WO1994015258A1 - Photodefinable polymers containing perfluorocyclobutane groups - Google Patents
Photodefinable polymers containing perfluorocyclobutane groups Download PDFInfo
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- WO1994015258A1 WO1994015258A1 PCT/US1993/011562 US9311562W WO9415258A1 WO 1994015258 A1 WO1994015258 A1 WO 1994015258A1 US 9311562 W US9311562 W US 9311562W WO 9415258 A1 WO9415258 A1 WO 9415258A1
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- bis
- trifluoroethenyloxyphenyl
- acetophenone
- pas
- propene
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- QTJSTTBYEOELOW-UHFFFAOYSA-N Cc(cc1)ccc1ON Chemical compound Cc(cc1)ccc1ON QTJSTTBYEOELOW-UHFFFAOYSA-N 0.000 description 1
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- C07C59/40—Unsaturated compounds
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- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
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- C07C65/28—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups having unsaturation outside the aromatic rings
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- C07C65/32—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups
- C07C65/40—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups containing singly bound oxygen-containing groups
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
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- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Definitions
- This invention relates to photoimageable polymers, particularly those polymers having perfluorocyclobutane groups.
- Photoimageable polymers are widely used, especially in the electronics industry to apply coatings of polymer to exact portions of an electronic device, often such that other materials, for instance metals can be applied in regions not coated with polymer.
- There are a number of ways of achieving the desired results conveniently classified into positive photoresists, in which the area exposed to light is removed, and negative photoresists, in which the area exposed to light is insolubilized and remains after the unexposed area is removed.
- Polyimide negative photoresists are widely used in electronics. Because most polyimides are nearly insoluble in common organic solvents, a soluble precursor is generally used.
- the precursor has a photosensitive group such as a methacrylate ester group.
- the photosensitive group results in crosslinking of the precursors on exposure to light of a certain wavelength, such that unexposed precursor can be removed by solvent washing. Then the remaining precursor is converted to polyimide by exposure to heat of 400°C. Exposure to such heat results in loss of the photosensitive groups and water. Loss of such materials requires removal of them and often results in bubbles and shrinkage of from 15 to 50 percent.
- Photodefinable polyimides that are not subjected to a high temperaure post-cure contain unreacted polyamic acid groups that contribute to increases in the dielectric constant and water absorption of the polymer. Such systems are described in references such as Rohde et al. " Recent Advances in Photoimageable Polyimides,” SPIE Vol. 539 Advances in Resist Technology and Processing II (1985).
- a photoimageable polymer which does not lose water or other materials in its formation or insolubilization, and therefore has less resulting shrinkage, which does not require heating to 300 or 400°C, shows a hypsochromic or bathochromic shift (that is a shift of the absorption maxiumum to shorter or longer wavelengths respectively) when irradiated and which has properties such as low dielectric constant, low dissipation factor, low moisture absorbance, low ionic mobility or ionic transport properties, optical clarity (to visible light) good planarizability, good compatibility of the prepolymer with a wide variety of organic solvents (such as ethers, ketones, aromatics, that is, compounds containing a benzene ring, either substituted or unsubstituted, including fused ring systems such as naphthalene, as is described by Andrew Streitwieser, Jr.
- organic solvents such as ethers, ketones, aromatics, that is, compounds containing a benzene ring
- the invention is a polymer having at least one photoactive site and more than one perfluorocyclobu tane group
- the invention also includes monomers containing photoactive sites or photoactive precursors for making such polymers
- the invention includes the uses of such polymers in coatings and in negative photoresists
- the invention includes processes of making such polymers and the monomers from which they are made
- Polymers of the invention have at least one photoactive site, that is a grouping of atoms capable of absorbing energy from incident photonic radiation such that the polymer becomes less soluble or dispersible in at least one solvent or dispersing medium than it was before exposure to the incident photonic radiation.
- Compounds of the invention also have such photoactive sites or photoactive precursors; in which case, a polymer made at least partially from such compounds containing photoactive sites becomes less soluble or dispersible upon photonic irradiation. Decreasing solubility or dispersibility is also evidenced by differential solubility between exposed and unexposed polymer, for example in a layer, a first o portion of which is exposed to incident photonic radiation and second portion of which remains unexposed.
- incident photonic radiation or “actinic radiation” refers to energy in the form of electromagnetic waves of a wavelength capable of exciting bonding or non- 5 bonding electrons in certain functional groups referred to herein as photoactive sites or the active portion of such sites to produce a chemical reaction.
- polymer is used herein to include any compound or compounds comprised of two or more like or different monomer units.
- polymer includes 0 prepolymers, dinners, trimers, tetramers and other oligomers.
- a solid, gel, or organic phase separates from a liquid medium; more solvent is required to dissolve or disperse the same weight of polymer; latex particles coalesce; an 5 emulsion separates or requires additional stirring.
- the polymer is optionally dissolved or dispersed in any medium effective therefor.
- polymers of the invention are advantageously dissolved in solvents such as ethers, ketones, aromatic hydrocarbons, polar aprotic solvents, halocarbon solvents and the like.
- mesitylene, diglyme, n-methylpyrrolidinone, and dimethylformamide are advantageously used in electronic 0 applications such as depositing a layer of polymer on a substrate such as a metal (for example copper, aluminum, indium, tin, silver, gold, platinum, cadminum and alloys thereof), silicon, silicon oxide, gallium arsenide, germanium arsenide, barrium ferrite, alloy of chromium and at least one other metal, ceramitized glass, indium tin oxide, glass, quartz, a like, similar, or different polymer (particularly epoxy resins, polycarbonates, polyesters, polyimides, 5 polystyrenes (particularly syndiotactic), benzocyclobutenes, acrylics, other perfluorocyclobutane-containing polymers having differenct aryl groups and combinations thereof), graphite, combinations of the.above and the like.
- a metal for example copper, aluminum, indium, tin, silver, gold
- the polymer may be dispersed in an aqueous and/or organic medium particularly in an aqueous medium.
- an aqueous and/or organic medium particularly in an aqueous medium.
- Reduced solubility or dispersibility is believed to be associated with increased molecular weight of the polymer, for instance from increasing chain length, or preferably crosslinking
- the decreased solubility or dispersibility is a result of chemical changes (chemical reactions), which more preferably result in the formation of covalent bonds. Formation of coatings and other layers of this type of polymer is advantageously as disclosed in U.S Patent 5,246,782 (Kennedy et al )
- Polymers of the invention additionally have more than one perfluorocyclobutane group.
- Methods of making polymers having perfluorocyclobutane groups are disclosed in U.S Patents 5,021,602; 5,023,386; 5,037,917, 5,037,918 and 5,037,919.
