTS USED TO GENERATE AN
ARRAY OF ZEOLITES
~P~rtic)n Amount of Amount of Amount of Amount of Amount of S Region 2.2 M 8.88M 2.2M ll.lM H20(~L) Solution of Solution of Solution of Solution of Na20-Al203 KOH (~L) Na20-2SiO2 NaOH (~L) ., SH2O (~L) SH20 (~L) G. Synthesis of An Array of Copper Oxide Compounds Usin~ Spravin~
DeDosl~on Techniques This eY~mple illustrates the synthesis of an array of copper oxide compounds using spraying deposition techniques. The rP~ct~nt~ are delivered to a 1.25 cm x 1.25 cm MgO substrate having 16 pre~lPfinP11 regions thereon. The re~t~nt~ -are delivered in the form of thin-films using a sprayer in combination with physical m~.~lring techniques. The sprayer used in this example is a Sinitek 8700-120MS
ultrasonic sprayer. At a water flow rate of 0.26 GPM and a frequency of 120 KHz, this W O96111878 PCTrUS95/13278 y~r can ~enPr~tP. a cone-line sprayi~ng pattern of 2 inches and a droplet ~ met~Pr of 18 microns.
The four conll)c nents used in this example to generate the array of inorganic m~tPri~l.c are Bi(N03)3, Cu(NO3)3, Ca(NO3)3 and Si(NO3h. These colll~nents
5 were dissolved in water to con~Pntraticm~ of 0.8 M, 2 M, 2 M and 2 M, respectively.
The pH of the Bi(N03)3 solution was about 0.9. In delivering the re~ct~nt~ to the pre~lefinP~l regions on the ,-lbsL-~Lt;, it is in~lL~t to control the flow rate of the sprayer as well as the ~ )eld~Ure of the substrate so that the reactant droplets dry immP~i~t~ly upon contact with the substrate s~rf~e. The flow rate used was kept at about 0.26 10 GPM, and the ~mp~Lule of the substrate was m~int~inP~ at about 210 C. In ~ lition, it is illll?olL~u~l to control the spraying time so that the amount, i.e., moles, of each reactant is apl~r~;m~tply the same. The spraying time was such that each of the thin-layer films deposited on the surface of the substrate had a thiclcnPss of about 1 to 4 microns.
Using a binary m~cking strategy, the aqueous solutions of Ca(NO3)3, Bi(N03)3, CU(N O3)3 and Si(N O3)3 were delivered, in this order, to the substrate using the following steps. As mPntionP~l, the MgO substrate had 16 pre~efineA regions 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16. In a first m~Cl~ing step, regions 9, 10, 11, 12, 13, 14, 15, and 16 were masked and an aqueous solution of Ca(NO3)3 was delivered to the exposed regions in the form of a thin-film. Thereafter, in a second m~king step, the mask was repositioned so that regions 3, 4, 7, 8, 11, 12, 15 and 16 were m~cl~P.1, and an aqueous solution of Bi(N03)3 was delivered to the exposed regions in the form of a thin-film. In a third m~C~ing step, regions 5, 6, 7, 8, 13, 14, 15 and 16 were m~Cl~p~
and an aqueous solution of Cu(NO3)3 was delivered to the exposed regions in the form of a thin-film. Finally, in a fourth m~k;ng step, regions 2, 4, 6, 8, 10, 12, 14 and 16 were m~kPIl, and an aqueous solution of Si(NO3)3 was delivered to the exposed regions in the form of a thin-film.
Once the components of interest were delivered to the al?pl~flate pred~PfinPd regions on the substrate, the substrate having the array of re~c t~nt~ thereon was o~i~li7~d at 300 C to remove any nitrogen from the array. Th~,~arler, the substrate was flash heated at 880 C for about :2 minutes and rapidly qu~Pnt~hP~d on a copper block.
Thereafter, the array of m~tPri~l~ was screened for superconducting m~tPri~l.
W O96/11878 PCTrUS9S/13278 H. Svnthesis of An Array of 16 D~fferent Zinc Silicate Phosphors This ~Y~mple illnstr~t~ the possible synthesis of an array of 16 dirre,cl~
zinc silicate phosphnrs. A 1 mm x 1 mm pyrex substrate having 16 preAefin~oA~ regions thereon is used in this example. Each of the predefin~d regions is 100 ~Lm x 100 f~m x S 500 ~m and, thus, the volume of each pred~PfinPA. region is about 5,000 pi~lit~rs. To ensure the re~t~nt~ in a given region do not move to adjacent regions, 3,000 picolit~r reaction volumes will be used.
The react~nt~ will be delivered ~imlllt~neously to each region on the ~ul sll~te using an inkjet di~ren~pr having three nO771~S. The first nozzle is connected to a .~s~v~Jir ~,.l~ini.~ a lM solution of ZnO in water. To gen~dte an array of 16 different phnsphors, the reactant amounts set forth in Table VI, infra, are delivered to the 16 pre~lefinPA~ regions on the substrate. The synthesis reaction is carried out under a ni~vgt;n atmosphere for a period of 2 hrs. at 1400C. Once formed, each of the 16 pre~lPfin~d reaction regions is screened for electroluminescent m~tPri~ or phosphors by r~ *n~ the sample with a sperific excitation wavelength and recording the emission spectra with a Perkin-Elmer LS50 spectrofluorimeter.
W 096/11878 PCTrUS95/13278 ~ABLE VI. VARIOUS REACTANT COMPONENTS USED TO GENERATE AN
ARRAY 0~ ZINC SIL~rCATE PHOSPHORS
Reaction Region SiO2 MnCO3 ZnO
(picoliters) 2 15a0 1350 150 3 15C~ 1275 225 4 15~0 1200 300
The pH of the Bi(N03)3 solution was about 0.9. In delivering the re~ct~nt~ to the pre~lefinP~l regions on the ,-lbsL-~Lt;, it is in~lL~t to control the flow rate of the sprayer as well as the ~ )eld~Ure of the substrate so that the reactant droplets dry immP~i~t~ly upon contact with the substrate s~rf~e. The flow rate used was kept at about 0.26 10 GPM, and the ~mp~Lule of the substrate was m~int~inP~ at about 210 C. In ~ lition, it is illll?olL~u~l to control the spraying time so that the amount, i.e., moles, of each reactant is apl~r~;m~tply the same. The spraying time was such that each of the thin-layer films deposited on the surface of the substrate had a thiclcnPss of about 1 to 4 microns.
Using a binary m~cking strategy, the aqueous solutions of Ca(NO3)3, Bi(N03)3, CU(N O3)3 and Si(N O3)3 were delivered, in this order, to the substrate using the following steps. As mPntionP~l, the MgO substrate had 16 pre~efineA regions 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16. In a first m~Cl~ing step, regions 9, 10, 11, 12, 13, 14, 15, and 16 were masked and an aqueous solution of Ca(NO3)3 was delivered to the exposed regions in the form of a thin-film. Thereafter, in a second m~king step, the mask was repositioned so that regions 3, 4, 7, 8, 11, 12, 15 and 16 were m~cl~P.1, and an aqueous solution of Bi(N03)3 was delivered to the exposed regions in the form of a thin-film. In a third m~C~ing step, regions 5, 6, 7, 8, 13, 14, 15 and 16 were m~Cl~p~
and an aqueous solution of Cu(NO3)3 was delivered to the exposed regions in the form of a thin-film. Finally, in a fourth m~k;ng step, regions 2, 4, 6, 8, 10, 12, 14 and 16 were m~kPIl, and an aqueous solution of Si(NO3)3 was delivered to the exposed regions in the form of a thin-film.
Once the components of interest were delivered to the al?pl~flate pred~PfinPd regions on the substrate, the substrate having the array of re~c t~nt~ thereon was o~i~li7~d at 300 C to remove any nitrogen from the array. Th~,~arler, the substrate was flash heated at 880 C for about :2 minutes and rapidly qu~Pnt~hP~d on a copper block.
Thereafter, the array of m~tPri~l~ was screened for superconducting m~tPri~l.
W O96/11878 PCTrUS9S/13278 H. Svnthesis of An Array of 16 D~fferent Zinc Silicate Phosphors This ~Y~mple illnstr~t~ the possible synthesis of an array of 16 dirre,cl~
zinc silicate phosphnrs. A 1 mm x 1 mm pyrex substrate having 16 preAefin~oA~ regions thereon is used in this example. Each of the predefin~d regions is 100 ~Lm x 100 f~m x S 500 ~m and, thus, the volume of each pred~PfinPA. region is about 5,000 pi~lit~rs. To ensure the re~t~nt~ in a given region do not move to adjacent regions, 3,000 picolit~r reaction volumes will be used.
The react~nt~ will be delivered ~imlllt~neously to each region on the ~ul sll~te using an inkjet di~ren~pr having three nO771~S. The first nozzle is connected to a .~s~v~Jir ~,.l~ini.~ a lM solution of ZnO in water. To gen~dte an array of 16 different phnsphors, the reactant amounts set forth in Table VI, infra, are delivered to the 16 pre~lefinPA~ regions on the substrate. The synthesis reaction is carried out under a ni~vgt;n atmosphere for a period of 2 hrs. at 1400C. Once formed, each of the 16 pre~lPfin~d reaction regions is screened for electroluminescent m~tPri~ or phosphors by r~ *n~ the sample with a sperific excitation wavelength and recording the emission spectra with a Perkin-Elmer LS50 spectrofluorimeter.
W 096/11878 PCTrUS95/13278 ~ABLE VI. VARIOUS REACTANT COMPONENTS USED TO GENERATE AN
ARRAY 0~ ZINC SIL~rCATE PHOSPHORS
Reaction Region SiO2 MnCO3 ZnO
(picoliters) 2 15a0 1350 150 3 15C~ 1275 225 4 15~0 1200 300
6 15~0 1050 450
7 15a0 975 525
8 1500 900 600
9 2000 950 50 1. Svnthesis of An Array of Copper Oxide Thin-Film Materials Usin~
Sputtering ~echniques 7n Combination With Photolitho~raphy Masking 25Techniques This example ill~lctr~tPs, the possible synthesis and screening of an array of copper oxide m~ttori~l.c. The re~t~nt~ are delivered to a 1.25 cm x 1.25 cm MgO
substrate having 256 predefined regions thereon. One side of the MgO substrate has a 30 rough side, while the other side is finely polished (1 micron diamond paste). An extremely clean and smooth surface is needed for good adhesion of the sputtered metal oxide layers. The re~ct~nt~ are delivered to the substrate in the form of thin-films using a ~ e~ system in combination with photolithography techniques, i.e., a p~ttPrnPd W O96/11878 PCTrUS95/13278 photoresist serves as the physical mask. The pattern of the photoresist detPrminPs where ~ulLel~ d m~t~ri~l iS deposited and where it will be lifted off.
Starting with a clean, finely polished substrate, the first step is to spin on the photoresist. Shipley 1400-31 is used as the photoresist because it has good heat resistant r~h~ tPri~ti~ s, i.e., it remains soluble after e~o~u,t: to te~ -.es of about 100C. The photoresist is deposited in two layers for a total t~i~knP~s of 3 microns.
The photoresist is applied to the substrate from a dropper bottle, and the s.lbsL dLe is spun at 600 rpm for 30 sec. Once the first photoresist layer is deposited, it is soft-baked at 90C for 15 min. Thel~Ler, the substrate is cooled, the second photoresist layer is deposited and then soft-baked at 90C for 5 min. The substrate is cooled and then immPrs~Pd in chlorobenzene for 10 min. Chlorobenzene modifies the surface of theresist, thereby removing the low-molecular-weight resin. As such, after tre~tmPnt with chlorobe~7~mP, the surface of the photoresist has a lower solubility in the developer than the underlying regions. In conjunction with back scattering of light at the photoresist-substrate interf~ce and the differential photoresist development rates, an overhang is created in the photoresist. This creates a discontinuity of the photoresist layer and L~lc~vc~ls enc~ps~ tion of the photoresist by thin metal layers.
Once the photoresist has been deposited, the substrate is ready to be exposed. A mask is s~lpctp~ based on the desired location of the first layer. The photoresist is exposed on a Canon Fine Pattern Projection Mask Aligner (FPA-141F).
The first layer of a 256 library contains 128 sites, each of the sites being 100 microns x 100 microns, with a 50 microns list~nce between sites. After exposure, the photoresist is developed in a micro~osi~ developer for 45 seconds and then rinsed in water for 1 min.
The substrate is now ready for deposition of the first layer. 300 A of BiO3 is s~uLL~l~d onto the substrate. Normally, the s~uueling temperature can exceed the limits of the photoresist. It is found, however, that with a low-power ~7~ . ing (150 watts) gun and a target substrate ~ t~nce of 10 cm, substrate heating has not been a problem, even for deposition periods lasting as long as 8 hours. A cooling block should be available in case the substrate temperature exceeded 100C.
The liftoff process is achieved by placing the substrate in an ultrasonic bath of acetone. The metal adheres at sites where the photoresist had been removed as a result of prior eA~JOSUlC~ and development, whereas the metal is lifted off where the resist W O96/11878 PCTrUS95/13278 rem~in~ after p~ . The acetone readily dissolves the photoresist and, thus, the metal peels off. The subsequent col.lpollent layers are deposited on the substrate in the same manner, except the next layer must be aligned to the first, and the sites at which the metal is to be deposited are ch~ng~d. In this example, the next layer is CuO, then 5 SrCO3 and then CaO.
Once the col--ponents o~F interest are delivered to the 256 pre~Pfin~l regions on the substrate, the substrate is placed in a furnace, and the co-ll~nents are subsequently reacted. Once reacted, each of the 256 pre~lefin~d regions can be screened for re~i~t~n~e using, for example, a 4-point contact probe.
XI. Conc~ iQn:
The present invention provides greatly improved m~tho~s and apparatus for the parallel deposition, synthesis and screening of an array of m7~t~ ri~1~ on a single substrate. It is to be understood that the above description is int~n-l~A to be illll~tr~tive 15 and not restrictive. Many embo~limpnt~ and variations of the invention will become a~arellt to those of skill in the art upon review of this disclosure. Merely by way of eY~mI~le a wide variety of process times, reaction temperatures and other reaction conditions may be utili7~d, as well as a different ordering of cert~in pr~s~in~ steps.
The scope of the invention should, therefore, be determined not with reference to the 20 above description, but instead should be determined with reference to the appended claims along with the full scope of equivalents to which such claims are entitl~d.
Sputtering ~echniques 7n Combination With Photolitho~raphy Masking 25Techniques This example ill~lctr~tPs, the possible synthesis and screening of an array of copper oxide m~ttori~l.c. The re~t~nt~ are delivered to a 1.25 cm x 1.25 cm MgO
substrate having 256 predefined regions thereon. One side of the MgO substrate has a 30 rough side, while the other side is finely polished (1 micron diamond paste). An extremely clean and smooth surface is needed for good adhesion of the sputtered metal oxide layers. The re~ct~nt~ are delivered to the substrate in the form of thin-films using a ~ e~ system in combination with photolithography techniques, i.e., a p~ttPrnPd W O96/11878 PCTrUS95/13278 photoresist serves as the physical mask. The pattern of the photoresist detPrminPs where ~ulLel~ d m~t~ri~l iS deposited and where it will be lifted off.
Starting with a clean, finely polished substrate, the first step is to spin on the photoresist. Shipley 1400-31 is used as the photoresist because it has good heat resistant r~h~ tPri~ti~ s, i.e., it remains soluble after e~o~u,t: to te~ -.es of about 100C. The photoresist is deposited in two layers for a total t~i~knP~s of 3 microns.
The photoresist is applied to the substrate from a dropper bottle, and the s.lbsL dLe is spun at 600 rpm for 30 sec. Once the first photoresist layer is deposited, it is soft-baked at 90C for 15 min. Thel~Ler, the substrate is cooled, the second photoresist layer is deposited and then soft-baked at 90C for 5 min. The substrate is cooled and then immPrs~Pd in chlorobenzene for 10 min. Chlorobenzene modifies the surface of theresist, thereby removing the low-molecular-weight resin. As such, after tre~tmPnt with chlorobe~7~mP, the surface of the photoresist has a lower solubility in the developer than the underlying regions. In conjunction with back scattering of light at the photoresist-substrate interf~ce and the differential photoresist development rates, an overhang is created in the photoresist. This creates a discontinuity of the photoresist layer and L~lc~vc~ls enc~ps~ tion of the photoresist by thin metal layers.
Once the photoresist has been deposited, the substrate is ready to be exposed. A mask is s~lpctp~ based on the desired location of the first layer. The photoresist is exposed on a Canon Fine Pattern Projection Mask Aligner (FPA-141F).
The first layer of a 256 library contains 128 sites, each of the sites being 100 microns x 100 microns, with a 50 microns list~nce between sites. After exposure, the photoresist is developed in a micro~osi~ developer for 45 seconds and then rinsed in water for 1 min.
The substrate is now ready for deposition of the first layer. 300 A of BiO3 is s~uLL~l~d onto the substrate. Normally, the s~uueling temperature can exceed the limits of the photoresist. It is found, however, that with a low-power ~7~ . ing (150 watts) gun and a target substrate ~ t~nce of 10 cm, substrate heating has not been a problem, even for deposition periods lasting as long as 8 hours. A cooling block should be available in case the substrate temperature exceeded 100C.
The liftoff process is achieved by placing the substrate in an ultrasonic bath of acetone. The metal adheres at sites where the photoresist had been removed as a result of prior eA~JOSUlC~ and development, whereas the metal is lifted off where the resist W O96/11878 PCTrUS95/13278 rem~in~ after p~ . The acetone readily dissolves the photoresist and, thus, the metal peels off. The subsequent col.lpollent layers are deposited on the substrate in the same manner, except the next layer must be aligned to the first, and the sites at which the metal is to be deposited are ch~ng~d. In this example, the next layer is CuO, then 5 SrCO3 and then CaO.
Once the col--ponents o~F interest are delivered to the 256 pre~Pfin~l regions on the substrate, the substrate is placed in a furnace, and the co-ll~nents are subsequently reacted. Once reacted, each of the 256 pre~lefin~d regions can be screened for re~i~t~n~e using, for example, a 4-point contact probe.