- U.S. Patent 5,021,602 (Clement et al.) discloses compounds of the formula:
- R and R' independently represent optionally inertly substituted hydrocarbyl groups
- X and X' represent any molecular structures which link R and R' with the perfluorocyclobutane ring
- n and n' are the number of G and G' groups, respectively
- G and G' independently represent any reactive functional groups or any groups convertible into reactive functional group and methods for making such compounds and forming polymers therefrom
- R represents an unsubstituted or inertly substituted hydrocarbyl group
- m is an integer of from 1 to 3 and methods for making such compounds and forming polymers therefrom.
- R represents an optionally substituted hydrocarbyl group
- X represents any group which links R and a trifluorovinyl (perfluorovinyl, trifluoroethenyl, or perfluoroethenyl) group
- n is the number of G groups
- G represents any reactive functional group or a group convertible into a reactive functional group and methods for making such compounds and forming polymers therefrom.
- R and R' preferably have from 6 to 100 carbon atoms, more preferably from 6 to 50 carbon atoms, most preferably from 6 to 25 carbon atoms.
- the molecular fragments designated R and R' in Formulas l-lll optionally have photoactive sites.
- Photoactive sites include those having at least two conjugated multiple bonds (wherein the term "multiple bonds” is used to include double, triple or aromatic bonds between two carbon atoms, between a carbon atom and a heteroatom such as an oxygen, nitrogen, sulfur, phosphorus or between two or more heteroatoms such as between sulfur and oxygen, phosphorus and oxygen or sulfur, nitrogen and oxygen, or nitrogen and nitrogen such that incident photonic radiation is absorbed by the molecule.
- multiple bonds is used to include double, triple or aromatic bonds between two carbon atoms, between a carbon atom and a heteroatom such as an oxygen, nitrogen, sulfur, phosphorus or between two or more heteroatoms such as between sulfur and oxygen, phosphorus and oxygen or sulfur, nitrogen and oxygen, or nitrogen and nitrogen such that incident photonic radiation is absorbed by the molecule.
- photoactive sites include molecular groups such as: R'
- O' for example acrylates, methacrylates, such
- each R" is H or a hydrocarbyl group which is optionally inertly substituted, preferably H or a hydrocarbyl group of from 1 to 12 carbon atoms, more preferably H or an alkyl hydrocarbyl group of from 1 to 6 carbon atoms; and Y stands for a bond to any
- n is independently an integer 0 to 11.
- n is independently an integer of from 0 to 11.
- n is independently an integer of from 1 to 12 and with optional addition unsaturation in the cycloalkylring
- Any photoactive site or compound containing such a site is optionally inertly substituted, that is substituted with any group which does not undesirably affect the function of the photoactive site.
- the photoactive site (represented hereinafter as "PAS") is optionally any part of a compound and optionally becomes part of a polymer backbone or side chain.
- PAS photoactive site
- a monomer is represented:
- PAS is a photoactive site or photoactive precursor as defined previously; and q is an integer of from 0 to 4.
- the photoactive sites are in the polymer backbone.
- the photoactive sites are in side chains such as when a compound such as
- photoactive sites are formed on already formed polymers having plural perfluorocyclobutane groups, such as by reaction of compounds having photoactive sites or photoactive precursors that are subsequently converted to photoactive sites with any polymer formed by a process taught in any of the already cited patents disclosing perfluorocyclobutane containing polymers.
- the compounds are suitably formed by methods disclosed in the cited references from starting materials having the desired photoactive s ⁇ te(s) or from starting materials having precursors for the photoactive sites
- zinc is used to form trifluorovinyl groups from bromotetrafluoroethyl groups
- precursors for photoactive sites containing carbon-carbon double bonds conjugated with aromatic rings and carbon- oxygen double bonds because such double bonds are often attacked by zinc under reaction conditions
- para-perfluoroethenyloxybenzaldehyde can be formed by reaction of zinc with para-bromotetrafluoroethoxybenzaldehyde; then for instance, the para- perfluoroethenyloxybenzaldehyde can be condensed in an aldol condensation with a ketone, either two moles of
- PAP and PAP' are photoactive precursors (any group(s) which can react to form a photoactive group), where PAP represents a group which can be modified to become photoactive (either a single group or a group illustrated by the benzaldehyde and acetophenone groups in the above illustration which can react, optionally with other reactants, to become a photoactive site);
- PAP, X and q are defined as for Formula VI; and each Z is independently iodine or bromine;
- Step d is suitably before or after step(s) b and/or c.
- Those skilled in the art are able to ascertain suitable order of steps from chemical sensitivity and reactivities of groups present with reactants used in the steps.
- groups represented by PAP, and PAS optionally include groups which are not photoactive along with the photoactive groups.
- the molecular structure between the X's in Formula IV is optionally not itself totally photoactive but has, for instance a pendant photoactive group or a reactive group to which a photoactive site may be attached.
- the step of modifying the photoactive precursor(s) optionally includes reactions which combine like or different precursors to form a photoactive site as illustrated by the condensation of aldehydes and ketones already discussed.
- one site in a molecule is chemically modified.
- a photoactive site of unsaturation carbon-carbon double bond
- a photoactive site may be modified via reactive substitution to change the quantum yield or absorption maximum of the chromophore.
- the compound 4-(trifluoroethenyloxy)- ⁇ -(4-nitrobenzylidene) acetophenone formed bythe Aldol condensation of 4-(trifluoroethenyloxy)acetophenone with 4-nitrobenzaldehyde, is suitably catalytically hydrogenated using palladium on carbon to reduce the nitro group to an amine, thereby changing the absorption spectrum of the chromophore.
- the resulting amine is optionally subsequently reacted with iodomethane to form the dimethylamine compound to further change the absorption characteristics of the chromophore.
- Steps (a) through (c) of the process are advantageously carried out as described in U.S. Patent 5,023,380.
- Compounds of Formula IV where q is at least 1 are homo or copolymerized to form polymers having photoactive sites and perfluorocyclobutane groups.
- a compound of Formula VI where q is 0 is used to form a compound of Formula IV where q is 0 and wherein the molecular structure represented by PAP includes a group reactive with at least one compound to become a photoactive site.
- the compound CF CF-X-PAP has onetrifluorovinyl group which is reacted into perfluorocyclobutane-containing polymers (by processes such as those disclosed in U.S. Patents 5,037,917 and 5,037,918), which polymers then have side chains corresponding to molecular structures represented by PAP.
- Exemplary of compounds of Formula VI where q is 0 are p- perfluoroethenyloxyacetophenones (optionally substituted for instance with cyano, nitro, sulfonate ester, sulfonamide, trifluoromethyl, carboxylic ester, aldehyde, ketone, or halo (preferably fluoro, bromo or chloro) groups in the ortho and/or meta positions) which are reactive, for instance under acid conditions (including hydrochloric acid in ethanol) with optionally substituted benzaldehydes.
- p- perfluoroethenyloxyacetophenones optionally substituted for instance with cyano, nitro, sulfonate ester, sulfonamide, trifluoromethyl, carboxylic ester, aldehyde, ketone, or halo (preferably fluoro, bromo or chloro) groups in the ortho and/or meta positions) which are reactive, for instance under acid conditions (
- Such electron donating substituents as methoxy, ethoxy, or dimethylamino groups para to an aldehyde or propenaldehyde group act to move the wavelength of light absorbed by the resulting chalcone group from 300-320 nm to 340-420 nm wavelengths, for instance 414 nm in the case of the p-dimethylammo substituted aldehyde
- Electron releasing groups such as secondary or tertiary amines, hydroxy groups, ethers, alkoxy groups preferably of from one to 12 carbon atoms or alkyl groups preferably having from 1 to 12 carbon atoms, on the benzaldehyde act to further induce charge separation and cause the resulting compound to absorb light at longer wavelengths.
- Benzaldehyde is illustrative of aldehydes useful in the process; such aldehydes include unsubstituted or inertly substituted, cinnamaldehydes, acroleins, furfural, heptadienals (and other polyene aldehydes), retinals, phenyl-2,4-pentadienal terephthaldehyde, naphthalenedicarboxaldehyde, furylpolyene aldehydes and combinations thereof.
- a compound of Formula VI where q is 0 is reacted with a compound having at least two, preferably at least three, trifluorovinyl groups such that a perfluorocyclobutane group is formed in a compound having at least one, preferably at least two, more preferably two, trifluorovinyl groups for subsequent polymer formation.
- Such compounds include reaction products of 1,1 ,1-tris (4'- trifluoroethenyloxyphenyl) ethane with compounds of Formula IV such as 1-acroyloxy-2-(4- trifluoroethenyloxy)-benzoyloxyethane and 1-methacroyloxy-2-(4-trifluoroethenyloxy)- benzoyloxyethane and the like.
- X, PAP, m and n are as defined for Formulas I and II, and Q is bromine, chlorine or iodine: and G" is a functional group G; as previously defined, or a functional group suitable for conversion into G: and each PAP' is independently the same or different photoactive precursor which react with one another to form a photoactive site;
- Step d' is carried out as step d in the process for making compounds of Formula VIII and optionally takes place between steps a' and b', b' and c', after c', or simultaneously with steps b' or c', but preferably after step c'. Also, step b' may take place before or after step c' or step d' : For instance; the hydroxy group of ⁇ -(4-hydroxybenzylidene)-4-trifluoro- ethenyloxyacetophenone may be converted to an acetate by treatment with acetyl chloride in tetrahydrofuran.
- Patent 5,021 ,602 to form compounds of Formula I. Polymers are formed as described in U.S. Patents 5,037,919; 5,021 ,602; 5,037,917 and 5,037,918, which are incorporated by reference in their entirities.
- These compounds are then heated to cause dimerization of the trifluoroethenyloxy end groups, thereby creating perfluorocyclobutane ring containing polymers with photoactive sites 5 included in the polymer backbone.
- These polymers are suitably dissolved and applied as coatings by any means within the skill in the art such as spin-coating, roll coating, spray coating, pad printing and the like.
- the coating is then exposed to light of the appropriate wavelength to crosslink the polymer. This photocuring process crosslinks the exposed polymer and thereby imparts increased solvent resistance, increased mechanical properties, and modified optical 0 properties with respect to the unexposed polymer or prepolymer.
- Alternative methods for preparing polymers of the invention include a process of preparing a compound of Formula XIII:
- PAS, R, and X are as defined for Formula IV and t is an integer of from 1 to 4 by
- R, X, PAP and t are as defined for Formula XIV are as each Z is independently bromine or iodine
- Step (d") is carried out as steps (d) and (d') and optionally occurs before step a", between steps a" and b" or b" and c", simultaneous with steps a", b", or " or, preferably,after step c".
- the acetyl group of 1-(4-acetophenyl)-1 ,1-bis(4- trifluoroethenyloxy)phenyl ethane is optionally combined via Aldol condensation with benzaldehyde or variously substituted benzaldehydes to form 1-(4-( ⁇ - benzylidene)acetophenyl)-1,1-bis(4-trifluoroethenyloxy phenyl)ethane.
- PAP is a molecular structure having a group reactive with at least one compound having or suitable for forming a photoactive site (a photoactive site-containing or photoactive precursor-containing compound).
- the step of reacting with such a compound is represented as at least a part of step d".
- the reacting and converting steps are optionally consective or separated by one or more of steps b" and c".
- Preferred species formed by such a process are compounds of the formula XVI:
- R is an unsubstituted or inertly substituted hydrocarbyl group preferably of from 1 to 10, more preferably of from 1 to 4 carbon atoms.
- R is optionally and advantageously substituted with functional groups which provide additional desirable properties to the polymer, for example a photosensitizing group such as those within the skill in the art.
- Compounds exemplary of Formula XIII include 1-(4-acroyloxyphenyl)-1,1-bis(4- trifluoroethenyloxyphenyl)ethane, 1-(4-methacroyloxyphenyl)-1 ,1-bis(4- trifluoroethenyloxyphenyl)ethane, 1-(4-acroyl phenyl)- 1,1 -bis(4- trifluoroethenyloxyphenyl)ethane, 1-(4-methacroylphenyl)-1 ,1-bis(4- trifluoroethenyloxyphenyl)ethane, 4-(1 ,1-bis(4-trifluoroethenyloxyphenyl)ethyl)- ⁇ - (benzylidene)acetophenone, 4-(1,1-bis(4-trifluoroethenyloxyphenyl)ethyl)- ⁇ -(4- dimethylamin
- Exemplary compounds of Formula IV include 4,4'-bis(trifluoroethenyloxy)- ⁇ - methylstilbene; 4,4'-bis(trifluoroethenyloxy)stilbene; 4-Trifluoroethenyloxy- ⁇ -(4- trifluoroethenyloxybenzylidene)acetophenone; 2,6-bis(4- trifluoroethenyloxybenzylidene)cyclohexanone; 2,6-bis(4-trifluoroethenyloxybenzylidene)-4- methylcyclohexanone; 1,4-bis(3-(4-trifluoroethenyloxyphenyl)-2-propene-1-onyl)benzene; 1,3- bis(3-(4-trifluoroethenyloxyphenyl)-2-propene-1-onyl)benzene; 1 ,4-bis(3-(4- trifluoroethenyloxy
- each R 4 is independently a linear or cyclic hydrocarbylidene or group preferably of from 1 to 20 carbon atoms (more preferably methylene, dicyclopentadienylene, isopropyiidenelene, fluorenylidene; and the like); and each R5 is independently a hydrogen or an unsubstituted or inertly substituted alkyl or alkyl ether group preferably of from 1 to 6 carbon atoms, preferably of 1 to 3 carbon atoms.