XI. Conc~ iQn:
The present invention provides greatly improved m~tho~s and apparatus for the parallel deposition, synthesis and screening of an array of m7~t~ ri~1~ on a single substrate. It is to be understood that the above description is int~n-l~A to be illll~tr~tive 15 and not restrictive. Many embo~limpnt~ and variations of the invention will become a~arellt to those of skill in the art upon review of this disclosure. Merely by way of eY~mI~le a wide variety of process times, reaction temperatures and other reaction conditions may be utili7~d, as well as a different ordering of cert~in pr~s~in~ steps.
The scope of the invention should, therefore, be determined not with reference to the 20 above description, but instead should be determined with reference to the appended claims along with the full scope of equivalents to which such claims are entitl~d.
Claims (105)
1. A giant magnetoresistive (GMR) cobalt oxide compound, said GMR cobalt oxide compound having the formula:
Ay(1-x)MyxCoOz wherein:
A is a metal selected from the group consisting of lanthanum (La), yttrium (Y), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yp) and lutecium (Lu);
M is a metal selected from the group consisting of calcium (Ca), strontium (Sr), barium (Ba), lead (Pb) and cadmium (Cd);
y has a value ranging from about 1 to about 2;
x has a value ranging from about 0.1 to about 0.9; and z has a value ranging from about 2 to about 4.
Ay(1-x)MyxCoOz wherein:
A is a metal selected from the group consisting of lanthanum (La), yttrium (Y), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yp) and lutecium (Lu);
M is a metal selected from the group consisting of calcium (Ca), strontium (Sr), barium (Ba), lead (Pb) and cadmium (Cd);
y has a value ranging from about 1 to about 2;
x has a value ranging from about 0.1 to about 0.9; and z has a value ranging from about 2 to about 4.
2. The GMR cobalt oxide compound of claim 1 wherein x has a value ranging from about 0.2 to about 0.7.
3. The GMR cobalt oxide compound of claim 1 wherein x has a value ranging from about 0.3 to about 0.5.
4. The GMR cobalt oxide compound of claim 1 wherein said compound has a layered, perovskite-related structure.
5. A giant magnetoresistive (GMR) cobalt oxide compound, said GMR cobalt oxide compound having the formula:
A1-xMxCoOz wherein:
A is a metal selected from the group consisting of lanthanum (La), yttrium (Y), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yp) and lutecium (Lu);
M is a metal selected from the group consisting of calcium (Ca), strontium (Sr), barium (Ba), lead (Pb) and cadmiun (Cd);
x has a value ranging from about 0.1 to about 0.9; and z has a value ranging from about 2 to about 4.
A1-xMxCoOz wherein:
A is a metal selected from the group consisting of lanthanum (La), yttrium (Y), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yp) and lutecium (Lu);
M is a metal selected from the group consisting of calcium (Ca), strontium (Sr), barium (Ba), lead (Pb) and cadmiun (Cd);
x has a value ranging from about 0.1 to about 0.9; and z has a value ranging from about 2 to about 4.
6. The GMR cobalt oxide compound of claim 5 wherein x has a value ranging from about 0.2 to about 0.7.
7. The GMR cobalt oxide compound of claim 5 wherein x has a value ranging from about 0.3 to about 0.5.
8. The GMR cobalt oxide compound of claim 5 wherein said compound has a layered, perovskite-related structure.
9. The GMR cobalt oxide compound of claim 5 wherein said compound has the formula:
La1-xMxCoOz wherein:
M is a metal selected from the group consisting of barium, calcium and strontium;
x has a value ranging from about 0.1 to about 0.9; and z has a value ranging from about 2 to about 4.
La1-xMxCoOz wherein:
M is a metal selected from the group consisting of barium, calcium and strontium;
x has a value ranging from about 0.1 to about 0.9; and z has a value ranging from about 2 to about 4.
10. The GMR cobalt oxide compound of claim 9 wherein M is barium.
11. The GMR cobalt oxide compound of claim 9 wherein M is calcium.
12. The GMR cobalt oxide compound of claim 9 wherein M is strontium,
13. A method of making an array of materials, said method comprising:
(a) delivering a first component of a first material and a first component of a second material to first and second regions on a substrate;
(b) delivering a second component of said first material and a second component of said second material to said first and second regions on said substrate; and (c) simultaneously reacting said components to form at least two materials.
(a) delivering a first component of a first material and a first component of a second material to first and second regions on a substrate;
(b) delivering a second component of said first material and a second component of said second material to said first and second regions on said substrate; and (c) simultaneously reacting said components to form at least two materials.
14. The method as recited in claim 13 wherein said materials are covalent network solids.
15. The method as recited in claim 13 wherein said materials are ionic solids.
16. The method as recited in claim 13 wherein said materials are molecular solids.
17. The method as recited in claim 13 wherein said materials are inorganic materials.
18. The method as recited in claim 17 wherein said inorganic materials are intermetallic materials.
19. The method as recited in claim 17 wherein said inorganic materials are metal alloys.
20. The method as recited in claim 17 wherein said inorganic materials are ceramic materials.
21. The method as recited in claim 13 wherein said materials are organometallic materials.
22. The method as recited in claim 13 wherein said materials are composite materials.
23. The method as recited in claim 13 wherein said materials are non-biological organic polymers.
24. The method as recited in claim 13 wherein said first component of said first material and said second component of said first material are simultaneously delivered to said first region.
25. The method as recited in claim 13 wherein said first component of said first material and said first component of said second material are simultaneously delivered to said first region and said second region, respectively.
26. The method as recited in claim 13 wherein said first component of said first material and said first component of said second material are the same, but are offered in different amounts.
27. The method as recited in claim 13 wherein said second component of said first material and said second component of said second material are the same, but are offered in different amounts.
28. The method as recited in claim 13 wherein said first component of said first material is delivered to said first region in a gradient of stoichiometries.
29. The method as recited in claim 13 wherein said first component of said first material and said first component of said second material are the same, but are offered to said first and second regions on said substrate in a gradient of stoichiomeritries.
30. The method as recited in claim 13 wherein the components of said materials are delivered to said first and second regions on said substrate from a pipette.
31. The method as recited in claim 13 wherein the components of said materials are delivered to said first and second regions on said substrate from an ink-jet dispenser.
32. The method as recited in claim 31 wherein said ink-jet dispenser is selected from the group consisting of a pulse pressure ink-jet dispenser, a bubble jet ink-jet dispenser and a slit jet ink-jet dispenser.
33. The method as recited in claim 13 wherein said steps of delivering said components each comprises the following steps:
(i) identifying a reference point on said substrate;
(ii) moving a dispenser of said component a fixed distance and direction from said reference point such that said dispenser is positioned approximately above said first region on said substrate;
(iii) delivering said component to said first region; and (iv) repeating steps (ii) and (iii) for each remaining component for each remaining region.
(i) identifying a reference point on said substrate;
(ii) moving a dispenser of said component a fixed distance and direction from said reference point such that said dispenser is positioned approximately above said first region on said substrate;
(iii) delivering said component to said first region; and (iv) repeating steps (ii) and (iii) for each remaining component for each remaining region.
34. The method as recited in claim 13 wherein said step of delivering said first component of said first material to said first region on said substrate comprises the steps of:
(i) placing a mask adjacent to said substrate, said mask permitting said first component of said first material to be delivered to said first region on said substrate, but not to said second region on said substrate;
(ii) delivering said first component of said first material to said first region on said substrate; and (iii) removing said mask.
(i) placing a mask adjacent to said substrate, said mask permitting said first component of said first material to be delivered to said first region on said substrate, but not to said second region on said substrate;
(ii) delivering said first component of said first material to said first region on said substrate; and (iii) removing said mask.
35. The method as recited in claim 13 wherein said step of delivering said first component of said first material to said first region on said substrate comprises the steps of:
(i) placing a mask adjacent to said substrate, said mask permitting said first component of said first material to be delivered to said first region on said substrate, but not to said second region on said substrate;
(ii) depositing a thin-film of said first component of said first material on said first region on said substrate; and iii) removing said mask.
(i) placing a mask adjacent to said substrate, said mask permitting said first component of said first material to be delivered to said first region on said substrate, but not to said second region on said substrate;
(ii) depositing a thin-film of said first component of said first material on said first region on said substrate; and iii) removing said mask.
36. The method as recited in claim 13 wherein said step of delivering said first component of said first material to said first region on said substrate comprises the steps of:
(i) placing a mask adjacent to said substrate, said mask permitting said first component of said first material to be delivered to said first region on said substrate, but not to said second region on said substrate;
(ii) spraying said first component of said first material onto said first region on said substrate; and iii) removing said mask.
(i) placing a mask adjacent to said substrate, said mask permitting said first component of said first material to be delivered to said first region on said substrate, but not to said second region on said substrate;
(ii) spraying said first component of said first material onto said first region on said substrate; and iii) removing said mask.
37. The method as recited in claim 13 wherein said step of delivering said first component of said first material to said first region on said substrate comprises the steps of:
(i) depositing a photoresist on said substrate;
(ii) selectively exposing said photoresist on said substrate;
(iii) selectively removing said photoresist from said substrate to expose said first region;
(iv) delivering said first component of said first material to said first region on said substrate; and (v) removing remaining photoresist from said substrate.
(i) depositing a photoresist on said substrate;
(ii) selectively exposing said photoresist on said substrate;
(iii) selectively removing said photoresist from said substrate to expose said first region;
(iv) delivering said first component of said first material to said first region on said substrate; and (v) removing remaining photoresist from said substrate.
38. The method as recited in claim 13 wherein said step of delivering said first component of said first material to said first region on said substrate comprises the steps of:
(i) delivering said first component of said first material to first and second regions on said substrate;
(ii) depositing a photoresist on said substrate;
(iii) selectively exposing said photoresist on said substrate;
(iv) selectively removing said photoresist from said second region on said substrate, thereby exposing said first component of said first material;
(v) etching off the exposed first component of said first material; and (vi) removing remaining photoresist from said substrate.
(i) delivering said first component of said first material to first and second regions on said substrate;
(ii) depositing a photoresist on said substrate;
(iii) selectively exposing said photoresist on said substrate;
(iv) selectively removing said photoresist from said second region on said substrate, thereby exposing said first component of said first material;
(v) etching off the exposed first component of said first material; and (vi) removing remaining photoresist from said substrate.
39. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 25 cm.
40. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 10 cm.
41. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 5 cm.
42. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 1 cm.
43. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 1 mm.
44. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 10,000 µm.
45. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 1,000 µm.
46. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 100 µm.
47. The method as recited in claim 13 wherein each of said materials is synthesized in an area of less than 1 µm.
48. The method as recited in claim 13 wherein at least 10 different materials are synthesized on said substrate.
49. The method as recited in claim 13 wherein at least 100 different materials are synthesized on said substrate.
50. The method as recited in claim 13 wherein at least 104 different materials are synthesized on said substrate.
51. The method as recited in claim 13 wherein at least 106 different materials are synthesized on said substrate.
52. The method as recited in claim 13 wherein at least 100 different materials are synthesized, and each different material is contained within an area of about 1 mm or less.
53. The method as recited in claim 13 further comprising the step of screening said array of materials for a useful property.
54. The method as recited in claim 53 wherein said useful property is an electrical property.
55. The method as recited in claim 53 wherein said useful property is a thermal property.
56. The method as recited in claim 53 wherein said useful property is a mechanical property.
57. The method as recited in claim 53 wherein said useful property is a morphological property.
58. The method as recited in claim 53 wherein said useful property is an optical property.
59. The method as recited in claim 53 wherein said useful property is a magnetic property.
60. The method as recited in claim 53 wherein said useful property is a chemical property.
61. The method as recited in claim 53 wherein said array of materials is screened in parallel.
62. The method as recited in claim 53 wherein said array of materials is screened sequentially.
63. An array of more than 10 different inorganic materials on a substrate at known locations thereon.
64. The array as recited in claim 63 wherein more than 100 different inorganic materials on a substrate at known locations thereon.
65. The array as recited in claim 63 wherein more than 10 3 different inorganic materials on a substrate at known locations thereon.
66. The array as recited in claim 63 wherein more than 10 6 different inorganic materials on a substrate at known locations thereon.
67. The array as recited in claim 63 wherein said inorganic materials are intermetallic: materials.
68. The array as recited in claim 63 wherein said inorganic materials are metal alloys.
69. The array as recited in claim 63 wherein said inorganic materials are ceramic materials.
70. The array as recited in claim 63 wherein said inorganic materials are inorganic-organic composite materials.
71. A method of making at least two different arrays of materials, said method comprising:
(a) delivering a first component of a first material to a first region on a first substrate and delivering said first component of said first material to a first region on a second substrate;
(b) delivering a first component of a second material to a second region on said first substrate and delivering said first component of said second material to a second region on said second substrate;
(c) delivering a second component of said first material to said first region on said first substrate and delivering said second component of said first material to said first region on said second substrate;
(d) delivering a second component of said second material to said second region on said first substrate and delivering said second component of said second material to said second region on said second substrate; and (e) reacting said components on said first substrate under a first set of reaction conditions and said components on said second substrate under a second set of reaction conditions to form at least two different arrays of at least two materials.
(a) delivering a first component of a first material to a first region on a first substrate and delivering said first component of said first material to a first region on a second substrate;
(b) delivering a first component of a second material to a second region on said first substrate and delivering said first component of said second material to a second region on said second substrate;
(c) delivering a second component of said first material to said first region on said first substrate and delivering said second component of said first material to said first region on said second substrate;
(d) delivering a second component of said second material to said second region on said first substrate and delivering said second component of said second material to said second region on said second substrate; and (e) reacting said components on said first substrate under a first set of reaction conditions and said components on said second substrate under a second set of reaction conditions to form at least two different arrays of at least two materials.
72. The method as recited in claim 71 wherein said materials are covalent network solids.
73. The method as recited in claim 71 wherein said materials are ionic solids
74. The method as recited in claim 71 wherein said materials are molecular solids.
75. The method as recited in claim 71 wherein said materials are inorganic materials.
76. The method as recited in claim 75 wherein said materials are intermetallic materials.
77. The method as recited in claim 75 wherein said inorganic materials are metal alloys.
78. The method as recited in claim 75 wherein said inorganic materials are ceramic materials.
79. The method as recited in claim 71 wherein said materials are organometallic materials.
80. The method as recited in claim 71 wherein said materials are composite materials.
81. The method as recited in claim 71 wherein said materials are non-biological organic polymers.
82. The method as recited in claim 71 wherein said first set of reaction conditions differs from said second set of reaction conditions in terms of the temperature at which the reactions are carried out.
83. The method as recited in claim 71 wherein said first set of reaction conditions differs from said second set of reaction conditions in terms of the pressure at which the reactions are carried out.
84. The method as recited in claim 71 wherein said first set of reaction conditions differs from said second set of reaction conditions in terms of the reaction times at which the reactions are carried out.
85. The method as recited in claim 71 wherein said first set of reaction conditions differs from said second set of reaction conditions in terms of the atmosphere in which the reactions are carried out.
86. The method as recited in claim 71 wherein said first component of said first material and said first component of said second material are the same, but are offered in different amounts.
87. A material having a useful property prepared by a process comprising the steps of:
(a) forming an array of different materials on a single substrate;
(b) screening said array for a material having said useful property; and (c) making additional amounts of said material having said useful property.
(a) forming an array of different materials on a single substrate;
(b) screening said array for a material having said useful property; and (c) making additional amounts of said material having said useful property.
88. The material as recited in claim 87 wherein step (a) of said process further comprises the steps of:
(i) delivering a first component of a first material and a first component of a second material to first and second regions on a substrate;
(ii) delivering a second component of said first material and a second component of said second material to first and second regions on said substrate; and (iii) simultaneously reacting said components to form said array of at least two different materials.
(i) delivering a first component of a first material and a first component of a second material to first and second regions on a substrate;
(ii) delivering a second component of said first material and a second component of said second material to first and second regions on said substrate; and (iii) simultaneously reacting said components to form said array of at least two different materials.