- Monomers containing trifluorovinyl or perfluorocyclobutane groups and photoactive groups are suitably homopolymerized or copolymerized, preferably copolymerized, for instance, with any monomer of the types disclosed by U. S. Patents 5,021 ,602; 5,023,380; 5,037,917; 5,037,918; or 5,037,919; by methods disclosed therein.
- Preferably sufficient monomer having at least one photoactive site or photoactive precursor to form a polymer which becomes less soluble or dispersible upon exposure to photonic radiation is used.
- At least 0.1 percent by molar composition of such monomers are used in a polymer, preferably at least 1 , more preferably from 1 to 100, most preferably from 5 to 25 mole percent of photoactive site containing monomers are used.
- the polymer is suitably linear, branched, crosslinked, or a mixture thereof.
- a photoactive monomer containing two trifluorovinyl groups is homopolymerized or copolymerized with another monomer containing two trifluorovinyl groups to form a substantially linear thermoplastic polymer with photoactive sites either pendant to or incorporated in the polymer backbone
- the molecular weight of such a system is advantageously made as high as possible while still maintaining desirable properties for processability, such as solubility in a solvent suitable for solution coating processes which are within the skill in the art, or melt processability such as extrusion, injection molding or melt blowing.
- the molar percent composition of the photoactive site is advantageously optimized to maintain the same features of processability. Optimization of molecular weight and molar composition of the photoactive site enhance the photochemical sensitivity as defined by Minsk et al. in The Journal of Applied Polymer Science, Volume 2, p. 302 (1959), or by Robertson et al. ibid, p. 308.
- the molecular weight of the polymer is advantageously as close to the gel point of the system as possible while still maintaining processability as defined above, including solvent solubility and/or melt processability.
- processability also involves the exclusion of gels or very high molecular weight fractions which may form before the gel point, but which adversely affect the processability of the polymer and the quality of the coatings and laminates obtained from these prepolymers in applications where properties such as plana ⁇ zation and optical uniformity are important
- the molar content of the photoactive site is optimized to provide maximum photochemical sensitivity as defined for the linear polymers
- weight average molecular weights on the order of 5,000 to 500,000, most preferably from 10,000 to 300,000 are useful in these systems
- the polymer is a thermoplastic, however, it is advantageously applied in a liquid media as described but at a weight average molecular weight greater than 20,000, preferably greater than 60,000.
- Such high molecular weight polymers are advantageously applied in liquid media, preferably solutions such as by spin coating, spray coating, dip coating, pad printing and other methods known to those skilled in the art.
- thermoset resins of the invention thermoplastics are advantageously applied in a sufficiently high molecular weight to obviate the need for a post bake step
- thermoplastic polymers of the invention are applied in melted form such as in a melt extruder, by melt coextrusion of a multilayer laminate, or by spin coating, dip coating or spray coating the polymer directly from the melt phase.
- the polymer may also be formed into a free standing film by melt extrusion, blow molding or other means known to those skilled in the art.
- the polymer is applied as a dry film as is within the skill in the art for instance as discussed in Printed Circuits Handbook, C. F. Combs, Jr., ed., second ed., McGraw- Hill, New York, 1979, pages 6-12 through 6-13.
- a film of photoactive polymer is advantageously supplied as a layer on one, or preferably between two, polymer sheets.
- the film is advantageously applied to a material such as a conductor, for example copper, is exposed to light such that the viscosity of the exposed photoactive polymer increases leaving the unexposed polymer unchanged for removal.
- Photoactive polymers prepared by any of the foregoing methods are advantageously used as coatings.
- the polymer is preferably prepared in an organic solvent, aqueous medium, emulsion, or latex or is dissolved or dispersed after formation or used as a dry film.
- the coating is applied to a surface by means within the state of the art, such as by spin coating, spray coating, plasma deposition, roll coating, pad printing, dip coating and the like. Then the polymer is exposed or at least a portion of the polymer is selectively exposed to photonic radiation of a wavelength which interacts directly or indirectly with the photoactive sites.
- sufficient photonic radiation is used to render the polymer less soluble or dispersible, more preferably essentially insoluble or not dispersible (that is insufficiently soluble or dispersible to be removed from the surface by rinsing in the solvent used for application or any other solvent(s) effective for removal of the unexposed portion of the polymer) or more viscous.
- the polymer is suitably applied to any surface such as the surface of flat, spherical, irregular shapes, such as glass plates, silicon or silicon oxide wafers such as those used in the production of semiconductor devices, glass beads, copper film, other polymers including for instance polycarbonate, polyimide, polyester, polytetrafluoroethylene or other fluoropolymers, polyquinolines, polybenzoxazoles, polybenzimidazoles, polyaryl sulfones , microelectronic circuitry including multilayer microelectronic circuitry devices or other surfaces of the like which optionally may be prepared by processes such as cleaning by washing with soap followed by rinsing with deionized water and then drying, either in an oven or with a stream of dry gas such as air, or cleaning by a plasma cleaning process such as oxygen plasma or sulfur hexafluoride plasma cleaning.
- a plasma cleaning process such as oxygen plasma or sulfur hexafluoride plasma cleaning.
- Other surface treatments may include preparing the surface with an adhesion promoter such as bis[3-(triethoxysilyl)propyl]amine using standard conditions such as those outlined in "Silicon Compounds - Register and Review,” published by Petrarch Systems Silanes and Silicones (1987), Petrarch Systems.
- an adhesion promoter such as bis[3-(triethoxysilyl)propyl]amine using standard conditions such as those outlined in "Silicon Compounds - Register and Review,” published by Petrarch Systems Silanes and Silicones (1987), Petrarch Systems.
- any incident photonic radiation which is effective to render the polymer less soluble or dispersible (hereinafter effective wavelength) is suitably used.
- Such radiation is advantageously at a wavelength which is absorbed by the photoactive site, preferably from 250 nm to 500 nm, for instance 405-436 nm for sites having the 4-dimethylaminochakone group, 300-365 nm for sites having the 4-methoxychalcone group, 254-280 nm for sites having the ⁇ - methylstilbene group, 300-365 nm for sites having the (unsubstituted) chalcone group, 300-365 nm for sites having the 1,4-pentadiene-3-one group, and the like.
- another compound can absorb the photonic radiation and change the available energy.
- photosensitizers such as benzophenone, 1 ,2-benzanthraquinone, or Michler's ketone are known in the art to absorb light at a wavelength different from the absorption of the photoactive site, and transfer the absorbed energy via collision processes from the photosensitizer to the photoactive site, activating the photoactive site for covalent reaction with an appropriate site for crosslinking.
- the photonic energy is suitably used directly or indirectly.
- the photosensitizer compounds are effective to increase the effective wavelength to those more commonly used in industry, use of wavelengths in the mid and deep ultraviolet (UV), that is wavelengths such as the 313 nm (nanometer) line for mid UV, and the 254 nm line for deep UV are advantageous especially for formation of coatings having very fine definition because resolution is improved.
- Most commonly used photoimageable polymers are active in the near U V region rather than the more desirable mid and deep U V.
- the photoactive group is active with a wavelength of incident photonic radiation of from 235 to 260 or from 250 to 275 to avoid optical density from the presence of aromatic groups.
- the photoactive group acts such that crosslinking occurs as a result of incident photonic energy.
- Crosslinking optionally occurs between like photoactive groups or between a photoactive group and a group which is not photoactive.
- Most photoactive compounds of the invention react to crosslink through chemical reactions at the photoactive site, and generally involve lower energy (longer o wavelength, for example greater than 320 nm) absorptions of molecules with large and diffuse molecular orbitals, usually spread out over one or more aromatic ring systems.
- a benzophenone chromophore reacts somewhat differently however, irradiation of benzophenone with light excites the benzophenone carbonyl group to the excited singlet state, which crosses to the chemically active triplet state.
- the n bond is broken and the triplet state can be considered as a 1 ,2 diradical, which is believed to abstract hydrogen from hydrogen-donor molecules such as hydrocarbons, alcohols, ethers, amines, thiols, sulphides, and phenols and produce a benzophenone ketyl radical, also called a diphenylhydroxymethyl radical orsemipinacal radical which radical reacts with another part of the polymer such that crosslinking occurs.
- hydrogen-donor molecules such as hydrocarbons, alcohols, ethers, amines, thiols, sulphides, and phenols
- benzophenone ketyl radical also called a diphenylhydroxymethyl radical orsemipinacal radical which radical reacts with another part of the polymer such that crosslinking occurs.
- crosslinking occurs such that the resulting group is not photoactive or photoabsorptive at the effective wavelength, preferably not photoactive at any wavelength.
- photoactive groups continue to absorb photonic radiation at substantially the same wavelength (a wavelength sufficiently close to the 5 effective wavelength to absorb at least a portion of the incident photonic radiation) after solubility or dispersibility is reduced, they prevent that photonic radiation from going deeper into the polymer to cause another photoactive group to react.
- a material having groups which absorb photonic radiation at a given wavelength are referred to as having optical density at that wavelength. At reduced optical density, there is transparency that permits the photonic 0 radiation to go deeper within a polymer.
- films having a high optical density are 5 generally limited to a thickness of less than 10 ⁇ m, but films of greater than 2 ⁇ m preferably greater than 5 ⁇ m more preferably greater than 10 ⁇ m are formed in the practice of the invention.
- Films of the invention are advantageously at least 0.01 ⁇ m, preferably at least 0.1 ⁇ m, more preferably at least 0.5 ⁇ m thick. Formation of such thick films also is facilitated by the lack of volatiles (water or molecules eliminated in formation of the final polymer film) formed in the practice of the invention
- Photoactive groups that result in crosslinking not having optical density at the effective wavelength include chalcones, cinnamates, acrylates, cinnamaldehydes, maleimides, 1 ,5-aryl-1 ,4-pentad ⁇ ene-3-ones naphthoqu ⁇ nones, couma ⁇ ns, (benzy dene) cyclohexanones, 2,6-b ⁇ s(benzyl ⁇ dene)cyclohexanones, 2-c ⁇ nnamyl ⁇ dene cyclohexanones, 1 ,9-b ⁇ s(aryl)-1 , 3,6,9- nonatetraene-5-ones, 2,6-b ⁇ s(c ⁇ nnamyl ⁇ dene)cyclohexanones, and stilbenes
- a negative photoresist For use as a negative photoresist, only a portion of the photoactive polymer is exposed to sufficient photonic radiation to render it less soluble or dispersible The remaining portion is referred to as unexposed and is removed by means within the skill in the art such as by a process known as developing, such as by spray development, which includes steps of spraying a film-coated substrate with a continuous stream of atomized or otherwise dispersed stream of a developing solvent for a sufficient time to efficiently remove the uncrosslinked portion of a polymer, followed by a drying step comprised of for instance either oven drying the substrate, or drying with a continuous stream of dry gas such as air or nitrogen, or a combination of both oven-drying and gas drying
- Alternative means of removing the less soluble portion of polymer include dunk rinsing, which involves immersing the substrate in a bath of the developing solvent for sufficient time to dissolve the uncrosslinked portion of the polymer
- the polymer When the polymer has remaining trifluorovinyl groups, such as in the case of oligomers or B-staged polymers, the polymer is advantageously heated sufficiently to allow at least a portion of the trifluorovinyl groups to form perfluorocyclobutane groups, advantageously further building molecular weight of the polymer such that it becomes less soluble, more oxidatively and thermally stable, less swellable by contact with solvent, and attains a low dielectric constant and a dissipation factor which is characteristic of the perfluorocyclobutane ring containing polymers
- Temperatures and conditions for forming perfluorocyclobutane groups are those disclosed in the previously cited patents
- Polymers formed in the practice of the invention advantageously have low moisture absorption, preferably moisture absorption of less than 2 percent, low dielectric constant, preferably below 3 5, low dissipation factor, preferably below 01 , flame retardency, good mechanical properties such as tensile modulus and flexural modulus of at least 150,000 psi (1 ,034,213 kPa) chemical resistance, such as resistance to hydrocarbon, aromatic ring-containing solvents including benzene, chlorobenzene, nitrobenzene, toluene, xylene, mesitylene, and the like, ketone or halocarbon solvents, and 5 high thermal-oxidati ve stability, preferably above 100°C, preferably 150°C, more preferably 200°C, (advantageously formulated without added antioxidant) Polymers with at least some of these properties are particularly useful in fabrication of dielectric polymer films for microelectronics applications
- 1,2- Dibromotetrafluoroethane (276 g, 1.06 mole) was added slowly over 30 minutes, and the reaction mixture was stirred at 24 C C for 8 hours After filtration and evaporation, the residue 30 was flushed through a column of alumina using hexane as the eluent Hexane was removed by evaporation, and the resulting residue weighed 109 4 g (0 19 mole) for an isolated yield of 42 percent
- a small sample (2.0g) of the 4,4'-bis(trifluoroethenyloxy)- ⁇ -methyl-stilbene monomer was placed in a 50 ml 3-necked round bottomed flask fitted with a mechanical stirrer and a temperature controller. The monomer was agitated slowly as nitrogen was bubbled through the liquid for 5 minutes. The temperature of the flask was raised to 160°C for 90 minutes, then to 180°C for 60 minutes, and finally to 200°C for 90 minutes. After it was cooled to room temperature, the resulting polymer was recovered by breaking pieces of the polymer out of the reaction flask, and a small portion of the polymer was dissolved in benzene.
- the benzene solution was filtered to remove any insoluble portion of the polymer and deposited on a salt plate for infrared (IR) analysis.
- the benzene was evaporated at 130°C in an oven to leave a thin polymer film deposited on the salt plate.