89. The material as recited in claim 88 wherein said first component of said first material and said first component of said second material are the same, but are offered in different concentrations,
90. The material as recited in claim 87 wherein said material is a covalent network solid.
91. The material as recited in claim 87 wherein said material is an ionic solids.
92. The material as recited in claim 87 wherein said material is a molecular solid.
93. The material as recited in claim 87 wherein said material is an inorganic material.
94. The material as recited in claim 93 wherein said inorganic material is an intermetallic material.
95. The material as recited in claim 93 wherein said inorganic material is a metal alloy.
96. The material as recited in claim 93 wherein said inorganic material is a ceramic material.
97. The material as recited in claim 87 wherein said material is an organometallic material.
98. The material as recited in claim 87 wherein said material is a composite material.
99. The material as recited in claim 87 wherein said material is a non-biological organic polymer.
100. The material as recited in claim 87 wherein said material is a high temperature superconductor.
101. The material as recited in claim 87 wherein said material is a magnetoresistive material.
102. The material as recited in claim 87 wherein said material is a zeolite.
103. The material as recited in claim 87 wherein said material is a phosphor.
104. The material as recited in claim 87 wherein said material is a conducting polymer.
105. The material as recited in claim 87 wherein said material is a ferro-electric material.
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Families Citing this family (570)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5605798A (en) | 1993-01-07 | 1997-02-25 | Sequenom, Inc. | DNA diagnostic based on mass spectrometry |
US6419881B1 (en) * | 1994-10-18 | 2002-07-16 | Symyx Technologies, Inc. | Combinatorial arrays of organometallic compounds and catalysts |
US5985356A (en) * | 1994-10-18 | 1999-11-16 | The Regents Of The University Of California | Combinatorial synthesis of novel materials |
US6045671A (en) * | 1994-10-18 | 2000-04-04 | Symyx Technologies, Inc. | Systems and methods for the combinatorial synthesis of novel materials |
US7767627B1 (en) * | 1994-10-18 | 2010-08-03 | Symyx Solutions, Inc. | Combinatorial synthesis of inorganic or composite materials |
US6440745B1 (en) * | 1994-10-18 | 2002-08-27 | Symyx Technologies | Combinatorial synthesis and screening of organometallic compounds and catalysts |
US6030917A (en) * | 1996-07-23 | 2000-02-29 | Symyx Technologies, Inc. | Combinatorial synthesis and analysis of organometallic compounds and catalysts |
US7166470B2 (en) | 1994-10-18 | 2007-01-23 | Symyx Technologies, Inc. | Formation of combinatorial arrays of materials using solution-based methodologies |
US5959098A (en) | 1996-04-17 | 1999-09-28 | Affymetrix, Inc. | Substrate preparation process |
CA2216645A1 (en) * | 1995-04-25 | 1996-11-21 | Irori | Remotely programmable matrices with memories and uses thereof |
US20030203390A1 (en) * | 1995-10-26 | 2003-10-30 | Kaye Paul H. | Coded particles for process sequence tracking in combinatorial compound library preparation |
US6660233B1 (en) * | 1996-01-16 | 2003-12-09 | Beckman Coulter, Inc. | Analytical biochemistry system with robotically carried bioarray |
US6063633A (en) | 1996-02-28 | 2000-05-16 | The University Of Houston | Catalyst testing process and apparatus |
AU2069597A (en) | 1996-03-04 | 1997-09-22 | Genetrace Systems, Inc. | Methods of screening nucleic acids using mass spectrometry |
US6706875B1 (en) * | 1996-04-17 | 2004-03-16 | Affyemtrix, Inc. | Substrate preparation process |
US20050009081A1 (en) * | 1996-07-23 | 2005-01-13 | Symyx Technologies, Inc. | Optical systems and methods for rapid screening of libraries of different materials |
US6441901B2 (en) | 1996-07-23 | 2002-08-27 | Symyx Technologies, Inc. | Optical systems and methods for rapid screening of libraries of different materials |
EP0985678B1 (en) * | 1996-07-23 | 2001-12-05 | Symyx Technologies (US/US) | Combinatorial synthesis and analysis of organometallic compounds and catalysts |
US6582921B2 (en) * | 1996-07-29 | 2003-06-24 | Nanosphere, Inc. | Nanoparticles having oligonucleotides attached thereto and uses thereof |
US5965363A (en) | 1996-09-19 | 1999-10-12 | Genetrace Systems Inc. | Methods of preparing nucleic acids for mass spectrometric analysis |
US6468806B1 (en) | 1996-10-02 | 2002-10-22 | Symyx Technologies, Inc. | Potential masking systems and methods for combinatorial library synthesis |
US6720186B1 (en) | 1998-04-03 | 2004-04-13 | Symyx Technologies, Inc. | Method of research for creating and testing novel catalysts, reactions and polymers |
ATE319988T1 (en) * | 1996-10-09 | 2006-03-15 | Symyx Technologies Inc | INFRARED SPECTROSCOPY AND LIBRARY IMAGING |
US6536944B1 (en) * | 1996-10-09 | 2003-03-25 | Symyx Technologies, Inc. | Parallel screen for rapid thermal characterization of materials |
US6738529B1 (en) | 1996-10-09 | 2004-05-18 | Symyx Technologies, Inc. | Analysis of chemical data from images |
US6024925A (en) * | 1997-01-23 | 2000-02-15 | Sequenom, Inc. | Systems and methods for preparing low volume analyte array elements |
US7285422B1 (en) | 1997-01-23 | 2007-10-23 | Sequenom, Inc. | Systems and methods for preparing and analyzing low volume analyte array elements |
ATE259056T1 (en) | 1996-11-06 | 2004-02-15 | Sequenom Inc | METHOD FOR MASS SPECTROMETRY |
US6713173B2 (en) * | 1996-11-16 | 2004-03-30 | Nanomagnetics Limited | Magnetizable device |
US20060003163A1 (en) * | 1996-11-16 | 2006-01-05 | Nanomagnetics Limited | Magnetic fluid |
AU5794498A (en) | 1996-12-10 | 1998-07-03 | Genetrace Systems, Inc. | Releasable nonvolatile mass-label molecules |
NO304355B1 (en) | 1997-02-20 | 1998-12-07 | Sinvent As | Multi-autoclave for methodical, automated synthesis of zeolites and other compounds |
AU6704398A (en) * | 1997-03-19 | 1998-10-12 | Biosepra Inc. | Multifunctional ceramic particles as solid supports for solid phase and com binatorial solid phase synthesis |
AU7801698A (en) * | 1997-06-09 | 1998-12-30 | Symyx Technologies, Inc. | Delivery and scavenging agents for combinatorial synthesis |
NZ516848A (en) * | 1997-06-20 | 2004-03-26 | Ciphergen Biosystems Inc | Retentate chromatography apparatus with applications in biology and medicine |
CA2294173C (en) * | 1997-06-30 | 2007-08-14 | Nathan S. Lewis | Compositionally different polymer-based sensor elements and methods for preparing same |
US6151123A (en) * | 1997-07-14 | 2000-11-21 | Symyx Technologies, Inc. | Systems and methods for employing optical probes to characterize material properties |
US7112449B1 (en) * | 2000-04-05 | 2006-09-26 | Nanogram Corporation | Combinatorial chemical synthesis |
WO1999005318A1 (en) * | 1997-07-22 | 1999-02-04 | Symyx Technologies | Encoding of organometallic libraries |
US6576906B1 (en) * | 1999-10-08 | 2003-06-10 | Symyx Technologies, Inc. | Method and apparatus for screening combinatorial libraries for semiconducting properties |
ATE235682T1 (en) * | 1997-09-11 | 2003-04-15 | Bioventures Inc | METHOD FOR CREATING HIGH DENSITY ARRAYS |
US20030180441A1 (en) * | 1997-09-30 | 2003-09-25 | Hitoshi Fukushima | Manufacture of a microsensor device and a method for evaluating the function of a liquid by the use thereof |
US20030104481A1 (en) * | 1997-09-30 | 2003-06-05 | Symyx Technologies | Potential masking systems and methods for combinatorial library synthesis |
US20030170913A1 (en) * | 1997-09-30 | 2003-09-11 | Hitoshi Fukushima | Manufacture of a microsensor device and a method for evaluating the function of a liquid by the use thereof |
US6818110B1 (en) | 1997-09-30 | 2004-11-16 | Symyx Technologies, Inc. | Combinatorial electrochemical deposition and testing system |
US6393895B1 (en) | 1997-10-08 | 2002-05-28 | Symyx Technologies, Inc. | Method and apparatus for characterizing materials by using a mechanical resonator |
US6494079B1 (en) * | 2001-03-07 | 2002-12-17 | Symyx Technologies, Inc. | Method and apparatus for characterizing materials by using a mechanical resonator |
US6426226B1 (en) * | 1997-10-10 | 2002-07-30 | Laboratory Catalyst Systems Llc | Method and apparatus for screening catalyst libraries |
CA2316188C (en) * | 1997-12-23 | 2005-02-15 | Studiengesellschaft Kohle Mbh | Method for combinatorial material development using differential thermal images |
JPH11189874A (en) * | 1997-12-25 | 1999-07-13 | Tdk Corp | Formation of thin film and device therefor |
US6893877B2 (en) | 1998-01-12 | 2005-05-17 | Massachusetts Institute Of Technology | Methods for screening substances in a microwell array |
JP4503828B2 (en) | 1998-02-11 | 2010-07-14 | ユニバーシティー オブ ヒューストン | Method and apparatus for chemical and biochemical reactions using photogenerating reagents |
US6087181A (en) * | 1998-03-16 | 2000-07-11 | Symyx Technologies | Sampling and detection of trace gas species by optical spectroscopy |
EP1065001B1 (en) * | 1998-03-19 | 2008-09-24 | Precision System Science Co., Ltd. | Apparatus for integrating processing of magnetic particles, and method of controlling the same |
US6866786B2 (en) * | 1998-04-03 | 2005-03-15 | Symyx Technologies, Inc. | Rapid characterization of polymers |
US6294388B1 (en) * | 1998-04-03 | 2001-09-25 | Symyx Technologies, Inc. | Indirect calibration of polymer characterization systems |
DE19822077A1 (en) * | 1998-05-16 | 1999-11-18 | Studiengesellschaft Kohle Mbh | Preparation of library of spatially separted solids by wet-chemical methods on a removable reaction plate, used e.g. to screen for new catalysts or materials |
US6149882A (en) * | 1998-06-09 | 2000-11-21 | Symyx Technologies, Inc. | Parallel fixed bed reactor and fluid contacting apparatus |
ATE423314T1 (en) | 1998-06-24 | 2009-03-15 | Illumina Inc | DECODING OF MATRIXED SENSORS BY MICROPARTICLES |
US6063436A (en) * | 1998-07-10 | 2000-05-16 | Litton Systems, Inc. | Use of multiple masks to control uniformity in coating deposition |
US6528026B2 (en) | 1998-08-13 | 2003-03-04 | Symyx Technologies, Inc. | Multi-temperature modular reactor and method of using same |
US6913934B2 (en) * | 1998-08-13 | 2005-07-05 | Symyx Technologies, Inc. | Apparatus and methods for parallel processing of multiple reaction mixtures |
US6455316B1 (en) | 1998-08-13 | 2002-09-24 | Symyx Technologies, Inc. | Parallel reactor with internal sensing and method of using same |
US6548026B1 (en) | 1998-08-13 | 2003-04-15 | Symyx Technologies, Inc. | Parallel reactor with internal sensing and method of using same |
US6306658B1 (en) | 1998-08-13 | 2001-10-23 | Symyx Technologies | Parallel reactor with internal sensing |
US6890492B1 (en) | 1998-08-13 | 2005-05-10 | Symyx Technologies, Inc. | Parallel reactor with internal sensing and method of using same |
US6759014B2 (en) * | 2001-01-26 | 2004-07-06 | Symyx Technologies, Inc. | Apparatus and methods for parallel processing of multiple reaction mixtures |
US6410332B1 (en) * | 1998-09-08 | 2002-06-25 | Symyx Technologies, Inc. | Sampling and analysis of reactions by trapping reaction components on a sorbent |
US6344084B1 (en) * | 1998-09-11 | 2002-02-05 | Japan Science And Technology Corporation | Combinatorial molecular layer epitaxy device |
WO2000017413A2 (en) * | 1998-09-18 | 2000-03-30 | Symyx Technologies | Formation of combinatorial arrays of materials using solution-based methodologies |
US6521793B1 (en) | 1998-10-08 | 2003-02-18 | Symyx Technologies, Inc. | Catalyst ligands, catalytic metal complexes and processes using same |
EP1164513A1 (en) * | 1998-10-19 | 2001-12-19 | Symyx Technologies, Inc. | Computer-implemented method for generating a library design for a combinatorial library of materials |
US7199809B1 (en) * | 1998-10-19 | 2007-04-03 | Symyx Technologies, Inc. | Graphic design of combinatorial material libraries |
US6535284B1 (en) * | 1998-10-19 | 2003-03-18 | Symyx Technologies, Inc. | Rheo-optical indexer and method of screening and characterizing arrays of materials |
JP3093184B2 (en) * | 1998-10-29 | 2000-10-03 | アプライド マテリアルズ インコーポレイテッド | Film forming method and apparatus |
US6485692B1 (en) | 1998-12-04 | 2002-11-26 | Symyx Technologies, Inc. | Continuous feed parallel reactor |
US6477479B1 (en) | 1998-12-11 | 2002-11-05 | Symyx Technologies | Sensor array for rapid materials characterization |
WO2000036410A1 (en) * | 1998-12-11 | 2000-06-22 | Symyx Technologies, Inc. | Sensor array-based system and method for rapid materials characterization |
US6438497B1 (en) | 1998-12-11 | 2002-08-20 | Symyx Technologies | Method for conducting sensor array-based rapid materials characterization |
WO2000036405A2 (en) * | 1998-12-18 | 2000-06-22 | Symyx Technologies, Inc. | Apparatus and method for characterizing libraries of different materials using x-ray scattering |
US6683446B1 (en) * | 1998-12-22 | 2004-01-27 | John Pope | Electrode array for development and testing of materials |
JP3959459B2 (en) | 1998-12-25 | 2007-08-15 | 独立行政法人産業技術総合研究所 | Catalyst performance evaluation system |
US6827979B2 (en) * | 1999-01-07 | 2004-12-07 | Northwestern University | Methods utilizing scanning probe microscope tips and products therefor or produced thereby |
US6635311B1 (en) * | 1999-01-07 | 2003-10-21 | Northwestern University | Methods utilizing scanning probe microscope tips and products therefor or products thereby |
US20020122873A1 (en) * | 2000-01-05 | 2002-09-05 | Mirkin Chad A. | Nanolithography methods and products therefor and produced thereby |
EP1164960A1 (en) * | 1999-01-13 | 2002-01-02 | LaserSight Technologies, Inc. | Profiling calibration plate |
US7491677B2 (en) * | 1999-01-15 | 2009-02-17 | Basf Catalysts Llc | Combinatorial synthesis |
US6830663B2 (en) * | 1999-01-26 | 2004-12-14 | Symyx Technologies, Inc. | Method for creating radial profiles on a substrate |
US6846460B1 (en) | 1999-01-29 | 2005-01-25 | Illumina, Inc. | Apparatus and method for separation of liquid phases of different density and for fluorous phase organic syntheses |
EP1161986A3 (en) * | 1999-02-17 | 2003-06-04 | Oxxel Oxide Electronics Technology, Inc. | Apparatus for combinatorial molecular beam epitaxy |
EP1077764A1 (en) * | 1999-02-17 | 2001-02-28 | Oxxel Oxide Electronics Technology, Inc. | Method for preparation of libraries using a combinatorial molecular beam epitaxy (combe) apparatus |
US20020042140A1 (en) * | 1999-03-03 | 2002-04-11 | Alfred Hagemeyer | Methods for analysis of heterogeneous catalysts in a multi-variable screening reactor |
US6749814B1 (en) * | 1999-03-03 | 2004-06-15 | Symyx Technologies, Inc. | Chemical processing microsystems comprising parallel flow microreactors and methods for using same |
US7150994B2 (en) * | 1999-03-03 | 2006-12-19 | Symyx Technologies, Inc. | Parallel flow process optimization reactor |
US6306578B1 (en) * | 1999-03-19 | 2001-10-23 | Genencor International, Inc. | Multi-through hole testing plate for high throughput screening |
SE513891C2 (en) * | 1999-03-22 | 2000-11-20 | Ericsson Telefon Ab L M | A magnetoresistive element and a method of producing a crystal structure |
US6689613B1 (en) | 1999-03-31 | 2004-02-10 | General Electric Company | Method for preparing and screening catalysts |
US6518218B1 (en) * | 1999-03-31 | 2003-02-11 | General Electric Company | Catalyst system for producing carbon fibrils |
US6855258B2 (en) * | 1999-04-02 | 2005-02-15 | Symyx Technologies, Inc. | Methods for characterization of polymers using multi-dimensional liquid chromatography with parallel second-dimension sampling |
US20020164812A1 (en) * | 1999-04-06 | 2002-11-07 | Uab Research Foundation | Method for screening crystallization conditions in solution crystal growth |
US7214540B2 (en) | 1999-04-06 | 2007-05-08 | Uab Research Foundation | Method for screening crystallization conditions in solution crystal growth |
US7250305B2 (en) | 2001-07-30 | 2007-07-31 | Uab Research Foundation | Use of dye to distinguish salt and protein crystals under microcrystallization conditions |
US7244396B2 (en) | 1999-04-06 | 2007-07-17 | Uab Research Foundation | Method for preparation of microarrays for screening of crystal growth conditions |
US7247490B2 (en) | 1999-04-06 | 2007-07-24 | Uab Research Foundation | Method for screening crystallization conditions in solution crystal growth |
US6511849B1 (en) * | 1999-04-23 | 2003-01-28 | The Sir Mortimer B. Davis - Jewish General Hospital | Microarrays of biological materials |
US6507945B1 (en) * | 1999-05-05 | 2003-01-14 | Symyx Technologies, Inc. | Synthesizing combinatorial libraries of materials |
DE60000583T3 (en) * | 1999-05-19 | 2009-04-30 | Eppendorf Array Technologies | METHOD FOR IDENTIFYING AND / OR QUANTIFYING A TARGET LINK |
US20030096321A1 (en) * | 1999-05-19 | 2003-05-22 | Jose Remacle | Method for the identification and/or the quantification of a target compound obtained from a biological sample upon chips |
US6573369B2 (en) | 1999-05-21 | 2003-06-03 | Bioforce Nanosciences, Inc. | Method and apparatus for solid state molecular analysis |
US20020042081A1 (en) * | 2000-10-10 | 2002-04-11 | Eric Henderson | Evaluating binding affinities by force stratification and force panning |
US20030073250A1 (en) * | 1999-05-21 | 2003-04-17 | Eric Henderson | Method and apparatus for solid state molecular analysis |
US20030186311A1 (en) * | 1999-05-21 | 2003-10-02 | Bioforce Nanosciences, Inc. | Parallel analysis of molecular interactions |
US6468410B1 (en) | 1999-06-14 | 2002-10-22 | Eveready Battery Company, Inc. | Method for synthesis and characterization of electrode materials |
US6630006B2 (en) * | 1999-06-18 | 2003-10-07 | The Regents Of The University Of California | Method for screening microcrystallizations for crystal formation |
TW512543B (en) * | 1999-06-28 | 2002-12-01 | Semiconductor Energy Lab | Method of manufacturing an electro-optical device |
NO312921B1 (en) | 1999-07-05 | 2002-07-15 | Sinvent As | Multitest compilation for evaluation, detection and monitoring of processes at elevated pressure |
US6770482B1 (en) * | 1999-07-16 | 2004-08-03 | General Electric | Method and apparatus for rapid screening of multiphase reactions |
US6572828B1 (en) | 1999-07-16 | 2003-06-03 | General Electric Company | Method and apparatus for high-throughput chemical screening |
US6307004B1 (en) | 1999-09-20 | 2001-10-23 | General Electric Company | Method for parallel melt-polymerization |
US20040209376A1 (en) * | 1999-10-01 | 2004-10-21 | Surromed, Inc. | Assemblies of differentiable segmented particles |
US7225082B1 (en) | 1999-10-01 | 2007-05-29 | Oxonica, Inc. | Colloidal rod particles as nanobar codes |
US20040178076A1 (en) * | 1999-10-01 | 2004-09-16 | Stonas Walter J. | Method of manufacture of colloidal rod particles as nanobarcodes |
US20050032226A1 (en) * | 1999-10-01 | 2005-02-10 | Natan Michael J. | Encoded nanoparticles in paper manufacture |
US6919009B2 (en) * | 1999-10-01 | 2005-07-19 | Nanoplex Technologies, Inc. | Method of manufacture of colloidal rod particles as nanobarcodes |
MXPA02003284A (en) * | 1999-10-01 | 2002-10-04 | Surromed Inc | Method of manufacture of colloidal rod particles as nanobar codes. |
US7045049B1 (en) * | 1999-10-01 | 2006-05-16 | Nanoplex Technologies, Inc. | Method of manufacture of colloidal rod particles as nanobar codes |
TW468283B (en) | 1999-10-12 | 2001-12-11 | Semiconductor Energy Lab | EL display device and a method of manufacturing the same |
TW471011B (en) | 1999-10-13 | 2002-01-01 | Semiconductor Energy Lab | Thin film forming apparatus |
WO2001032320A1 (en) * | 1999-10-29 | 2001-05-10 | Avery Dennison Corporation | An improved combinatorial testing method and apparatus for coat material formulations and methods |
US7094607B1 (en) | 1999-10-29 | 2006-08-22 | Avery Dennison Corporation | Apparatus for high-throughput production of coat material arrays, and analytical methods using such arrays |
US20030134033A1 (en) * | 1999-10-29 | 2003-07-17 | Avery Dennison Corporation | Combinatorial screening/testing apparatus and method |
US7448258B2 (en) * | 1999-10-29 | 2008-11-11 | Avery Dennison Corporation | High throughput screening for moisture barrier characteristics of materials |
US6602714B1 (en) | 1999-11-09 | 2003-08-05 | Sri International | Viscosity and mass sensor for the high-throughput synthesis, screening and characterization of combinatorial libraries |
US7033840B1 (en) | 1999-11-09 | 2006-04-25 | Sri International | Reaction calorimeter and differential scanning calorimeter for the high-throughput synthesis, screening and characterization of combinatorial libraries |
DE19955789A1 (en) * | 1999-11-19 | 2001-05-23 | Basf Ag | Process for combinatorial production of a library of materials |
DE19959973A1 (en) | 1999-12-13 | 2001-06-21 | Basf Ag | Process for combinatorial production and testing of heterogeneous catalysts |
DE19959974A1 (en) | 1999-12-13 | 2001-06-21 | Basf Ag | Process for the production of material libraries by electrochemical deposition |
US6770245B2 (en) | 1999-12-15 | 2004-08-03 | Uop Llc | Multiple parallel processing assembly |
US6368865B1 (en) | 1999-12-15 | 2002-04-09 | Uop Llc | Combinatorial process for performing catalytic chemical reactions |
US6627445B1 (en) | 1999-12-15 | 2003-09-30 | Uop Llc | Process for simultaneously evaluating a plurality of catalysts |
US6342185B1 (en) | 1999-12-15 | 2002-01-29 | Uop Llc | Combinatorial catalytic reactor |
US6576196B1 (en) | 1999-12-15 | 2003-06-10 | Uop Llc | Multiple parallel catalytic reactor assembly |
US6776963B1 (en) | 1999-12-15 | 2004-08-17 | Uop Llc | Multiple parallel catalytic reactor assembly |
US20050118637A9 (en) * | 2000-01-07 | 2005-06-02 | Levinson Douglas A. | Method and system for planning, performing, and assessing high-throughput screening of multicomponent chemical compositions and solid forms of compounds |
US20050095696A9 (en) * | 2000-01-07 | 2005-05-05 | Lemmo Anthony V. | Apparatus and method for high-throughput preparation and characterization of compositions |
US20070020662A1 (en) * | 2000-01-07 | 2007-01-25 | Transform Pharmaceuticals, Inc. | Computerized control of high-throughput experimental processing and digital analysis of comparative samples for a compound of interest |
IL150524A0 (en) * | 2000-01-07 | 2003-02-12 | Transform Pharmaceuticals Inc | High-throughput formation, identification, and analysis of diverse solid-forms |
US20040252299A9 (en) * | 2000-01-07 | 2004-12-16 | Lemmo Anthony V. | Apparatus and method for high-throughput preparation and spectroscopic classification and characterization of compositions |
US20050089923A9 (en) * | 2000-01-07 | 2005-04-28 | Levinson Douglas A. | Method and system for planning, performing, and assessing high-throughput screening of multicomponent chemical compositions and solid forms of compounds |
US7108970B2 (en) * | 2000-01-07 | 2006-09-19 | Transform Pharmaceuticals, Inc. | Rapid identification of conditions, compounds, or compositions that inhibit, prevent, induce, modify, or reverse transitions of physical state |
US20070021929A1 (en) * | 2000-01-07 | 2007-01-25 | Transform Pharmaceuticals, Inc. | Computing methods for control of high-throughput experimental processing, digital analysis, and re-arraying comparative samples in computer-designed arrays |
EP1255690B1 (en) * | 2000-01-31 | 2004-09-29 | DiagnoSwiss S.A. | Method for fabricating micro-structures with various surface properties in multilayer body by plasma etching |
TW495808B (en) * | 2000-02-04 | 2002-07-21 | Semiconductor Energy Lab | Thin film formation apparatus and method of manufacturing self-light-emitting device using thin film formation apparatus |
US20020013224A1 (en) * | 2000-02-08 | 2002-01-31 | Diamond Gary M. | Catalysts, metal complexes, compositions and arrays containing erbium |
US6693033B2 (en) | 2000-02-10 | 2004-02-17 | Motorola, Inc. | Method of removing an amorphous oxide from a monocrystalline surface |
US20020151040A1 (en) | 2000-02-18 | 2002-10-17 | Matthew O' Keefe | Apparatus and methods for parallel processing of microvolume liquid reactions |
US6627571B1 (en) | 2000-03-01 | 2003-09-30 | Symyx Technologies, Inc. | Method and system for the situ synthesis of a combinatorial library of supported catalyst materials |
DE60108482T2 (en) | 2000-03-07 | 2006-02-16 | Symyx Technologies, Inc., Santa Clara | PROCESS OPTIMIZING REACTOR WITH PARALLEL FLOW |
US6897015B2 (en) * | 2000-03-07 | 2005-05-24 | Bioforce Nanosciences, Inc. | Device and method of use for detection and characterization of pathogens and biological materials |
US6491759B1 (en) | 2000-03-14 | 2002-12-10 | Neocera, Inc. | Combinatorial synthesis system |
DE10012962B4 (en) * | 2000-03-16 | 2005-08-04 | Peter Prof. Dr. Bäuerle | Process for the parallel synthesis of at least two coumarin derivatives and substituted coumarin derivatives and Arylboronsäurepropandiolester |
DE10012847A1 (en) | 2000-03-16 | 2001-09-27 | Hte Gmbh | Combinatorial properties inspection method for building blocks of material libraries, e.g. catalyst, involves measuring different parameters of two building blocks by infrared thermography and mass spectrometry |
US7216113B1 (en) * | 2000-03-24 | 2007-05-08 | Symyx Technologies, Inc. | Remote Execution of Materials Library Designs |
GB0008563D0 (en) * | 2000-04-07 | 2000-05-24 | Cambridge Discovery Chemistry | Investigating different physical and/or chemical forms of materials |
US6497799B1 (en) * | 2000-04-14 | 2002-12-24 | Seagate Technology Llc | Method and apparatus for sputter deposition of multilayer films |
US6983233B1 (en) | 2000-04-19 | 2006-01-03 | Symyx Technologies, Inc. | Combinatorial parameter space experiment design |
US6911129B1 (en) | 2000-05-08 | 2005-06-28 | Intematix Corporation | Combinatorial synthesis of material chips |
CA2344946A1 (en) * | 2000-05-10 | 2001-11-10 | Symyx Technologies, Inc. | Polymer libraries on a substrate, method of forming polymer libraries on a substrate and characterization methods with same |
TWI220927B (en) * | 2000-05-12 | 2004-09-11 | Rong-Seng Chang | Method for producing a micro-carrier |
US6562411B2 (en) | 2000-05-24 | 2003-05-13 | Agfa-Gevaert | Combinatorial coating for developing novel materials |
US6393898B1 (en) | 2000-05-25 | 2002-05-28 | Symyx Technologies, Inc. | High throughput viscometer and method of using same |
US6664067B1 (en) | 2000-05-26 | 2003-12-16 | Symyx Technologies, Inc. | Instrument for high throughput measurement of material physical properties and method of using same |
US20050048614A1 (en) * | 2000-06-13 | 2005-03-03 | Children's Medical Center Corporation | Biosynthetic oncolytic molecules and uses therefor |
ATE423221T1 (en) | 2000-06-13 | 2009-03-15 | Univ Boston | USE OF MASS-MATCHED NUCLEOTIDES IN THE ANALYSIS OF OLIGONUCLEOTIDE MIXTURES AND IN HIGH-MULTIPLEX NUCLEIC ACID SEQUENCING |
US7078164B1 (en) | 2000-06-19 | 2006-07-18 | Symyx Technologies, Inc. | High throughput screen for identifying polymerization catalysts from potential catalysts |
DE10031587A1 (en) * | 2000-06-29 | 2002-01-10 | Basf Ag | Dosing of microscale suspensions for the production of material samples in combinatorial materials research and their testing |
AU2001264987A1 (en) * | 2000-06-30 | 2002-01-14 | Motorola, Inc., A Corporation Of The State Of Delware | Hybrid semiconductor structure and device |
US20020019011A1 (en) * | 2000-07-07 | 2002-02-14 | Stockwell Brent R. | Methods for identifying combinations of entities as therapeutics |
US20040253627A1 (en) * | 2000-07-07 | 2004-12-16 | Grant Zimmermann | System and method for multidimensional evaluation of combinations of compositions |
AU2001273317A1 (en) * | 2000-07-07 | 2002-01-21 | Symyx Technologies, Inc. | Methods for analysis of heterogeneous catalysts in a multi-variable screening reactor |
DE10034893A1 (en) * | 2000-07-18 | 2002-01-31 | Basf Ag | Arrays of n aqueous polymer dispersions and m formulations of aqueous polymer dispersions |
US6555946B1 (en) | 2000-07-24 | 2003-04-29 | Motorola, Inc. | Acoustic wave device and process for forming the same |
AU2001273445A1 (en) * | 2000-07-24 | 2002-02-05 | Chevron U.S.A. Inc. | Methods for optimizing the synthesis of hydrocarbons from synthesis gas |
AU2001278915A1 (en) * | 2000-07-24 | 2002-02-05 | Chevron U.S.A. Inc. | Use of combinatorial chemistry to optimize multi-step synthesis |
US6558624B1 (en) | 2000-07-25 | 2003-05-06 | General Electric Company | Method and analytical system for rapid screening of combinatorial libraries |
US6599693B1 (en) * | 2000-07-31 | 2003-07-29 | Agilent Technologies Inc. | Array fabrication |
US6544477B1 (en) * | 2000-08-01 | 2003-04-08 | Regents Of The University Of Minnesota | Apparatus for generating a temperature gradient |
US6701774B2 (en) * | 2000-08-02 | 2004-03-09 | Symyx Technologies, Inc. | Parallel gas chromatograph with microdetector array |
US6484567B1 (en) * | 2000-08-03 | 2002-11-26 | Symyx Technologies, Inc. | Rheometer for rapidly measuring small quantity samples |
US7008769B2 (en) * | 2000-08-15 | 2006-03-07 | Bioforce Nanosciences, Inc. | Nanoscale molecular arrayer |
AU2001291769A1 (en) * | 2000-08-17 | 2002-02-25 | Basf Aktiengesellschaft | Procedure and device to develop nanodispersants |
US6864091B1 (en) | 2000-08-31 | 2005-03-08 | Symyx Technologies, Inc. | Sampling probe |
DE10131581B4 (en) * | 2000-09-12 | 2008-04-03 | Robert Bosch Gmbh | Method and device for generating and checking composite arrangements |
EP1245278A3 (en) * | 2000-09-15 | 2003-12-10 | Agfa-Gevaert | A web material having microwells for combinatorial applications |
US6420178B1 (en) * | 2000-09-20 | 2002-07-16 | General Electric Company | High throughput screening method, array assembly and system |
US6780648B1 (en) | 2000-09-20 | 2004-08-24 | General Electric Company | Method and system for selectively distributing luminescence material precursors |
US6868715B1 (en) | 2000-09-20 | 2005-03-22 | General Electric Company | Method and apparatus for rapid determination of polymer molecular weight |
US6544795B1 (en) | 2000-09-20 | 2003-04-08 | General Electric Company | Method and apparatus for rapid determination of fries rearrangement products in aromatic polycarbonate resins |
US6666541B2 (en) * | 2000-09-25 | 2003-12-23 | Picoliter Inc. | Acoustic ejection of fluids from a plurality of reservoirs |
US6612686B2 (en) | 2000-09-25 | 2003-09-02 | Picoliter Inc. | Focused acoustic energy in the preparation and screening of combinatorial libraries |
US6746104B2 (en) * | 2000-09-25 | 2004-06-08 | Picoliter Inc. | Method for generating molecular arrays on porous surfaces |
US6808934B2 (en) | 2000-09-25 | 2004-10-26 | Picoliter Inc. | High-throughput biomolecular crystallization and biomolecular crystal screening |
US20020037359A1 (en) | 2000-09-25 | 2002-03-28 | Mutz Mitchell W. | Focused acoustic energy in the preparation of peptide arrays |
ATE315957T1 (en) | 2000-09-25 | 2006-02-15 | Picoliter Inc | SOUND EXHAUST OF FLUID FROM SEVERAL CONTAINER |
US20020061258A1 (en) * | 2000-09-25 | 2002-05-23 | Mutz Mitchell W. | Focused acoustic energy in the preparation and screening of combinatorial libraries |
US7900505B2 (en) * | 2000-09-25 | 2011-03-08 | Labcyte Inc. | Acoustic assessment of fluids in a plurality of reservoirs |
US6496250B1 (en) | 2000-09-29 | 2002-12-17 | General Electric Company | Combinatorial method foe development of optical ceramics |
AU2001296460A1 (en) * | 2000-10-02 | 2002-04-15 | Surromed, Inc. | Method of manufacture of colloidal rod particles as nanobarcodes |
US6638838B1 (en) | 2000-10-02 | 2003-10-28 | Motorola, Inc. | Semiconductor structure including a partially annealed layer and method of forming the same |
WO2002029076A1 (en) * | 2000-10-03 | 2002-04-11 | Mirari Biosciences, Inc. | Methods and compositions for directed microwave chemistry |
US7348182B2 (en) * | 2000-10-03 | 2008-03-25 | Mirari Biosciences, Inc. | Directed microwave chemistry |
US20040209303A1 (en) | 2000-10-03 | 2004-10-21 | Martin Mark T. | Methods and compositions for directed microwave chemistry |
CA2425779C (en) | 2000-10-12 | 2013-08-06 | University Of Rochester | Compositions that inhibit proliferation of cancer cells |
WO2002033389A1 (en) * | 2000-10-19 | 2002-04-25 | General Electric Company | Methods for nondestructive evaluation of defects in a transparent coating |
US6541264B1 (en) | 2000-10-19 | 2003-04-01 | General Electric Company | Aromatic polycarbonate characterization |
AU2002239740A1 (en) * | 2000-10-20 | 2002-06-11 | Chad A. Mirkin | Nanolithography methods and products therefor and produced thereby |
US6482264B1 (en) | 2000-10-26 | 2002-11-19 | General Electric Company | Systems and methods for fabrication of coating libraries |
CA2426686A1 (en) | 2000-10-30 | 2002-07-18 | Sequenom, Inc. | Method and apparatus for delivery of submicroliter volumes onto a substrate |
US6567751B1 (en) | 2000-11-03 | 2003-05-20 | General Electric Company | Methods and computer system for combinatorial analysis of lighting phosphors |
US6900321B2 (en) | 2000-11-07 | 2005-05-31 | Symyx Technologies, Inc. | Substituted pyridyl amine complexes, and catalysts |
JP2002163005A (en) * | 2000-11-29 | 2002-06-07 | Nikon Corp | Method of designing control system, control system, method of regulating control system, and method for exposure |
DE10059890A1 (en) * | 2000-12-01 | 2002-06-20 | Hte Ag | Method for producing a large number of building blocks of a material library |
US6749776B2 (en) | 2000-12-04 | 2004-06-15 | General Electric Company | Method for rapid screening of emission-mix using a combinatorial chemistry approach |
WO2002048841A2 (en) | 2000-12-15 | 2002-06-20 | Symyx Technologies, Inc. | Methods and apparatus for designing high-dimensional combinatorial experiments |