- the resulting polymer film deposited on the salt plate was washed extensively with benzene in an effort to dissolve and thereby remove the polymer film which had originally been deposited from benzene solution After being washed in 50 ml of benzene for 5 minutes, the salt plate was removed and the benzene allowed to evaporate to dryness The IR spectrum of the salt plate was taken again, and no measurable loss of absorption intensity of the polymer film was observed with respect to the film before washing with benzene.
- Example 2 Copolyme ⁇ zation of 20 Mole Percent 4,4'-Bis(trifluoroethenyloxy)- ⁇ - methylstilbene with 80 mole Percent 1 ,1 ,1-Tris(4-trifluoroethenyloxyphenyl)ethane (TVE Monomer) and Subsequent Photocrossl inking of the Copolymer
- the resulting prepolymer was cooled to room temperature, and a I.O g sample of the prepolymer was removed from the flask. This sample was combined with 10 ml of benzene in a 100 ml Erhlenmeyer flask and heated to 45°C with stirring for 1 hour. The resulting polymer solution was deposited on a NaCl salt plate and the benzene solvent was evaporated to dryness in a drying oven at 120°C.
- IR analysis of this salt plate showed an absorption spectrum of the copolymer, with characteristic IR absorptions at 1605 cm-1, 1594 cm-1, and 1505 cm-1 , corresponding to the aromatic ring absorptions of the polymer system, and at 1206 cm-1, 1 175 cm-1 , and 1 141 cm-1 , corresponding to the absorption of the carbon-fluorine bonds.
- UV light After irradiation of the film with UV light at 254 nm wavelength for 64 hours, a broad absorption band of moderate intensity from 1685 cm-1 to 1772 cm-1 appeared The salt plate was immersed in benzene and washed by swirling the benzene solvent over the salt plate for two minutes.
- Dimethylsulfoxide (210 ml) and toluene (75 ml) were placed in a 500 ml 5-necked round bottomed flask equipped with a mechanical stirrer, a Barrett trap topped with a nitrogen padded reflux condenser, and a thermocouple attached to a temperature controller which controls a heating mantle on the flask through a Variac rheostat power supply.
- the solution was deoxygenated by bubbling nitrogen into the reactor for 10 minutes.
- Potassium hydroxide (KOH) 23.0 g, 0.35 mole as 85.5 percent pellets, the remainder was water was added to the solution and the mixture was heated to 1 10°C to dissolve the KOH. 4-
- Hydroxybenzaldehyde (42.7 g) was added in two equal portions. The solution was heated to reflux to begin water removal. When 14 ml of lower phase had been collected in the Barrett trap, the trap was replaced with a Soxhlet extractor containing anhydrous Na2S04 (sodium sulfate), and the residual water in the toluene was removed by distilling the toluene through this Na2S04 drying bed. Toluene (50 ml) was removed by simple distillation, and the resulting mixture was cooled to 60°C. 1,2-Dibromotetrafluoroethane (140 g, 0.538 moles) was added slowly and the mixture was heated to 70°C.
- Na2S04 sodium sulfate
- Method 2 Powdered 4-hydroxybenzaldehyde (351.4 g, 2.584 mole) was added slowly to a stirred solution of KOH (169.5g, 2.584 mole as 85.5 percent pellets also containing 15 percent water) in 1600 ml of methanol which had been thoroughly deoxygenated by introducing nitrogen through a gas dispersion tube for a period of 15 minutes. The mixture was stirred for 1 hour under a nitrogen atmosphere, then evaporated to yield a purple solid. This solid product was placed in a vacuum drying oven at 5 mm Hg (665 Pa) and 1 10°C for 5 hours, then removed, ground into a fine powder and placed in the vacuum drying oven at 5 mm Hg (665 Pa) and 1 10°C overnight.
- Acetonitrile (300 ml) and granular zinc (30.0 g) were combined in a 1 liter round bottomed flask and stirred at 75°C under nitrogen as 4-(2- bromotetrafluoroethoxy)benzaldehyde (1 1 1 39 g, 0 37 mole) was added slowly by dropping addition funnel The resulting mixture was stirred and heated at 79°C for 12 hours After filtration to remove zinc salts and unreacted zinc, the acetonitrile was removed under vacuum on a rotary evaporator The resulting oily residue was flash distilled on a rotary evaporator under high vacuum (26.6 Pa) to provide 47.33g (0.234 mole) of a water white oil in 63.3 percent yield.
- Mass Spectrometric Analysis: m/e 51 (56 percent); 77 (65 percent); 105 (31 percent); 127 (37 percent); 154 (21 percent); 201 (34 percent); 202 (100 percent); 203 (70 percent).
- the compound was prepared from methyl-4-hydroxy-benzoic acid, salts or esters thereof or from phenol.
- Acetone (0.70g, 0.012 mole) and 4-trifluoroethenyloxybenzaldehyde (5.0g, 0.0247 mole) were combined in reagent alcohol (90 percent ethanol, 5 percent methanol, and 5 percent isopropyl alcohol, available from Fisher Scientific) (30 ml) in a 250 ml jacketed 3-necked round bottom flask equipped with a mechanical stirrer, a nitrogen padded reflux condenser with a downstream gas flow indicator (a bubbler)and an inlet gas dispersion tube.
- the solution was cooled to 0°C with stirring by circulating chilled glycol through the jacket of the reaction vessel, and was deoxygenated by introducing nitrogen through a gas dispersion tube into the solution for 15 minutes.
- Reagent alcohol (1 10 ml) and 4-trifluoroethenyloxybenzaldehyde (20. Og, 0.099 mole) were combined in the apparatus of Method 1 (with the addition of a septum on one neck of the apparatus, through which was introduced the needle of a syringe containing the reagent acetone), deoxygenated as in Method 1 and cooled to 0°C with stirring. The temperature was maintained at 0°-5°C as the alcohol solution was saturated with anhydrous HCI as in Method 1.
- the second plate was placed in a round bottomed flask, and the flask was deoxygenated carefully with nitrogen This plate was then subjected to irradiation with a 15 watt GE F15T8/BLB blackl ⁇ ght (360 nm) for 90 minutes
- the two salt plates were then analyzed by IR spectroscopy
- the first salt plate (experimental control) exhibited a complex absorption structure in the region normally associated with carbon-carbon double bonds, with small to medium absorptions at 1674 cm-1 , 1657 cm-1 , 1623 cm-1, 1604 cm-1 , and 1585 cm-1
- the IR spectrum of the plate which had been subjected to irradiation at 360 nm showed only a single absorption band in this region at 1606 cm-1 , all other absorptions in this region becoming minimal This indicated that irradiation of the polymer film on the second salt plate had effected a change in
- the second salt plate was then placed back in the round bottomed flask and irradiated with the blacklight for an additional 16 hours, while the first plate was returned to dark storage for the same period of time. Subsequent IR analysis of the two plates showed no noticeable differences from the spectra taken previously, after the second plate had experienced only 90 minutes of irradiation at 360 nm.