US7085773B2 (en) | 2001-01-05 | 2006-08-01 | Symyx Technologies, Inc. | Laboratory database system and methods for combinatorial materials research |
US6658429B2 (en) | 2001-01-05 | 2003-12-02 | Symyx Technologies, Inc. | Laboratory database system and methods for combinatorial materials research |
US6918309B2 (en) * | 2001-01-17 | 2005-07-19 | Irm Llc | Sample deposition method and system |
US6406916B1 (en) | 2001-01-22 | 2002-06-18 | General Electric Company | Method and apparatus for rapid quantitation of a dihydric phenol |
US7250950B2 (en) * | 2001-01-29 | 2007-07-31 | Symyx Technologies, Inc. | Systems, methods and computer program products for determining parameters for chemical synthesis |
USH2193H1 (en) * | 2001-01-30 | 2007-07-03 | The United States Of America As Represented By The Secretary Of The Air Force | Method of growing homoepitaxial silicon carbide |
US6607918B2 (en) * | 2001-02-01 | 2003-08-19 | General Electric Company | Fluorescent labeling method and substrate |
JP4285632B2 (en) * | 2001-02-23 | 2009-06-24 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Compound having giant magnetoresistance and spin-polarized tunnel, method for producing and using the same |
US20020160527A1 (en) * | 2001-02-26 | 2002-10-31 | 3M Innovative Properties Company | Combinatorial library comprising pouches as packages for library members and method therefor |
US6673646B2 (en) | 2001-02-28 | 2004-01-06 | Motorola, Inc. | Growth of compound semiconductor structures on patterned oxide films and process for fabricating same |
US7118917B2 (en) * | 2001-03-07 | 2006-10-10 | Symyx Technologies, Inc. | Parallel flow reactor having improved thermal control |
US20020142304A1 (en) * | 2001-03-09 | 2002-10-03 | Anderson Daniel G. | Uses and methods of making microarrays of polymeric biomaterials |
JP3388731B2 (en) * | 2001-03-16 | 2003-03-24 | 科学技術振興事業団 | Method and apparatus for measuring thermoelectric properties of combinatorial samples |
US7731905B2 (en) * | 2001-03-26 | 2010-06-08 | Canon Kabushiki Kaisha | Process for producing probe carrier and apparatus thereof |
JP2002289614A (en) * | 2001-03-26 | 2002-10-04 | Nec Corp | Methods for evaluating dielectric film, calibrating temperature of thermal treatment equipment, and manufacturing semiconductor memory device |
US20020176927A1 (en) * | 2001-03-29 | 2002-11-28 | Kodas Toivo T. | Combinatorial synthesis of material systems |
US7514263B2 (en) | 2001-04-02 | 2009-04-07 | 3M Innovative Properties Company | Continuous process for the production of combinatorial libraries of materials |
US20020146745A1 (en) * | 2001-04-03 | 2002-10-10 | Surromed, Inc. | Methods and reagents for multiplexed analyte capture, surface array self-assembly, and analysis of complex biological samples |
US20020172620A1 (en) * | 2001-04-04 | 2002-11-21 | Potyrailo Radislav Alexandrovich | Systems and methods for rapid evaluation of chemical resistance of materials |
US6692708B2 (en) | 2001-04-05 | 2004-02-17 | Symyx Technologies, Inc. | Parallel reactor for sampling and conducting in situ flow-through reactions and a method of using same |
US7670429B2 (en) | 2001-04-05 | 2010-03-02 | The California Institute Of Technology | High throughput screening of crystallization of materials |
US20060129329A1 (en) * | 2001-04-09 | 2006-06-15 | Kobylecki Ryszard J | Investigating different physical and/or chemical forms of materials |
DE10119926A1 (en) * | 2001-04-23 | 2002-10-24 | Ernst Muenstermann | Process for optimizing the composition and/or mechanical properties of one or more layers deposited during a PVD, CVD and/or PCVD process comprises depositing layer(s) on vaporizing |
US6943036B2 (en) * | 2001-04-30 | 2005-09-13 | Agilent Technologies, Inc. | Error detection in chemical array fabrication |
DE10122491A1 (en) | 2001-05-10 | 2002-11-14 | Bayer Ag | Device and method for carrying out experiments in parallel |
US7858385B2 (en) | 2001-05-16 | 2010-12-28 | Los Alamos National Security, Llc | Method for detecting binding events using micro-X-ray fluorescence spectrometry |
WO2002099003A2 (en) * | 2001-06-06 | 2002-12-12 | Monsanto Technology Llc | Parallel reactor system and method |
WO2002099414A1 (en) | 2001-06-06 | 2002-12-12 | Symyx Technologies, Inc. | Flow detectors having mechanical oscillators, and use thereof in flow characterization systems |
WO2002102820A1 (en) | 2001-06-20 | 2002-12-27 | Nuevolution A/S | Nucleoside derivatives for library preparation |
US6709989B2 (en) | 2001-06-21 | 2004-03-23 | Motorola, Inc. | Method for fabricating a semiconductor structure including a metal oxide interface with silicon |
WO2003001179A2 (en) * | 2001-06-21 | 2003-01-03 | Virginia Tech Intellectual Properties, Inc. | Electro-optical detection device |
US6838052B2 (en) * | 2001-06-29 | 2005-01-04 | Symyx Technologies, Inc. | In-situ injection and materials screening device |
US6992321B2 (en) * | 2001-07-13 | 2006-01-31 | Motorola, Inc. | Structure and method for fabricating semiconductor structures and devices utilizing piezoelectric materials |
US20030134273A1 (en) * | 2001-07-17 | 2003-07-17 | Eric Henderson | Combined molecular binding detection through force microscopy and mass spectrometry |
JP4606660B2 (en) * | 2001-07-17 | 2011-01-05 | Sabicイノベーティブプラスチックスジャパン合同会社 | Polycarbonate production method and polycarbonate production apparatus |
US6646293B2 (en) | 2001-07-18 | 2003-11-11 | Motorola, Inc. | Structure for fabricating high electron mobility transistors utilizing the formation of complaint substrates |
US6693298B2 (en) | 2001-07-20 | 2004-02-17 | Motorola, Inc. | Structure and method for fabricating epitaxial semiconductor on insulator (SOI) structures and devices utilizing the formation of a compliant substrate for materials used to form same |
US6667196B2 (en) | 2001-07-25 | 2003-12-23 | Motorola, Inc. | Method for real-time monitoring and controlling perovskite oxide film growth and semiconductor structure formed using the method |
US6589856B2 (en) | 2001-08-06 | 2003-07-08 | Motorola, Inc. | Method and apparatus for controlling anti-phase domains in semiconductor structures and devices |
US6639249B2 (en) | 2001-08-06 | 2003-10-28 | Motorola, Inc. | Structure and method for fabrication for a solid-state lighting device |
DE10139553B4 (en) * | 2001-08-10 | 2008-04-10 | Robert Bosch Gmbh | Method for producing a material library |
WO2003014732A1 (en) | 2001-08-10 | 2003-02-20 | Symyx Technologies, Inc. | Apparatuses and methods for creating and testing pre-formulations and systems for same |
US6673667B2 (en) | 2001-08-15 | 2004-01-06 | Motorola, Inc. | Method for manufacturing a substantially integral monolithic apparatus including a plurality of semiconductor materials |
US6736017B2 (en) | 2001-08-24 | 2004-05-18 | Symyx Technologies, Inc. | High throughput mechanical rapid serial property testing of materials libraries |
US6769292B2 (en) * | 2001-08-24 | 2004-08-03 | Symyx Technologies, Inc | High throughput rheological testing of materials |
US6650102B2 (en) * | 2001-08-24 | 2003-11-18 | Symyx Technologies, Inc. | High throughput mechanical property testing of materials libraries using a piezoelectric |
US6772642B2 (en) | 2001-08-24 | 2004-08-10 | Damian A. Hajduk | High throughput mechanical property and bulge testing of materials libraries |
US6837115B2 (en) * | 2001-08-24 | 2005-01-04 | Symyx Technologies, Inc. | High throughput mechanical rapid serial property testing of materials libraries |
US6690179B2 (en) * | 2001-08-24 | 2004-02-10 | Symyx Technologies, Inc. | High throughput mechanical property testing of materials libraries using capacitance |
US6860148B2 (en) | 2001-08-24 | 2005-03-01 | Symyx Technologies, Inc. | High throughput fabric handle screening |
US6857309B2 (en) | 2001-08-24 | 2005-02-22 | Symyx Technologies, Inc. | High throughput mechanical rapid serial property testing of materials libraries |
US6730228B2 (en) * | 2001-08-28 | 2004-05-04 | Symyx Technologies, Inc. | Methods and apparatus for characterization of polymers using multi-dimensional liquid chromatography with regular second-dimension sampling |
TW573125B (en) * | 2001-08-29 | 2004-01-21 | Combinatorx Inc | A screening system for identifying drug-drug interactions and methods of use thereof |
US7404862B2 (en) * | 2001-09-04 | 2008-07-29 | The Trustees Of Princeton University | Device and method for organic vapor jet deposition |
US8535759B2 (en) * | 2001-09-04 | 2013-09-17 | The Trustees Of Princeton University | Method and apparatus for depositing material using a dynamic pressure |
US20030106492A1 (en) * | 2001-09-07 | 2003-06-12 | Douglas Levinson | Apparatus and method for high-throughput preparation, visualization and screening of compositions |
US6808685B2 (en) | 2001-09-17 | 2004-10-26 | Uop Llc | Apparatus and method for generating a plurality of isolated effluents |
US20030055587A1 (en) * | 2001-09-17 | 2003-03-20 | Symyx Technologies, Inc. | Rapid throughput surface topographical analysis |
JP2003088750A (en) * | 2001-09-19 | 2003-03-25 | National Institute Of Advanced Industrial & Technology | Production method for inorganic material |
US7042488B2 (en) | 2001-09-27 | 2006-05-09 | Fujinon Corporation | Electronic endoscope for highlighting blood vessel |
US20030068446A1 (en) * | 2001-10-02 | 2003-04-10 | Northwestern University | Protein and peptide nanoarrays |
US6758951B2 (en) | 2001-10-11 | 2004-07-06 | Symyx Technologies, Inc. | Synthesis and characterization of materials for electrochemical cells |
US6689218B2 (en) * | 2001-10-23 | 2004-02-10 | General Electric Company | Systems for the deposition and curing of coating compositions |
US6544334B1 (en) | 2001-10-23 | 2003-04-08 | General Electric Company | Systems and methods for the deposition and curing of coating compositions |
US7148683B2 (en) | 2001-10-25 | 2006-12-12 | Intematix Corporation | Detection with evanescent wave probe |
US7122689B2 (en) | 2001-11-06 | 2006-10-17 | Symyx Technologies, Inc. | Titanium substituted pyridyl amine complexes, catalysts and processes for polymerizing ethylene and stryene |
US7361310B1 (en) | 2001-11-30 | 2008-04-22 | Northwestern University | Direct write nanolithographic deposition of nucleic acids from nanoscopic tips |
US6881363B2 (en) | 2001-12-07 | 2005-04-19 | Symyx Technologies, Inc. | High throughput preparation and analysis of materials |
US20030143329A1 (en) * | 2002-01-30 | 2003-07-31 | Shchegrova Svetlana V. | Error correction in array fabrication |
US7013709B2 (en) | 2002-01-31 | 2006-03-21 | Symyx Technologies, Inc. | High throughput preparation and analysis of plastically shaped material samples |
JP2005532263A (en) | 2002-02-06 | 2005-10-27 | ヴァイコー テクノロジーズ, インコーポレイテッド | Anti-infarction molecule |
US20030162179A1 (en) * | 2002-02-27 | 2003-08-28 | General Electric Company | Fabrication, performance testing, and screening of three dimensional arrays of materials |
US6684683B2 (en) * | 2002-02-27 | 2004-02-03 | General Electric Company | Method and apparatus for characterizing the barrier properties of members of combinatorial libraries |
US6902704B2 (en) * | 2002-02-28 | 2005-06-07 | Equistar Chemicals, L.P | Injection pump assembly for a combinatorial reactor and related method |
US6869806B2 (en) * | 2002-03-14 | 2005-03-22 | Wisys Technology Foundation, Inc. | Method and apparatus for the production of a semiconductor compatible ferromagnetic film |
DE60324778D1 (en) | 2002-03-15 | 2009-01-02 | Nuevolution As | AN IMPROVED METHOD FOR SYNTHESIS OF MATTRESS-RELATED MOLECULES |
US6916621B2 (en) | 2002-03-27 | 2005-07-12 | Spectral Genomics, Inc. | Methods for array-based comparitive binding assays |
US20030190260A1 (en) * | 2002-04-05 | 2003-10-09 | Symyx Technologies, Inc. | Combinatorial chemistry reactor system |
US6949267B2 (en) | 2002-04-08 | 2005-09-27 | Engelhard Corporation | Combinatorial synthesis |
US6869904B2 (en) * | 2002-04-24 | 2005-03-22 | Symyx Technologies, Inc. | Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom |
US7091292B2 (en) * | 2002-04-24 | 2006-08-15 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
US7060848B2 (en) * | 2002-04-24 | 2006-06-13 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
US20030203500A1 (en) * | 2002-04-26 | 2003-10-30 | Symyx Technologies, Inc. | High throughput testing of fluid samples using an electric field |
GB0210237D0 (en) * | 2002-05-03 | 2002-06-12 | Bp Chem Int Ltd | Injector system |
US20030219456A1 (en) * | 2002-05-21 | 2003-11-27 | Taing Ok | Method of utilization of zygosaccharomyces rouxii |
US6928877B2 (en) * | 2002-05-24 | 2005-08-16 | Symyx Technologies, Inc. | High throughput microbalance and methods of using same |
US20040071888A1 (en) * | 2002-05-30 | 2004-04-15 | Symyx Technologies, Inc. | Apparatus and method of research for creating and testing thin films |
US20050239193A1 (en) * | 2002-05-30 | 2005-10-27 | Bioforce Nanosciences, Inc. | Device and method of use for detection and characterization of microorganisms and microparticles |
DE10230455A1 (en) * | 2002-07-06 | 2004-01-22 | Robert Bosch Gmbh | Method for setting or locally changing a magnetization in a layer of a magnetoresistive layer arrangement, heating stamp for heating the magnetoresistive layer arrangement and their use |
AU2003247266A1 (en) | 2002-08-01 | 2004-02-23 | Nuevolution A/S | Multi-step synthesis of templated molecules |
US7042035B2 (en) * | 2002-08-02 | 2006-05-09 | Unity Semiconductor Corporation | Memory array with high temperature wiring |
US7632916B2 (en) | 2002-08-02 | 2009-12-15 | 3M Innovative Properties Company | Process to modify polymeric materials and resulting compositions |
AU2003257181A1 (en) | 2002-08-05 | 2004-02-23 | University Of Rochester | Protein transducing domain/deaminase chimeric proteins, related compounds, and uses thereof |
WO2004013622A1 (en) * | 2002-08-06 | 2004-02-12 | Ssci, Inc. | Method of comparing x-ray diffraction patterns using the fundamental parameter method |
US20050019747A1 (en) * | 2002-08-07 | 2005-01-27 | Anderson Daniel G. | Nanoliter-scale synthesis of arrayed biomaterials and screening thereof |
US20040028804A1 (en) * | 2002-08-07 | 2004-02-12 | Anderson Daniel G. | Production of polymeric microarrays |
US8277753B2 (en) | 2002-08-23 | 2012-10-02 | Life Technologies Corporation | Microfluidic transfer pin |
US7247346B1 (en) | 2002-08-28 | 2007-07-24 | Nanosolar, Inc. | Combinatorial fabrication and high-throughput screening of optoelectronic devices |
US7135288B2 (en) | 2002-09-27 | 2006-11-14 | Ut-Battelle, Llc | Combinatorial synthesis of ceramic materials |
US7043969B2 (en) * | 2002-10-18 | 2006-05-16 | Symyx Technologies, Inc. | Machine fluid sensor and method |
DE10248639B4 (en) * | 2002-10-18 | 2005-03-17 | Ticona Gmbh | Process and device for the combinatorial production of mixtures and their use |
US7112443B2 (en) | 2002-10-18 | 2006-09-26 | Symyx Technologies, Inc. | High throughput permeability testing of materials libraries |
WO2004036207A2 (en) * | 2002-10-18 | 2004-04-29 | Symyx Technologies, Inc. | Environmental control system fluid sensing system and method comprising a sesnsor with a mechanical resonator |
US20040115722A1 (en) * | 2002-10-25 | 2004-06-17 | Mel Kronick | Biopolymeric arrays and methods of producing the same |
US7635564B2 (en) * | 2002-10-25 | 2009-12-22 | Agilent Technologies, Inc. | Biopolymeric arrays having replicate elements |
DK1558744T3 (en) | 2002-10-30 | 2011-10-10 | Nuevolution As | Enzymatic coding |
US20100210027A9 (en) * | 2002-11-04 | 2010-08-19 | Hongming Chen | Method for determining effect of preformulation forms on their dissolution rates |
US7108992B2 (en) * | 2002-11-27 | 2006-09-19 | St. Jude Children's Research Hospital | ATM kinase compositions and methods |
US7141217B2 (en) | 2002-12-05 | 2006-11-28 | Uop Llc | Elevated pressure apparatus and method for generating a plurality of isolated effluents |
US20080211491A1 (en) * | 2002-12-09 | 2008-09-04 | Ferro Solutions, Inc. | High sensitivity, passive magnetic field sensor and method of manufacture |
US20090062886A1 (en) * | 2002-12-09 | 2009-03-05 | Ferro Solutions, Inc. | Systems and methods for delivering electrical energy in the body |
US7808236B1 (en) | 2002-12-09 | 2010-10-05 | Ferro Solutions, Inc. | Energy harvester utilizing external magnetic field |
US7952349B2 (en) * | 2002-12-09 | 2011-05-31 | Ferro Solutions, Inc. | Apparatus and method utilizing magnetic field |
ATE450609T1 (en) | 2002-12-19 | 2009-12-15 | Nuevolution As | SYNTHESIS METHOD GUIDED BY QUASI-RANDOM STRUCTURES AND FUNCTIONS |
US7160513B2 (en) * | 2002-12-20 | 2007-01-09 | Symyx Technologies, Inc. | Batch reactor with injection system |
US7682565B2 (en) | 2002-12-20 | 2010-03-23 | Biotrove, Inc. | Assay apparatus and method using microfluidic arrays |
EP1583845A4 (en) * | 2003-01-02 | 2006-06-28 | Bioforce Nanosciences Inc | Method and apparatus for molecular analysis in small sample volumes |