- the two salt plates were then simultaneously placed in a 250 ml evaporating dish containing 50 ml of CH 2 CI 2 , just enough to completely immerse the plates.
- the evaporating dish was then swirled gently for 1 minute to wash the solvent back and forth across the surfaces of the salt plates.
- the two plates were then removed and analyzed again by IR spectroscopy.
- the first plate which had been stored in the dark, shows no absorption spectrum at all, indicating that the polymer film which was deposited there had been completely washed away by the CH CI 2 treatment.
- the second salt plate which had been subjected to irradiation with light at 360 nm, showed no decrease in the absorption spectrum after the CH 2 CI 2 treatment, indicating that the irradiated film was still substaintally intact.
- This example demonstrated that a polymer film which had been subjected to photonic radiation was rendered insoluble in a solvent in which it was initially soluble.
- the mixture was stirred slowly under high vacuum (266 Pa) and heated to distill the DMSO through the Soxhlet drying apparatus for 4 hours.
- the solution was vented to o atmospheric pressure under nitrogen and cooled to room temperature.
- Analysis of the DMSO solution indicates a water content of 420 ppm (parts per million by weight) by Karl Fisher titration.
- the reaction mixture was chilled to 18°C ⁇ n an ice water bath, and addition of 1 ,2- dibromotetrafluoroethane (400.0 g, 1.54 mole) was carried out over 45 minutes.
- the mixture was held at 18 G C for 30 minutes, then allowed to warm to room temperature. Over the course 5 of one hour the temperature was raised to 50°C and was maintained at 50°C for 18 hours.
- Mass Spectrometric Analysis: m/e 299 (85.8 percent); 300 (30.1 percent); 301 (100 percent); 315 (19.9 percent), 317 (19.9 percent).
- 4-(2-Bromotetrafluoroethoxy)acetophenone (82.0 g, 0.406 mole) was combined with 175 ml of acetonitrile and placed in an addition funnel attached to a 500 ml round 0 bottomed flask equipped with a reflux condenser, a mechanical stirrer, and a thermocouple attached to a temperature controller which controls a heating mantle on the flask through a Va ⁇ ac rheostat power supply.
- An additional 25 ml of acetonitrile was placed in the 500 ml flask along with granular zinc (32.0 g, 0.4895 mole).
- the resulting zinc slurry was stirred and heated to 78°C, at which point the addition of 4-(2-bromotetrafluoroethoxy)acetophenone was 5 begun. The addition was carried out over a period of 45 minutes, during which time the heat was increased to the reflux temperature of the mixture (82°C). After the resulting mixture was stirred at reflux for 5 hours, analysis of the reaction mixture by gas chromatography indicates that all of the starting acetophenone product had been consumed.
- the reaction mixture was then cooled to room temperature and decanted away from the unreacted zinc granules into water (400 ml) which had been acidified with 20 ml of 12 N HCI.
- This aqueous mixture was extracted with dichloromethane (2 times, 250 ml each). This extract was evaporated to provide a yellow oil which was distilled on a rotary evaporator at 85°C and 2 mm Hg (266 Pa).
- the resulting product was flushed through a short bed of neutral aluminum oxide using hexane as an eluent to provide 27.9 g (0.138 mole, 34 percent yield) of the 4-trifluoroethenyloxyacetophenone product as a water white oil.
- Mass Spectrometric Analysis: m/e 76 (22.4 percent); 91 (41.0 percent); 104 (38.5 percent); 201 (100 percent); 216 (22.1 percent); 217 (12 percent).
- the compound was prepared from ethyl phenol or phenol.
- Reagent alcohol 150 ml, Fisher Scientific
- 4-trifluoroethenyloxyacetophenone 25.0 g, 0.1 16 mole
- 4- trifluoroethenyloxybenzaldehyde 23.4 g, 0.1 16 mole
- the flask was equipped with a mechanical stirrer, a thermometer, and a gas dispersion tube.
- the mixture was stirred as chilled glycol coolant was circulated through the flask jacket to cool the mixture to 3°-5°C.
- Nitrogen gas was bubbled into the mixture through the gas dispersion tube to deoxygenate the solution.
- the inlet gas was then switched from nitrogen to anhydrous HCI and the feed rate was controlled to maintain a solution temperature of 5°C. This HCI feed was continued for 4.5 hours, at which point the HCI feed was stopped and the stirring was continued for an additional hour.
- Mass Spectrometric Analysis: m/e 102 (20.4 percent); 104 ( 17.1 percent); 178 (19.8 percent); 201 ( 17.2 percent); 206 (21.0 percent); 303 (37.3 percent); 399 (51.4 percent); 400 ( 100 percent); 401 (50,9%).
- the solution was deoxygenated by introducing nitrogen through a gas dispersion tube for 15 minutes. Potassium hydroxide pellets (125.4g, 85 percent KOH by weight, the balance being water) were added to the solution and heating was begun. The nitrogen gas dispersion tube was removed and replaced with a glass stopper when the KOH pellets were completely dissolved, that was when the solution temperature reaches 1 10°C. The solution was heated to reflux (138°C), and water was removed through the Barrett trap via azeotropic distillation with the toluene. A total of 99 ml of lower phase was removed from the Barrett trap over the course of 6 hours. The Barrett trap was then removed and replaced with a Soxhlet extractor containing activated 5A molecular sieves.
- the toluene was then distilled through the Soxhlet extractor drying bed for 3 hours.
- the Soxhlet extractor was then removed and replaced with the Barrett trap, and toluene (200 ml) was removed through the Barrett trap by simple distillation.
- the resulting solution was then cooled to 30°C, and the addition of 1 ,2-dibromotetrafluoroethane (600.0g, 2.31 mole) was begun. The addition was carried out at 30°-35°C over a period of 45 minutes. When the addition was complete, the mixture was heated slowly to 75°C over 1 hour and stirred at 75°C overnight.
- the hexane was chilled in an ice bath to cause the crystallization of the product. After filtration to remove the precipitate, the hexane filtrate was concentrated by evaporation on a rotary evaporator at 60°C and chilled again to cause the crystallization of the product. After filtration the precipitate fractions were combined to afford 208.6g (0.35 mole, 36.6 percent yield) of the product ⁇ -(4-(2-bromotetrafluoroethoxy)benzyl ⁇ dene)-4-(2- bromotetrafluoroethoxy)acetophenone as a light green solid with a melting point of 89°-90°C.
- Mass Spectrometric Analysis: m/e 63 (16.9 percent); 92 (14.3 percent); 165 (15.8 percent); 299 (17.0 percent); 401 (55.0 percent); 402 (23.4 percent); 403 (60.5 percent); 404 (20.8 percent); 417 (12.7 percent); 419 (16.1 percent); 596 (62.3 percent); 597 (75.1 percent); 598 (100.0 percent); 599 (47.7 percent); 600 (47.6 percent).