ES2721655T3 (en) | 2003-01-17 | 2019-08-02 | Univ Missouri | Corrosion resistant coatings |
US7213034B2 (en) * | 2003-01-24 | 2007-05-01 | Symyx Technologies, Inc. | User-configurable generic experiment class for combinatorial materials research |
US6984902B1 (en) * | 2003-02-03 | 2006-01-10 | Ferro Solutions, Inc. | High efficiency vibration energy harvester |
US7485390B2 (en) * | 2003-02-12 | 2009-02-03 | Symyx Technologies, Inc. | Combinatorial methods for preparing electrocatalysts |
WO2004074429A2 (en) | 2003-02-21 | 2004-09-02 | Nuevolution A/S | Method for producing second-generation library |
KR100538092B1 (en) * | 2003-02-27 | 2005-12-21 | 삼성전자주식회사 | Method of monitoring a depth profile of impurities density |
US20040180452A1 (en) * | 2003-03-14 | 2004-09-16 | Yongjie Cui | Method and apparatus for the production of a semiconductor compatible ferromagnetic film |
GB2399541A (en) * | 2003-03-18 | 2004-09-22 | Nanomagnetics Ltd | Production of nanoparticulate thin films |
DE602004013753D1 (en) * | 2003-03-21 | 2008-06-26 | Hella Kgaa Hueck & Co | RESONATOR SENSOR UNIT |
EP1644717A2 (en) * | 2003-03-21 | 2006-04-12 | Symyx Technologies, Inc. | Mechanical resonator |
US7721590B2 (en) | 2003-03-21 | 2010-05-25 | MEAS France | Resonator sensor assembly |
US7569952B1 (en) | 2003-04-18 | 2009-08-04 | Ferro Solutions, Inc. | High efficiency, inductive vibration energy harvester |
US6946842B2 (en) * | 2003-05-28 | 2005-09-20 | Elliott Kirk Gozansky | Analytical instrument and processes |
US6805175B1 (en) | 2003-06-12 | 2004-10-19 | Symyx Technologies, Inc. | Powder transfer method and apparatus |
US7134459B2 (en) * | 2003-06-12 | 2006-11-14 | Symyx Technologies, Inc. | Methods and apparatus for mixing powdered samples |
US7672791B2 (en) * | 2003-06-13 | 2010-03-02 | International Business Machines Corporation | Method of performing three-dimensional molecular superposition and similarity searches in databases of flexible molecules |
WO2004113869A2 (en) * | 2003-06-17 | 2004-12-29 | Surromed, Inc. | Labeling and authentication of metal objects |
DE10327839A1 (en) * | 2003-06-20 | 2005-01-05 | Arvinmeritor Gmbh | Vehicle roof module |
US7393920B2 (en) | 2003-06-23 | 2008-07-01 | Cem Corporation | Microwave-assisted peptide synthesis |
US7902488B2 (en) * | 2003-06-23 | 2011-03-08 | Cem Corporation | Microwave-assisted peptide synthesis |
EP1649066A4 (en) * | 2003-07-11 | 2006-10-11 | Surromed Inc | Multiplexed molecular beacon assay for detection of pathogens |
EP1649265A1 (en) | 2003-07-28 | 2006-04-26 | Symyx Technologies, Inc. | Parallel infrared spectroscopy apparatus and method |
US20060222790A1 (en) * | 2003-07-30 | 2006-10-05 | The Regents Of The University Of California | Preparation of library that includes monodisperse nanoclusters |
DE10335968A1 (en) | 2003-08-06 | 2005-02-24 | Basf Ag | Sequential production of a library of solids (especially heterogeneous catalysts) comprises dosing solutions, emulsions and/or dispersions into a mixer and drying, with variations and repetition |
US7361257B2 (en) * | 2003-08-15 | 2008-04-22 | Symyx Technologies, Inc. | Electrochemical screening system |
US7427341B2 (en) * | 2003-08-15 | 2008-09-23 | Symyx Technologies, Inc. | System for synthesis of electrode array |
KR100559792B1 (en) * | 2003-08-29 | 2006-03-15 | 한국과학기술원 | The method for producing thin film or powder array using liquid source misted chemical deposition process |
US7919431B2 (en) * | 2003-09-03 | 2011-04-05 | Synfuels International, Inc. | Catalyst formulation for hydrogenation |
US20050054116A1 (en) * | 2003-09-05 | 2005-03-10 | Potyrailo Radislav A. | Method of manufacturing and evaluating sensor coatings and the sensors derived therefrom |
US20050136536A1 (en) * | 2003-09-15 | 2005-06-23 | Anderson Daniel G. | Embryonic epithelial cells |
ATE447626T1 (en) | 2003-09-18 | 2009-11-15 | Nuevolution As | METHOD FOR OBTAINING STRUCTURAL INFORMATION FROM ENCODED MOLECULES AND FOR SELECTING COMPOUNDS |
US7462490B2 (en) | 2003-10-31 | 2008-12-09 | Chevron Oronite Company Llc | Combinatorial lubricating oil composition libraries |
US7150182B2 (en) * | 2003-10-31 | 2006-12-19 | Chevron Oronite Company, Llc | High throughput screening methods for lubricating oil compositions |
US7069203B2 (en) * | 2003-10-31 | 2006-06-27 | Chevron Oronite Company Llc | Method and system of product development process for chemical compositions using high volume modeling |
US20050095714A1 (en) * | 2003-10-31 | 2005-05-05 | Wollenberg Robert H. | High throughput preparation of lubricating oil compositions for combinatorial libraries |
US7579192B2 (en) * | 2003-10-31 | 2009-08-25 | Chevron Oronite Company Llc | High throughput screening methods for lubricating oil compositions |
US20050095717A1 (en) * | 2003-10-31 | 2005-05-05 | Wollenberg Robert H. | High throughput screening methods for lubricating oil compositions |
US20050130229A1 (en) * | 2003-12-16 | 2005-06-16 | Symyx Technologies, Inc. | Indexing scheme for formulation workflows |
DE10361099B3 (en) * | 2003-12-22 | 2005-05-25 | Robert Bosch Gmbh | Device for analyzing material samples arranged on a sample plate comprises a support for the sample plate and a contacting unit for electrically contacting the material samples, and a measuring head inserted in a housing support |
US20050172896A1 (en) * | 2004-02-10 | 2005-08-11 | Tihiro Ohkawa | Injector for plasma mass filter |
US7306948B2 (en) * | 2004-02-13 | 2007-12-11 | Chevron Oronite Company Llc | High throughput screening methods for lubricating oil compositions |
US7985592B2 (en) | 2004-02-13 | 2011-07-26 | Chevron Oronite Company Llc | High throughput screening methods for lubricating oil compositions |
US7137289B2 (en) | 2004-02-13 | 2006-11-21 | Chevron Oronite Company, Llc | High throughput screening methods for lubricating oil compositions |
US8249816B2 (en) * | 2004-02-13 | 2012-08-21 | Chevron Oronite Company, Llc | High throughput screening methods for fuel compositions |
US8105554B2 (en) | 2004-03-12 | 2012-01-31 | Life Technologies Corporation | Nanoliter array loading |
US20070300142A1 (en) * | 2005-04-01 | 2007-12-27 | King Martin T | Contextual dynamic advertising based upon captured rendered text |
CA2562838A1 (en) * | 2004-04-14 | 2005-10-27 | Catalyst Design, Inc. | Smart combinatorial operando spectroscopy catalytic system |
WO2005116650A2 (en) * | 2004-04-19 | 2005-12-08 | Sdc Materials, Llc | High throughput discovery of materials through vapor phase synthesis |
US7589041B2 (en) | 2004-04-23 | 2009-09-15 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials, and methods of making and using the same |
US7553670B2 (en) * | 2004-04-28 | 2009-06-30 | 3M Innovative Properties Company | Method for monitoring a polymerization in a three-dimensional sample |
US7341872B1 (en) | 2004-04-29 | 2008-03-11 | Uop Llc | Multiautoclave with set of vessels for combinatorial synthesis of zeolites and other materials |
JP2007535681A (en) * | 2004-04-30 | 2007-12-06 | バイオフォース・ナノサイエンシィズ・インコーポレーテッド | Method and apparatus for depositing material on a surface |
US20050278308A1 (en) * | 2004-06-01 | 2005-12-15 | Barstow James F | Methods and systems for data integration |
DE102005025644A1 (en) * | 2004-06-03 | 2006-01-26 | MDL Information Systems, Inc., San Leandro | Method and device for visual application design |
DE602005017627D1 (en) * | 2004-06-16 | 2009-12-24 | Dow Global Technologies Inc | DEVICE AND METHOD FOR ZIEGLER NATTA RESEARCH |
JP5188178B2 (en) | 2004-06-16 | 2013-04-24 | ダウ グローバル テクノロジーズ エルエルシー | Techniques for selecting polymerization modifiers. |
WO2006043985A1 (en) | 2004-06-16 | 2006-04-27 | Dow Global Technologies Inc. | Method for identifying ziegler-natta cocatalyst |
WO2006135372A2 (en) * | 2004-07-02 | 2006-12-21 | Kepler Keith D | Combinatorial method and apparatus for screening electrochemical materials |
JP4678620B2 (en) * | 2004-08-30 | 2011-04-27 | 独立行政法人科学技術振興機構 | Multi-source mechanism for film deposition equipment |
US7597852B2 (en) * | 2004-09-03 | 2009-10-06 | Symyx Solutions, Inc. | Substrate for sample analyses |
US7507337B2 (en) * | 2004-09-03 | 2009-03-24 | Symyx Technologies, Inc. | System and method for rapid chromatography with fluid temperature and mobile phase composition control |
CN103852573B (en) | 2004-09-15 | 2017-01-04 | 英国石油国际有限公司 | The method of assessment refinery feedstock |
US7749881B2 (en) * | 2005-05-18 | 2010-07-06 | Intermolecular, Inc. | Formation of a masking layer on a dielectric region to facilitate formation of a capping layer on electrically conductive regions separated by the dielectric region |
US20060060301A1 (en) * | 2004-09-17 | 2006-03-23 | Lazovsky David E | Substrate processing using molecular self-assembly |
US7390739B2 (en) * | 2005-05-18 | 2008-06-24 | Lazovsky David E | Formation of a masking layer on a dielectric region to facilitate formation of a capping layer on electrically conductive regions separated by the dielectric region |
US8882914B2 (en) * | 2004-09-17 | 2014-11-11 | Intermolecular, Inc. | Processing substrates using site-isolated processing |
US8084400B2 (en) * | 2005-10-11 | 2011-12-27 | Intermolecular, Inc. | Methods for discretized processing and process sequence integration of regions of a substrate |
US20060292846A1 (en) * | 2004-09-17 | 2006-12-28 | Pinto Gustavo A | Material management in substrate processing |
US7387980B2 (en) * | 2004-09-22 | 2008-06-17 | Symyx Technologies, Inc. | Methods of using heterocycle-amine ligands, compositions, complexes, and catalysts |
US7256296B2 (en) * | 2004-09-22 | 2007-08-14 | Symyx Technologies, Inc. | Heterocycle-amine ligands, compositions, complexes, and catalysts |
EP1810001A4 (en) | 2004-10-08 | 2008-08-27 | Sdc Materials Llc | An apparatus for and method of sampling and collecting powders flowing in a gas stream |
KR100624442B1 (en) * | 2004-11-03 | 2006-09-15 | 삼성전자주식회사 | Method for preparing thin film of ferroelectric |
US7309658B2 (en) * | 2004-11-22 | 2007-12-18 | Intermolecular, Inc. | Molecular self-assembly in substrate processing |
US7879710B2 (en) * | 2005-05-18 | 2011-02-01 | Intermolecular, Inc. | Substrate processing including a masking layer |
US7705157B2 (en) * | 2004-12-16 | 2010-04-27 | Symyx Solutions, Inc. | Phenol-heterocyclic ligands, metal complexes, and their uses as catalysts |
GB0501102D0 (en) | 2005-01-19 | 2005-02-23 | Bp Chem Int Ltd | Process |
US20060165895A1 (en) * | 2005-01-24 | 2006-07-27 | Julio Cartagena | System and a method for synthesizing nanoparticle arrays in-situ |
US7818666B2 (en) * | 2005-01-27 | 2010-10-19 | Symyx Solutions, Inc. | Parsing, evaluating leaf, and branch nodes, and navigating the nodes based on the evaluation |
DE102005007872B3 (en) * | 2005-02-21 | 2006-06-22 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Temperature measurement in microfluidic channel of microfluidic device, comprises irradiating volume element of the channel by pulsed laser, elastic scattering and detecting Raman light and converting the Raman light to signals |
KR100631972B1 (en) | 2005-02-28 | 2006-10-11 | 삼성전기주식회사 | Method for manufacturing superlattice semiconductor structure using chemical vapor deposition process |
US9125968B2 (en) * | 2005-03-30 | 2015-09-08 | Boston Scientific Scimed, Inc. | Polymeric/ceramic composite materials for use in medical devices |
JP5129119B2 (en) | 2005-04-05 | 2013-01-23 | コーニング インコーポレイテッド | Label-free biosensors and cells |
US20060249372A1 (en) * | 2005-04-11 | 2006-11-09 | Intematix Corporation | Biased target ion bean deposition (BTIBD) for the production of combinatorial materials libraries |
CZ2005294A3 (en) * | 2005-05-09 | 2007-01-31 | Bvt Technologies A. S. | Nanostructured working electrode of electrochemical sensor, process for its manufacture and sensor comprising such working electrode |
WO2006127020A1 (en) | 2005-05-19 | 2006-11-30 | The Government Of The United States Of America, As Represented By The Secretary, Department Of Health And Human Services, Centers For Disease Control And Prevention | FUNCTIONAL EPITOPES OF STREPTOCOCCUS PNEUMONIAE PsaA ANTIGEN AND USES THEREOF |
US7420442B1 (en) * | 2005-06-08 | 2008-09-02 | Sandia Corporation | Micromachined microwave signal control device and method for making same |
WO2007022110A2 (en) * | 2005-08-12 | 2007-02-22 | Symyx Technologies, Inc. | Event-based library process design |
US9550162B2 (en) * | 2005-09-19 | 2017-01-24 | Intematix Corporation | Printing liquid solution arrays for inorganic combinatorial libraries |
US8008395B2 (en) * | 2005-09-27 | 2011-08-30 | Boston Scientific Scimed, Inc. | Organic-inorganic hybrid particle material and polymer compositions containing same |
US7955436B2 (en) * | 2006-02-24 | 2011-06-07 | Intermolecular, Inc. | Systems and methods for sealing in site-isolated reactors |
US7544574B2 (en) * | 2005-10-11 | 2009-06-09 | Intermolecular, Inc. | Methods for discretized processing of regions of a substrate |
US8776717B2 (en) * | 2005-10-11 | 2014-07-15 | Intermolecular, Inc. | Systems for discretized processing of regions of a substrate |
EP2392645A1 (en) | 2005-10-14 | 2011-12-07 | MUSC Foundation For Research Development | Targeting PAX2 for the induction of DEFB1-mediated tumor immunity and cancer therapy |
US8080534B2 (en) | 2005-10-14 | 2011-12-20 | Phigenix, Inc | Targeting PAX2 for the treatment of breast cancer |
US20070102290A1 (en) * | 2005-11-10 | 2007-05-10 | The Circle For The Promotion Of Science And Engineering | Novel material development apparatus and novel material development method using arc plasma |
HUE056836T2 (en) | 2005-12-01 | 2022-03-28 | Nuevolution As | Enzymatic encoding methods for efficient synthesis of large libraries |
EP2359930A1 (en) | 2005-12-16 | 2011-08-24 | Dow Global Technologies LLC | A polymer prepared in the presence of metal complexes bearing a polydentate heteroatom ligand |
US20070148697A1 (en) * | 2005-12-27 | 2007-06-28 | Boston Scientific Scimed, Inc. | Methods and system for high throughput screening of polymer materials for medical devices |
JP5284108B2 (en) * | 2006-02-10 | 2013-09-11 | インターモレキュラー, インコーポレイテッド | Method and system for combinatorial change of materials, unit processes and process sequences |
US8772772B2 (en) * | 2006-05-18 | 2014-07-08 | Intermolecular, Inc. | System and method for increasing productivity of combinatorial screening |
JP2007224747A (en) * | 2006-02-21 | 2007-09-06 | Mitsubishi Motors Corp | Exhaust emission control filter and exhaust emission control device of diesel engine |
US20070269611A1 (en) * | 2006-03-31 | 2007-11-22 | Intematix Corporation | Systems and methods of combinatorial synthesis |
US20070232556A1 (en) * | 2006-03-31 | 2007-10-04 | Montine Thomas J | Methods and compositions for the treatment of neurological diseases and disorders |
US7750634B1 (en) * | 2006-05-22 | 2010-07-06 | Christensen Charles L | Methods and apparatus for detecting elements and compounds |
US7867904B2 (en) * | 2006-07-19 | 2011-01-11 | Intermolecular, Inc. | Method and system for isolated and discretized process sequence integration |
US20080113877A1 (en) * | 2006-08-16 | 2008-05-15 | Intematix Corporation | Liquid solution deposition of composition gradient materials |
US20080076679A1 (en) * | 2006-08-16 | 2008-03-27 | Intematix Corporation | Systems and methods of combinatorial synthesis using laser-assisted thermal activation |
US8310332B2 (en) * | 2008-10-08 | 2012-11-13 | Cooper Technologies Company | High current amorphous powder core inductor |
US9589716B2 (en) | 2006-09-12 | 2017-03-07 | Cooper Technologies Company | Laminated magnetic component and manufacture with soft magnetic powder polymer composite sheets |
US8378777B2 (en) | 2008-07-29 | 2013-02-19 | Cooper Technologies Company | Magnetic electrical device |
US8941457B2 (en) * | 2006-09-12 | 2015-01-27 | Cooper Technologies Company | Miniature power inductor and methods of manufacture |
US7791445B2 (en) * | 2006-09-12 | 2010-09-07 | Cooper Technologies Company | Low profile layered coil and cores for magnetic components |
US8466764B2 (en) * | 2006-09-12 | 2013-06-18 | Cooper Technologies Company | Low profile layered coil and cores for magnetic components |
US7615385B2 (en) | 2006-09-20 | 2009-11-10 | Hypres, Inc | Double-masking technique for increasing fabrication yield in superconducting electronics |
US20100190689A1 (en) | 2006-09-21 | 2010-07-29 | University Of Rochester | Compositions and methods related to protein displacement therapy for myotonic distrophy |
US8231831B2 (en) * | 2006-10-06 | 2012-07-31 | Sharp Laboratories Of America, Inc. | Micro-pixelated fluid-assay structure |
US8236244B2 (en) * | 2006-10-06 | 2012-08-07 | Sharp Laboratories Of America, Inc. | Micro-pixelated fluid-assay structure with on-board addressable, pixel-specific functionalization |
US8232108B2 (en) * | 2006-10-06 | 2012-07-31 | Sharp Laboratories Of America, Inc. | Method of making micro-pixelated fluid-assay structure |
US8236571B2 (en) * | 2006-10-06 | 2012-08-07 | Sharp Laboratories Of America, Inc. | Method of making micro-pixelated fluid-assay precursor structure |
US8232109B2 (en) * | 2006-10-06 | 2012-07-31 | Sharp Laboratories Of America, Inc. | Micro-pixelated active-matrix fluid-assay performance |
US8236245B2 (en) * | 2006-10-06 | 2012-08-07 | Sharp Laboratories Of America, Inc. | Micro-pixelated fluid-assay precursor structure |
US7619229B2 (en) | 2006-10-16 | 2009-11-17 | Varian Semiconductor Equipment Associates, Inc. | Technique for matching performance of ion implantation devices using an in-situ mask |
BRPI0715568A2 (en) | 2006-10-19 | 2013-07-02 | Nanomech, Llc | Methods and apparatus for making coatings using ultrasonic spray deposition |
KR101478985B1 (en) | 2006-10-19 | 2015-01-06 | 더 보드 오브 트러스티스 오브 더 유니버시티 오브 아칸소 | Method and apparatus for making coatings using electrostatic spray |
WO2008136852A2 (en) | 2006-11-01 | 2008-11-13 | University Of Rochester | Methods and compositions related to the structure and function of apobec3g |
ES2319007B1 (en) * | 2006-12-07 | 2010-02-16 | Rive Technology, Inc. | METHODS FOR MANUFACTURING MESOSTRUCTURED ZEOLITICAL MATERIALS. |
JP2007183266A (en) * | 2006-12-25 | 2007-07-19 | Seiko Epson Corp | Composition probing method and method for probing composition of electrode catalyst for fuel cell |
US8011317B2 (en) * | 2006-12-29 | 2011-09-06 | Intermolecular, Inc. | Advanced mixing system for integrated tool having site-isolated reactors |
EP2136911A2 (en) * | 2007-01-19 | 2009-12-30 | Biodot, Inc. | Systems and methods for high speed array printing and hybridization |
US20080178535A1 (en) * | 2007-01-26 | 2008-07-31 | Diamond Innovations, Inc. | Graded drilling cutter |
EP2117576B1 (en) | 2007-02-08 | 2014-04-16 | University Of Utah Research Foundation | Methods and compositions related to inhibition of viral entry |
US20080242559A1 (en) * | 2007-03-28 | 2008-10-02 | Northwestern University | Protein and peptide arrays |
US8281332B2 (en) * | 2007-05-02 | 2012-10-02 | Google Inc. | Animated video overlays |
US7678419B2 (en) | 2007-05-11 | 2010-03-16 | Sdc Materials, Inc. | Formation of catalytic regions within porous structures using supercritical phase processing |
EP2042232A1 (en) | 2007-07-25 | 2009-04-01 | Symyx Technologies, Inc. | Systems and methods for mixing materials |
US8771483B2 (en) * | 2007-09-05 | 2014-07-08 | Intermolecular, Inc. | Combinatorial process system |
WO2009039122A2 (en) | 2007-09-17 | 2009-03-26 | Sequenom, Inc. | Integrated robotic sample transfer device |
US8481449B1 (en) | 2007-10-15 | 2013-07-09 | SDCmaterials, Inc. | Method and system for forming plug and play oxide catalysts |
US8206498B2 (en) * | 2007-10-25 | 2012-06-26 | Rive Technology, Inc. | Methods of recovery of pore-forming agents for mesostructured materials |
US20090155994A1 (en) * | 2007-12-12 | 2009-06-18 | Hawkins Gilbert A | Forming thin film transistors using ablative films with pre-patterned conductors |
US8129288B2 (en) * | 2008-05-02 | 2012-03-06 | Intermolecular, Inc. | Combinatorial plasma enhanced deposition techniques |
WO2009091393A2 (en) * | 2008-01-15 | 2009-07-23 | Uop Llc | Multiautoclave with set of vessels for combinatorial synthesis of zeolites and other materials |
US8882917B1 (en) | 2009-12-31 | 2014-11-11 | Intermolecular, Inc. | Substrate processing including correction for deposition location |
USD627900S1 (en) | 2008-05-07 | 2010-11-23 | SDCmaterials, Inc. | Glove box |
US20090286944A1 (en) * | 2008-05-15 | 2009-11-19 | Symyx Technologies, Inc. | Select phenol-heterocycle ligands, metal complexes formed therefrom, and their uses as catalysts |
US9859043B2 (en) | 2008-07-11 | 2018-01-02 | Cooper Technologies Company | Magnetic components and methods of manufacturing the same |
US8279037B2 (en) * | 2008-07-11 | 2012-10-02 | Cooper Technologies Company | Magnetic components and methods of manufacturing the same |
US9558881B2 (en) | 2008-07-11 | 2017-01-31 | Cooper Technologies Company | High current power inductor |
US8659379B2 (en) | 2008-07-11 | 2014-02-25 | Cooper Technologies Company | Magnetic components and methods of manufacturing the same |
US9126175B2 (en) * | 2008-08-13 | 2015-09-08 | California Institute Of Technology | High-throughput screening and device for photocatalysts |
AU2009281732A1 (en) | 2008-08-15 | 2010-02-18 | Georgetown University | Na channels, disease, and related assays and compositions |
US7947531B1 (en) | 2008-08-28 | 2011-05-24 | Intermolecular, Inc. | Combinatorial evaluation of dry semiconductor processes |
US9306078B2 (en) * | 2008-09-08 | 2016-04-05 | Cbrite Inc. | Stable amorphous metal oxide semiconductor |
JP5315156B2 (en) * | 2008-09-19 | 2013-10-16 | 日東電工株式会社 | Manufacturing method of sensor substrate |
EP2184102A1 (en) * | 2008-11-11 | 2010-05-12 | Stichting Dutch Polymer Institute | Particle manufacturing method, particle libraries and use thereof |
JP5711663B2 (en) * | 2008-11-27 | 2015-05-07 | エイエムシー・アブレイシブズ・マーケティング・アンド・コンサルティング・リミテッド・ライアビリティ・パートナーシップAmc Abrasives Marketing & Consulting Llp | Dental care products with diamond particles |
WO2010065617A1 (en) | 2008-12-02 | 2010-06-10 | University Of Utah Research Foundation | Pde1 as a target therapeutic in heart disease |
US8524625B2 (en) * | 2009-01-19 | 2013-09-03 | Rive Technology, Inc. | Compositions and methods for improving the hydrothermal stability of mesostructured zeolites by rare earth ion exchange |
US8486369B2 (en) * | 2009-01-19 | 2013-07-16 | Rive Technology, Inc. | Introduction of mesoporosity in low Si/Al zeolites |
US20100277267A1 (en) * | 2009-05-04 | 2010-11-04 | Robert James Bogert | Magnetic components and methods of manufacturing the same |
FR2946462B1 (en) | 2009-06-09 | 2011-07-01 | Commissariat Energie Atomique | METHOD FOR PRODUCING AT LEAST ONE MICROCOMPONENT WITH A SINGLE MASK |
US20120149663A1 (en) | 2009-08-18 | 2012-06-14 | Georgetown University | Boronic acid compositions and methods related to cancer |
US8563325B1 (en) | 2009-09-29 | 2013-10-22 | Sandia Corporation | Coaxial microreactor for particle synthesis |
US20110081293A1 (en) | 2009-10-07 | 2011-04-07 | Sanford-Burnham Medical Research Institute | Methods and compositions related to clot-binding lipid compounds |
US20120128314A1 (en) * | 2009-10-09 | 2012-05-24 | Xiaosong Wu | D1451 methods for formulating radiation curable supercoatings for optical fiber |
JP2013508543A (en) * | 2009-10-15 | 2013-03-07 | アーケマ・インコーポレイテッド | Deposition of doped ZnO films on polymer substrates by UV-assisted chemical vapor deposition |
US8685875B2 (en) | 2009-10-20 | 2014-04-01 | Rive Technology, Inc. | Methods for enhancing the mesoporosity of zeolite-containing materials |
US8501122B2 (en) | 2009-12-08 | 2013-08-06 | Affymetrix, Inc. | Manufacturing and processing polymer arrays |
US9126191B2 (en) | 2009-12-15 | 2015-09-08 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
US8652992B2 (en) | 2009-12-15 | 2014-02-18 | SDCmaterials, Inc. | Pinning and affixing nano-active material |
US8803025B2 (en) | 2009-12-15 | 2014-08-12 | SDCmaterials, Inc. | Non-plugging D.C. plasma gun |
US9039916B1 (en) | 2009-12-15 | 2015-05-26 | SDCmaterials, Inc. | In situ oxide removal, dispersal and drying for copper copper-oxide |
US8557727B2 (en) | 2009-12-15 | 2013-10-15 | SDCmaterials, Inc. | Method of forming a catalyst with inhibited mobility of nano-active material |
US8545652B1 (en) | 2009-12-15 | 2013-10-01 | SDCmaterials, Inc. | Impact resistant material |
US9149797B2 (en) | 2009-12-15 | 2015-10-06 | SDCmaterials, Inc. | Catalyst production method and system |
US8470112B1 (en) | 2009-12-15 | 2013-06-25 | SDCmaterials, Inc. | Workflow for novel composite materials |
JP2013515008A (en) | 2009-12-18 | 2013-05-02 | サンフォード−バーナム メディカル リサーチ インスティテュート | Methods and compositions relating to clot-binding compounds |
US20110171121A1 (en) * | 2010-01-08 | 2011-07-14 | Rive Technology, Inc. | Compositions and methods for making stabilized mesoporous materials |
US8301214B1 (en) | 2010-01-08 | 2012-10-30 | Hypres, Inc. | System and method for providing multi-conductive layer metallic interconnects for superconducting integrated circuits |
US8568828B2 (en) * | 2010-02-12 | 2013-10-29 | Alliance For Sustainable Energy, Llc | Amorphous tin-cadmium oxide films and the production thereof |
ES2713873T3 (en) | 2010-04-16 | 2019-05-24 | Nuevolution As | Bifunctional complexes and methods for making and using such complexes |
RU2459194C2 (en) * | 2010-05-17 | 2012-08-20 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Method of determining density of high-temperature metallic melts (versions) |
WO2011163476A2 (en) * | 2010-06-25 | 2011-12-29 | The General Hospital Corporation | Colorimetric method and device for detecting analyte quantities in fluids and materials |
US9448195B2 (en) * | 2010-07-16 | 2016-09-20 | University Of Utah Research Foundation | Electrophysiological recording system and methods of using same |
CN102002649B (en) * | 2010-09-16 | 2013-08-14 | 南京理工大学 | High-toughness magnesium based block body metal glass composite material and preparation method thereof |
JP6104810B2 (en) * | 2010-11-23 | 2017-03-29 | アンドリュー・アライアンス・ソシエテ・アノニムAndrew Alliance S.A. | Apparatus and method for programmable operation of a pipette |
US8410884B2 (en) | 2011-01-20 | 2013-04-02 | Hitran Corporation | Compact high short circuit current reactor |
US8669202B2 (en) | 2011-02-23 | 2014-03-11 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PtPd catalysts |
JP6205345B2 (en) | 2011-03-28 | 2017-09-27 | ユニヴァーシティー オブ ユタ リサーチ ファウンデーション | Methods and compositions for inhibition of viral entry |
AU2012240093B2 (en) | 2011-04-08 | 2015-06-11 | W. R. Grace & Co.-Conn. | Mesoporous framework-modified zeolites |
CN103648647B (en) * | 2011-07-07 | 2015-04-01 | 霍尔格·彼尼克 | Cuvette module having an electrically conductive cuvette carrier |
CA2845129A1 (en) | 2011-08-19 | 2013-02-28 | SDCmaterials, Inc. | Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions |
US9175382B2 (en) * | 2011-10-25 | 2015-11-03 | Intermolecular, Inc. | High metal ionization sputter gun |
CN103930369A (en) | 2012-01-13 | 2014-07-16 | 瑞弗科技有限公司 | Introduction of mesoporosity into low silica zeolites |
US9376324B2 (en) | 2012-01-13 | 2016-06-28 | Rive Technology, Inc. | Introduction of mesoporosity into zeolite materials with sequential acid, surfactant, and base treatment |
WO2013109406A1 (en) * | 2012-01-17 | 2013-07-25 | The Scripps Research Institute | Apparatus and method for producing specimens for electron microscopy |
GB201209239D0 (en) * | 2012-05-25 | 2012-07-04 | Univ Glasgow | Methods of evolutionary synthesis including embodied chemical synthesis |
WO2014074649A1 (en) * | 2012-11-06 | 2014-05-15 | Purdue Research Foundation | Methods for directed irradiation synthesis with ion and thermal beams |
US9156025B2 (en) | 2012-11-21 | 2015-10-13 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
US9511352B2 (en) | 2012-11-21 | 2016-12-06 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
US20140178583A1 (en) * | 2012-12-20 | 2014-06-26 | Intermolecular, Inc. | Combinatorial Methods and Systems for Developing Thermochromic Materials and Devices |
US8765660B1 (en) | 2013-03-08 | 2014-07-01 | Rive Technology, Inc. | Separation of surfactants from polar solids |
US8863311B1 (en) * | 2013-07-18 | 2014-10-14 | National Taiwan University | Radio-frequency reflectometry scanning tunneling microscope |
EP3024571B1 (en) | 2013-07-25 | 2020-05-27 | Umicore AG & Co. KG | Washcoats and coated substrates for catalytic converters |
US9517448B2 (en) | 2013-10-22 | 2016-12-13 | SDCmaterials, Inc. | Compositions of lean NOx trap (LNT) systems and methods of making and using same |
WO2015061477A1 (en) | 2013-10-22 | 2015-04-30 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
CN103526193A (en) * | 2013-10-22 | 2014-01-22 | 核工业北京地质研究院 | Source preparing method by nickel foil auto-deposition |
US9662640B2 (en) | 2013-12-27 | 2017-05-30 | Rive Technology, Inc. | Introducing mesoporosity into zeolite materials with a modified acid pre-treatment step |
EP3119500A4 (en) | 2014-03-21 | 2017-12-13 | SDC Materials, Inc. | Compositions for passive nox adsorption (pna) systems |
JP6498216B2 (en) * | 2014-05-21 | 2019-04-10 | デー.スワロフスキー カーゲーD.Swarovski KG | Method for partially coating the surface of an object |
WO2016094816A1 (en) | 2014-12-11 | 2016-06-16 | Rive Technology, Inc. | Preparation of mesoporous zeolites with reduced processing |
US10626019B2 (en) | 2014-12-30 | 2020-04-21 | W. R. Grace & Co.-Conn. | Methods for preparing zeolites with surfactant-templated mesoporosity and tunable aluminum content |
KR102420015B1 (en) * | 2015-08-28 | 2022-07-12 | 삼성전자주식회사 | Shower head of Combinatorial Spatial Atomic Layer Deposition apparatus |
US10991867B2 (en) | 2016-05-24 | 2021-04-27 | University Of Utah Research Foundation | High-performance terbium-based thermoelectric materials |
WO2019034953A1 (en) * | 2017-08-18 | 2019-02-21 | 3M Innovative Properties Company | Magnetic film |
CN112041663A (en) * | 2018-03-02 | 2020-12-04 | 建新公司 | Multivariate spectral analysis and monitoring for bio-manufacturing |
JP2022532494A (en) * | 2019-05-16 | 2022-07-15 | ドラゴンフライ エナジー コーポレイション | Systems and methods for dry powder coating layers of electrochemical cells |
CN110308113B (en) * | 2019-07-04 | 2021-06-22 | 中南林业科技大学 | A quasi-spherical fruit device of all-round upset for near infrared spectrum detects |
CN110498615A (en) * | 2019-09-27 | 2019-11-26 | 大连交通大学 | A method of densification CuO film is prepared using sol-gel spin-coating method |
US11752700B2 (en) | 2019-10-01 | 2023-09-12 | Massachusetts Institute Of Technology | Systems and methods for formulating material in a data-driven manner |
KR20210108790A (en) * | 2020-02-26 | 2021-09-03 | 삼성전자주식회사 | deposition apapratus and deposition method |
EP3971319A4 (en) * | 2020-03-18 | 2023-01-04 | Thermalytica, Inc. | Vapor deposition device |
US11542597B2 (en) | 2020-04-08 | 2023-01-03 | Applied Materials, Inc. | Selective deposition of metal oxide by pulsed chemical vapor deposition |
US11610652B2 (en) | 2020-05-06 | 2023-03-21 | Toyota Research Institute, Inc. | Autonomous inorganic material synthesis machine |
RU2745223C1 (en) * | 2020-06-17 | 2021-03-22 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method for combinatorial production of new compositions of materials in a multicomponent system |
CN112675798B (en) * | 2020-12-14 | 2022-11-08 | 上海天马微电子有限公司 | Microfluidic reaction device and microfluidic reaction driving method |
CN112973816B (en) * | 2021-04-15 | 2022-10-04 | 上海理工大学 | Differential shunt device and preparation method and application thereof |
DE102021113282A1 (en) | 2021-05-21 | 2022-11-24 | Ruhr-Universität Bochum, Körperschaft des öffentlichen Rechts | Apparatus and method for creating a layer of material on a substrate surface from multiple material sources |
CN114441506B (en) * | 2022-04-08 | 2022-06-21 | 港湾之星健康生物(深圳)有限公司 | Quantum magneto-optical sensor |
Family Cites Families (130)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB844359A (en) * | 1958-03-06 | 1960-08-10 | Rockcote Paint Company | Improvements relating to display devices |
US2981607A (en) * | 1958-07-11 | 1961-04-25 | Western Electric Co | Non-destructive tests for distinguishing between objects formed of dissimilar metals |
US3010880A (en) * | 1959-05-08 | 1961-11-28 | Media Inc | Device for determining bacterial sensitivities |
US3227522A (en) * | 1961-09-19 | 1966-01-04 | Ankh Lab Inc | Assaying apparatus |
NL283619A (en) * | 1961-10-06 | |||
US3377209A (en) * | 1964-05-01 | 1968-04-09 | Ca Nat Research Council | Method of making p-n junctions by hydrothermally growing |
US3323644A (en) * | 1965-01-25 | 1967-06-06 | Miles C Wells | Coin holder and visual display |
US3536452A (en) | 1965-04-21 | 1970-10-27 | Marathon Oil Co | Multiple reactor apparatus |
US3520716A (en) | 1966-06-07 | 1970-07-14 | Tokyo Shibaura Electric Co | Method of vapor depositing multicomponent film |
US3431077A (en) | 1966-07-18 | 1969-03-04 | Joseph D Danforth | Analytical apparatus |
US3474004A (en) * | 1967-09-21 | 1969-10-21 | Aaron J Fink | Disposable culture device |
US3505023A (en) | 1967-11-13 | 1970-04-07 | Research Corp | Thermally conditioned spot plate |
US3652457A (en) * | 1968-09-30 | 1972-03-28 | Chevron Res | Hydrothermal method of manufacturing a hydrocarbon conversion catalyst containing at least one hydrogenating component and the catalyst so manufactured |
US3709979A (en) * | 1970-04-23 | 1973-01-09 | Mobil Oil Corp | Crystalline zeolite zsm-11 |
JPS4934573B1 (en) * | 1970-11-06 | 1974-09-14 | ||
US3812254A (en) * | 1971-06-25 | 1974-05-21 | Ppg Industries Inc | Control of pythium spp.and sclerotium spp.using azides |
DE2160008B2 (en) | 1971-12-03 | 1973-11-15 | Robert Bosch Gmbh, 7000 Stuttgart | Method and device for producing a pattern in a metal layer vapor-deposited on a carrier, and the use thereof |