- Example 5 or 1 ,5-B ⁇ s(4-t ⁇ fluoroethenyloxyphenyl)-1,4-pentad ⁇ ene-3-one (hereinafter bischalcone monomer) prepared by the process of Example 3 and B-staged according to the procedure outlined below
- TVE monomer (30 g) and chalcone monomer ( 1.18 g) were placed in a long cylindrical reaction vessel equipped with a three necked glass head, a TeflonTM (polytetrafluoroethylene commercially available from E.l.
- silicon oxide wafers were pretreated with an adhesion promoter according to the following method
- the prepolymer of 5 mole percent chalcone/95 mole percent TVE monomer from Example 6 above was dissolved to make a 50 percent solid solution in mesitylene
- the prepolymer solution was filtered from a syringe through a 0 2 micron (0 002 mm) filter (to remove small particles) into a 100 mL clean bottle
- the term 'clean bottle' isused to refer to a bottle which hasbeen cleaned to contain less than 0 001 particle of size 0 30 micron or larger per milliliter of volume
- the prepolymer solution (2 mL) was then deposited onto a 10 cm round silicon oxide wafer using a spread cycle of 500 rpm for 3 seconds and a spin cycle of 5000 rpm for 30 seconds to give a film of excellent quality (no large variation in film thickness as noted by the absence of unassisted visually detected colored interference patterns on the wafer)
- the prepolymer film was prebaked at 80°C for
- the exposed film was then developed by soaking in xylene solvent for 15 seconds and then dried under a stream of nitrogen at a temperature of 25 C C
- a negative relief of the pattern on the quartz mask was sucessfully transferred to the polymer upon development as indicated by uncrosslinked areas within the pattern which were washed away by the developing solvent (xylene)
- Example 1 1 Following the general procedure of Example 1 1 , further examples of processing good quality thin films of photodefinable prepolymers onto 10 cm silicon oxide substrates were outlined in the following examples of the invention
- Example 12 (10 mole percent chalcone / 90 mole percent TVE) B-Staging Conditions: 4.0 hours at 150°C;
- UV exposure time 999 seconds
- Example 13 (10 mole percent chalcone/ 90 mole percent TVE)
- UV exposure time 999 seconds
- Example 14 (10 mole percent chalcone / 90 mole percent TVE)
- UV exposure time 999 seconds
- Example 15 (10 mole percent chalcone / 90 mole percent TVE)
- UV exposure time 999 seconds
- Example 16 (50 mole percent chalcone / 50 mole percent TVE)
- Example 17 (10 mole percent bischalcone / 90 mole percent TVE)
- UV exposure time 500 seconds
- Chalcone monomer was ⁇ -(4-trifluoroethenyloxybenzylidene)-4-trifluoroethenyloxyacetophenone.
- G a good quality film was obtained.
- the difference between G and E was a subjective evaluation based on the surface appearance of the film, such as a good (G) quality coating appeared smooth and uniform with a non-gloss or matte finish, and an excellent (E) quality film appeared smooth and uniform with a glossy finish.
- Each coated quartz wafer was exposed to UV light for 999 seconds between the wavelengths of 290-350 nm.
- the UV absorption spectra for each wafer was analyzed between
- the spectra of the photocrosslinkable copolymer before photoexposure had the characteristic lambda max (that was the wavelength of maximum absorbance of the prepolymer film in the region of 260 nm to 450 nm); the spectra of the photoexposed prepolymer films had a decrease of absorbance at the position of the lambda 0 rnax of the photocrosslinkable copolymer.
- the lambda max for the chalcone and bischalcone containing prepolymers were 314 and 330 nm, respectively.
- This product had a melting point of 70.0 C -71.5°C.
- Example 24 Copolymerization of ⁇ -(4-methoxybenzyl ⁇ dene)-4- trif I uoroethenyloxyacetophenone with TVE Monomer: ⁇ -(4-methoxybenzylidene)-4-trifluoroethenyloxyacetophenone ( 1.3544 g, 0.00405 mole) was combined with TVE monomer (20.02 g, 0.0366 mole) and mesitylene solvent (21.37 g) in the apparatus of Example 22, and was deoxygenated thoroughly by introducing nitrogen through a gas dispersion tube for 10 minutes, and thereafter maintaining the solution under a nitrogen atmosphere.
- the solution was heated to 160 c C for 3 hours and 10 minutes, after which time it was cooled and the solution was checked by GPC analysis to ascertain the molecular weight of the prepolymer.
- the weight average molecular weight of the prepolymer was 379,400.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6515164A JPH08505168A (en) | 1992-12-24 | 1993-12-01 | Photoimageable Polymers Containing Perfluorocyclobutane Groups |
EP94902456A EP0676062A1 (en) | 1992-12-24 | 1993-12-01 | Photodefinable polymers containing perfluorocyclobutane groups |
KR1019950702639A KR960700462A (en) | 1992-12-24 | 1993-12-01 | Photodefinable polymers containing perfluorocyclobuatane groupos |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US07/996,452 US5426164A (en) | 1992-12-24 | 1992-12-24 | Photodefinable polymers containing perfluorocyclobutane groups |
US07/996,452 | 1992-12-24 |
Publications (1)
Publication Number | Publication Date |
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WO1994015258A1 true WO1994015258A1 (en) | 1994-07-07 |
Family
ID=25542944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1993/011562 WO1994015258A1 (en) | 1992-12-24 | 1993-12-01 | Photodefinable polymers containing perfluorocyclobutane groups |
Country Status (6)
Country | Link |
---|---|
US (2) | US5426164A (en) |
EP (1) | EP0676062A1 (en) |
JP (1) | JPH08505168A (en) |
KR (1) | KR960700462A (en) |
CA (1) | CA2151151A1 (en) |
WO (1) | WO1994015258A1 (en) |
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EP1690133A1 (en) * | 2003-10-20 | 2006-08-16 | The University of North Carolina at Chapel Hill | Fluorinated photoresists prepared, deposited, developed and removed in carbon dioxide |
EP1690133A4 (en) * | 2003-10-20 | 2008-03-26 | Univ North Carolina | Fluorinated photoresists prepared, deposited, developed and removed in carbon dioxide |
EP1726581A1 (en) * | 2005-05-25 | 2006-11-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Synthesis of novel monomers containing the Trifluorovinylidene-group and the Cyanato-group and polymers thereof |
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Also Published As
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KR960700462A (en) | 1996-01-20 |
EP0676062A1 (en) | 1995-10-11 |
CA2151151A1 (en) | 1994-07-07 |
US5426164A (en) | 1995-06-20 |
US5489623A (en) | 1996-02-06 |
JPH08505168A (en) | 1996-06-04 |
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