US3819490A (en) * | 1971-12-08 | 1974-06-25 | E Klingstrom | Testing device for use when making bacteriological tests |
US3919589A (en) | 1973-04-06 | 1975-11-11 | Rca Corp | Electroluminescent cell with a current-limiting layer of high resistivity |
US3868221A (en) * | 1973-08-31 | 1975-02-25 | Bell Telephone Labor Inc | Method and apparatus for degradation testing of stabilized polymers |
GB1436859A (en) * | 1973-12-01 | 1976-05-26 | Tioxide Group Ltd | Glazing composition |
SE380099B (en) | 1974-02-07 | 1975-10-27 | Monega Anstalt | |
US3871935A (en) * | 1974-03-14 | 1975-03-18 | Bell Telephone Labor Inc | Method of encapsulating and terminating the fibers of an optical fiber ribbon |
JPS5744753Y2 (en) | 1975-03-15 | 1982-10-02 | ||
US4099923A (en) * | 1977-01-17 | 1978-07-11 | The Standard Oil Company | Automatic catalytic screening unit |
DE2714939C3 (en) | 1977-04-02 | 1980-08-14 | Hoechst Ag, 6000 Frankfurt | Method and device for investigating the effectiveness of solid catalysts |
US4225575A (en) | 1978-05-15 | 1980-09-30 | Ventrex Laboratories, Inc. | Method and apparatus for performing in vitro clinical diagnostic tests using a solid phase assay system |
US4185468A (en) | 1978-02-28 | 1980-01-29 | Adams Clyde M Jr | Apparatus for separation, refinement, extraction and/or concentration by liquation |
US4160804A (en) * | 1978-08-02 | 1979-07-10 | Victory Thomas J | Device for assaying gold and other metals |
FR2450162A1 (en) * | 1978-11-20 | 1980-09-26 | Anurdi | Coloured panels for decorative use - has design made from modular squares in rows with effect depending on controlled basic colour shading |
US4263010A (en) | 1979-10-31 | 1981-04-21 | University Patents, Inc. | Control method and apparatus for crystallizer process control |
US4468419A (en) * | 1980-03-03 | 1984-08-28 | Fabrik, Inc. | Method of making a dinnerware article |
US5328549A (en) | 1980-04-10 | 1994-07-12 | Massachusetts Institute Of Technology | Method of producing sheets of crystalline material and devices made therefrom |
IL60254A (en) | 1980-06-08 | 1983-11-30 | Yeda Res & Dev | Resolution of amino acids |
US4416632A (en) * | 1981-04-02 | 1983-11-22 | Avalon Industries, Inc. | Paint-by-numbers kit |
US4422151A (en) * | 1981-06-01 | 1983-12-20 | Gilson Robert E | Liquid handling apparatus |
JPS58223618A (en) * | 1982-06-14 | 1983-12-26 | Sumitomo Alum Smelt Co Ltd | Compound oxide for electrically conductive filler |
US4489133A (en) | 1982-11-16 | 1984-12-18 | The Board Of Trustees Of The Leland Stanford Jr. University | Two-dimensional crystallization technique |
US4845069A (en) * | 1983-09-29 | 1989-07-04 | The Dow Chemical Company | Porous amorphous metallo phosphates process for preparing porous amorphous metallo phosphates |
EP0164206B1 (en) * | 1984-05-02 | 1988-11-02 | Brendan James Hamill | An apparatus for the chemical synthesis of oligonucleotides |
GB8421603D0 (en) * | 1984-08-24 | 1984-09-26 | British Petroleum Co Plc | Synthetic smectites and stabilised pillared analogues |
JPS6171954A (en) * | 1984-09-14 | 1986-04-12 | Hitachi Seiko Ltd | Grinding method with cup-shaped grinding wheel |
US4591215A (en) * | 1984-09-17 | 1986-05-27 | Howard Robbins | Merchandising and display device |
US5045916A (en) * | 1985-01-22 | 1991-09-03 | Fairchild Semiconductor Corporation | Extended silicide and external contact technology |
DD234941A1 (en) * | 1985-02-28 | 1986-04-16 | Leuna Werke Veb | METHOD AND ARRANGEMENT FOR CATALYST ACTIVITY DETERMINATION |
GB2176932A (en) * | 1985-05-28 | 1987-01-07 | Agricultural Genetics Co | Sample plate for immunosorbent electron microscopy |
IT1186974B (en) * | 1985-06-18 | 1987-12-16 | Alberto Koelowicz | IMPROVEMENTS IN THE JOINTING DEVICES TO BIND THE SUPERIMPOSED FABRICS OF CLOTHING OR ARTICLES WITH THEM PACKED |
US4735778A (en) * | 1985-08-28 | 1988-04-05 | Kureha Kagaku Kohyo Kabushiki Kaisha | Microtiter plate |
US4774058A (en) * | 1985-09-26 | 1988-09-27 | Mehl Ehrenfried L | Apparatus for, and methods of, operating upon a fluid |
US5242675A (en) | 1985-10-15 | 1993-09-07 | Exxon Research & Engineering Company | Zeolite L |
JPS62106000A (en) | 1985-10-30 | 1987-05-16 | Fujitsu Ltd | Apparatus for automatic production of biopolymer crystal |
US4728591A (en) * | 1986-03-07 | 1988-03-01 | Trustees Of Boston University | Self-assembled nanometer lithographic masks and templates and method for parallel fabrication of nanometer scale multi-device structures |
GB2194847A (en) | 1986-09-05 | 1988-03-16 | Marconi Co Ltd | Image converter |
US4859538A (en) | 1986-11-20 | 1989-08-22 | Ribi Hans O | Novel lipid-protein compositions and articles and methods for their preparation |
US5096867A (en) * | 1990-06-04 | 1992-03-17 | Exxon Chemical Patents Inc. | Monocyclopentadienyl transition metal olefin polymerization catalysts |
US5198401A (en) * | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
CA1339019C (en) * | 1987-02-05 | 1997-03-25 | Sumitomo Electric Industries, Ltd. | Process for preparing a superconducting thin film |
US5306411A (en) * | 1989-05-25 | 1994-04-26 | The Standard Oil Company | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions |
US5364765A (en) * | 1987-05-28 | 1994-11-15 | Abbott William A | Method and reagent system for assaying isoenzyme profiles |
US4837374A (en) * | 1987-06-01 | 1989-06-06 | Brown James R | Microreactor for analyzing thin solid samples |
US4814056A (en) * | 1987-06-23 | 1989-03-21 | Vac-Tec Systems, Inc. | Apparatus for producing graded-composition coatings |
US4990216A (en) | 1987-10-27 | 1991-02-05 | Fujitsu Limited | Process and apparatus for preparation of single crystal of biopolymer |
US4958335A (en) * | 1987-12-23 | 1990-09-18 | Oki Electric Industry Co., Ltd. | Optical head assembly with a minimum of inertia and feasible for high high-speed access |
US5034359A (en) * | 1988-04-08 | 1991-07-23 | Kabushiki Kaisha Toshiba | Insulating composition |
US5039614A (en) | 1988-06-16 | 1991-08-13 | Armenag Dekmezian | Method and apparatus for collecting samples for analysis of chemical composition |
US4956335A (en) * | 1988-06-20 | 1990-09-11 | Eastman Kodak Company | Conductive articles and processes for their preparation |
SE8802403D0 (en) * | 1988-06-28 | 1988-06-28 | Pharmacia Ab | MUST BE USED IN EXCLUSIVE EPIC TESTING TO PAVISA CONTACT ALERGY |
JPH03505966A (en) * | 1988-07-14 | 1991-12-26 | ベイラー カレッジ オブ メディシン | Solid-phase assembly and reassembly method for biopolymers |
US5281540A (en) * | 1988-08-02 | 1994-01-25 | Abbott Laboratories | Test array for performing assays |
US5118648A (en) * | 1988-10-05 | 1992-06-02 | Mobil Oil Corporation | Particulate polymer-supported olefin polymerization catalyst |
US5024992A (en) * | 1988-10-28 | 1991-06-18 | The Regents Of The University Of California | Preparation of highly oxidized RBa2 Cu4 O8 superconductors |
US5120707A (en) * | 1989-05-22 | 1992-06-09 | Allied-Signal, Inc. | Superconducting ceramics by electrodeposition of metals with embedment of particulate matter, followed by oxidation |
US5527681A (en) | 1989-06-07 | 1996-06-18 | Affymax Technologies N.V. | Immobilized molecular synthesis of systematically substituted compounds |
US5744101A (en) | 1989-06-07 | 1998-04-28 | Affymax Technologies N.V. | Photolabile nucleoside protecting groups |
US5424186A (en) * | 1989-06-07 | 1995-06-13 | Affymax Technologies N.V. | Very large scale immobilized polymer synthesis |
US5143854A (en) * | 1989-06-07 | 1992-09-01 | Affymax Technologies N.V. | Large scale photolithographic solid phase synthesis of polypeptides and receptor binding screening thereof |
WO1991002975A1 (en) | 1989-08-21 | 1991-03-07 | The Board Of Regents Of The University Of Washington | Multiple-probe diagnostic sensor |
US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
JPH03174386A (en) * | 1989-11-30 | 1991-07-29 | Nippon Dempa Kogyo Co Ltd | Autoclave |
CZ280777B6 (en) * | 1990-02-02 | 1996-04-17 | Ústav Organické Chemie A Biochemie Avčr | Process of multistep synthesis of peptides on planar carriers and apparatus for making the same |
JPH0450804A (en) * | 1990-06-15 | 1992-02-19 | Ricoh Co Ltd | Manufacture of mirolens array |
US5308411A (en) * | 1990-06-20 | 1994-05-03 | Nippon Steel Corporation | Ultrahigh silicon, grain-oriented electrical steel sheet and process for producing the same |
US5801113A (en) | 1990-06-22 | 1998-09-01 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
JPH0710730B2 (en) * | 1990-11-22 | 1995-02-08 | 信越化学工業株式会社 | Method for producing rare earth oxide |
DE69133293T2 (en) * | 1990-12-06 | 2004-05-27 | Affymetrix, Inc., Santa Clara | Processes and reagents for immobilized polymer synthesis on a very large scale |
AU9136391A (en) * | 1990-12-27 | 1992-08-17 | Exxon Chemical Patents Inc. | An amido transition metal compound and a catalyst system for the production of isotactic polypropylene |
US5200910A (en) | 1991-01-30 | 1993-04-06 | The Board Of Trustees Of The Leland Stanford University | Method for modelling the electron density of a crystal |
JPH06102535B2 (en) * | 1991-03-01 | 1994-12-14 | 住金ホトンセラミックス株式会社 | Kaolinite synthesizer |
US5236998A (en) | 1991-03-07 | 1993-08-17 | Occidental Chemical Corporation | Process for the manufacture of linear polyethylene containing α-alkene commonomers |
US5365458A (en) * | 1991-03-29 | 1994-11-15 | Nippon Densan Corporation | Motor eccentricity measuring apparatus |
EP0514715B1 (en) | 1991-05-17 | 1997-12-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for producing a particulate zeolite |
US5200023A (en) | 1991-08-30 | 1993-04-06 | International Business Machines Corp. | Infrared thermographic method and apparatus for etch process monitoring and control |
US5474796A (en) * | 1991-09-04 | 1995-12-12 | Protogene Laboratories, Inc. | Method and apparatus for conducting an array of chemical reactions on a support surface |
US5294198A (en) | 1991-10-01 | 1994-03-15 | Cincinnati Electronics Corporation | Infrared inspection system and method employing emissivity indications |
MX9205727A (en) * | 1991-10-09 | 1993-04-01 | Schering Corp | DEVICE FOR THE FORMATION OF CRYSTALS AND AUTOMATED CRYSTALLIZATION SYSTEM |
IL103674A0 (en) * | 1991-11-19 | 1993-04-04 | Houston Advanced Res Center | Method and apparatus for molecule detection |
EP1086742B2 (en) * | 1991-11-22 | 2007-03-14 | Affymetrix, Inc. (a Delaware Corporation) | Combinatorial strategies for polymer synthesis |
US5384261A (en) * | 1991-11-22 | 1995-01-24 | Affymax Technologies N.V. | Very large scale immobilized polymer synthesis using mechanically directed flow paths |
US5871713A (en) | 1991-12-04 | 1999-02-16 | Guerbet S.A. | Macromolecular polyamine iodine-containing compound, process for its preparation and its use as a contrast agent |
US5344236A (en) | 1992-01-23 | 1994-09-06 | Fishman Iiya M | Method for evaluation of quality of the interface between layer and substrate |
JP2962024B2 (en) * | 1992-02-04 | 1999-10-12 | 松下電器産業株式会社 | Method for manufacturing optical waveguide and method for manufacturing optical wavelength conversion element |
US5367403A (en) * | 1992-04-08 | 1994-11-22 | Matsushita Electric Industrial Co., Ltd. | Optical element and method of fabricating the same |
JP2882234B2 (en) | 1992-04-08 | 1999-04-12 | 松下電器産業株式会社 | Method of manufacturing polarization splitting element and optical information processing device |
JP3231836B2 (en) * | 1992-04-17 | 2001-11-26 | 日東電工株式会社 | Lens array plate, liquid crystal display device and optical connector |
US5541061A (en) * | 1992-04-29 | 1996-07-30 | Affymax Technologies N.V. | Methods for screening factorial chemical libraries |
US5264722A (en) * | 1992-06-12 | 1993-11-23 | The United States Of America As Represented By The Secretary Of The Navy | Nanochannel glass matrix used in making mesoscopic structures |
US5256241A (en) | 1992-08-28 | 1993-10-26 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Method for controlling protein crystallization |
US5288514A (en) * | 1992-09-14 | 1994-02-22 | The Regents Of The University Of California | Solid phase and combinatorial synthesis of benzodiazepine compounds on a solid support |
US5324483B1 (en) * | 1992-10-08 | 1996-09-24 | Warner Lambert Co | Apparatus for multiple simultaneous synthesis |
US5356756A (en) * | 1992-10-26 | 1994-10-18 | The United States Of America As Represented By The Secretary Of Commerce | Application of microsubstrates for materials processing |
JPH06171954A (en) * | 1992-12-03 | 1994-06-21 | Mitsubishi Materials Corp | Production of lanthanum strontium cobaltate powder |
US5679548A (en) | 1993-02-02 | 1997-10-21 | The Scripps Research Institute | Methods for producing polypeptide metal binding sites and compositions thereof |
JPH06230204A (en) * | 1993-02-05 | 1994-08-19 | Asahi Optical Co Ltd | Production of synthetic resin optical element having refractive index distribution |
US5378916A (en) * | 1993-02-17 | 1995-01-03 | Xerox Corporation | Color imaging charge-coupled array with multiple photosensitive regions |
US5342581A (en) * | 1993-04-19 | 1994-08-30 | Sanadi Ashok R | Apparatus for preventing cross-contamination of multi-well test plates |
US5766875A (en) * | 1993-07-30 | 1998-06-16 | Molecular Devices Corporation | Metabolic monitoring of cells in a microplate reader |
JP3307732B2 (en) * | 1993-09-03 | 2002-07-24 | 英俊 長本 | Resistive material and resistivity control method |
US5622719A (en) | 1993-09-10 | 1997-04-22 | Fuisz Technologies Ltd. | Process and apparatus for making rapidly dissolving dosage units and product therefrom |
US5416613A (en) | 1993-10-29 | 1995-05-16 | Xerox Corporation | Color printer calibration test pattern |
AU677145B2 (en) | 1993-12-21 | 1997-04-10 | Mobil Oil Corporation | Catalyst composition |
JPH07226884A (en) | 1994-02-14 | 1995-08-22 | Mitsubishi Electric Corp | Solid-state image pickup device |
US6015880A (en) | 1994-03-16 | 2000-01-18 | California Institute Of Technology | Method and substrate for performing multiple sequential reactions on a matrix |
US5450372A (en) * | 1994-03-30 | 1995-09-12 | At&T Corp. | Magnetoresistive microphone and acoustic sensing devices |
JPH07309623A (en) * | 1994-05-18 | 1995-11-28 | Shin Etsu Chem Co Ltd | Production of angular rare earth element-ammonium oxalate double salt and angular oxide of rare earth element |
US5985356A (en) * | 1994-10-18 | 1999-11-16 | The Regents Of The University Of California | Combinatorial synthesis of novel materials |
US5688696A (en) | 1994-12-12 | 1997-11-18 | Selectide Corporation | Combinatorial libraries having a predetermined frequency of each species of test compound |
DE19548221C1 (en) | 1995-12-22 | 1997-05-15 | Biotest Pharma Gmbh | Oral use of immunoglobulin preparations for the treatment and prophylaxis of chronic pain |
US6063633A (en) | 1996-02-28 | 2000-05-16 | The University Of Houston | Catalyst testing process and apparatus |
IT1283191B1 (en) * | 1996-03-05 | 1998-04-16 | Luigi Ramari | QUICK CONNECTOR WITH AUTOMATIC ENGAGEMENT AND RELEASE BY MOVING AN EXTERNAL BODY |
US6200023B1 (en) * | 1999-03-15 | 2001-03-13 | Steag Rtp Systems, Inc. | Method for determining the temperature in a thermal processing chamber |
-
1994
- 1994-10-18 US US08/327,513 patent/US5985356A/en not_active Expired - Lifetime
-
1995
- 1995-05-08 US US08/438,043 patent/US5776359A/en not_active Expired - Fee Related
- 1995-06-07 US US08/482,921 patent/US6326090B1/en not_active Expired - Lifetime
- 1995-10-18 JP JP51341396A patent/JP3893152B2/en not_active Expired - Lifetime
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- 1995-10-18 DE DE69535128T patent/DE69535128T2/en not_active Expired - Lifetime
- 1995-10-18 EP EP05012305A patent/EP1579908B1/en not_active Expired - Lifetime
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- 1995-10-18 AU AU39577/95A patent/AU3957795A/en not_active Abandoned
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1997
- 1997-04-17 NO NO971777A patent/NO971777L/en not_active Application Discontinuation
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- 1998-07-27 US US09/122,932 patent/US6410331B1/en not_active Expired - Lifetime
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- 1998-07-31 US US09/127,195 patent/US6346290B1/en not_active Expired - Lifetime
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- 2000-11-28 US US09/728,201 patent/US6649413B1/en not_active Expired - Fee Related
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- 2001-02-26 US US09/794,228 patent/US20010055669A1/en not_active Abandoned
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- 2002-02-11 US US10/074,745 patent/US7034091B2/en not_active Expired - Fee Related
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- 2003-01-23 US US10/350,703 patent/US20040014077A1/en not_active Abandoned
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