CN103788101B - Cross-linked metalloporphyrin nanocrystal and preparation method thereof, and manufacturing method for optical detector - Google Patents
Cross-linked metalloporphyrin nanocrystal and preparation method thereof, and manufacturing method for optical detector Download PDFInfo
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- CN103788101B CN103788101B CN201210427590.7A CN201210427590A CN103788101B CN 103788101 B CN103788101 B CN 103788101B CN 201210427590 A CN201210427590 A CN 201210427590A CN 103788101 B CN103788101 B CN 103788101B
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 230000003287 optical effect Effects 0.000 title abstract 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 54
- 150000004032 porphyrins Chemical class 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 15
- 230000004888 barrier function Effects 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007639 printing Methods 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
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- 238000004528 spin coating Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
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- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 150000004033 porphyrin derivatives Chemical class 0.000 claims description 5
- 238000007650 screen-printing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 235000021419 vinegar Nutrition 0.000 claims 2
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- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000002070 nanowire Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract 1
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- 238000004544 sputter deposition Methods 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 3
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DLEUNWLRLOYQQI-UHFFFAOYSA-N [Ni].OC1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Ni].OC1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 DLEUNWLRLOYQQI-UHFFFAOYSA-N 0.000 description 2
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- WNGGWVAYNUANOX-UHFFFAOYSA-N [N]1C2=CC=C1C=C(N1)C=C(O)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 Chemical compound [N]1C2=CC=C1C=C(N1)C=C(O)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 WNGGWVAYNUANOX-UHFFFAOYSA-N 0.000 description 1
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/48—Photometry, e.g. photographic exposure meter using chemical effects
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of preparation and application of nano-materials, especially to a cross-linked metalloporphyrin nanocrystal and a preparation method thereof and a manufacturing method for an optical detector. The cross-linked metalloporphyrin nanocrystal is of a one-dimensional netted or dendritic structure formed by mutual crosslinking of metalloporphyrin nanowires. A metalloporphyrin compound and an organic solvent are mixed to obtain a mixed solution, and annealing is carried out so as to obtain the cross-linked metalloporphyrin nanocrystal. The invention further provides the manufacturing method for the optical detector with the metalloporphyrin nanocrystal as an organic detection layer. The preparation method provided by the invention is easy to operate and has low energy consumption and a wide application scope; the prepared optical detector has the characteristics of preparation through solubilization, high flexibility and sensitivity, good stability, etc. and has wide application values.
Description
Technical field
The present invention relates to nano material preparation and applied technical field, especially a kind of metalloporphyrin with cross-linked structure
And its application in photodetection field.
Background technology
Organic photodetector has the advantages that high sensitivity, low noise, repeatability due to it, causes people widely to note
Meaning.From the point of view of the material of detector light detector layer, mainly include film type and monocrystalline type.It is easy to based on the photo-detector of film type
Realize flexible, large-area preparation, but the light detector layer of film type is usually the structure of polycrystalline or amorphous, leads to big dark-state
Electric current, low resolution.Comparatively speaking, organic single-crystal especially one-dimensional nano structure monocrystalline has big specific surface area, lacks
Lattice defect the advantages of, the detector therefore with one-dimensional nano structure as light detector layer shows high resolution.However, by
Poor in the controllability of monocrystalline, the photo-detector repeatability therefore with above-mentioned one-dimensional nano structure as light detector layer is poor,
It is difficult to realize large-area preparation.Therefore, how to realize simple to operate, degree of crystallinity high, specific surface area is big, it is large-area to be applied to
The preparation of light detector layer, is to realize organic photodetector low cost, need a key solving in high sensitivity preparation process
Problem.
Porphyrin compound is as the important composition of O_2 carrier and biological enzyme in photosynthetic center, life body
Part, has excellent effect in terms of energy transfer, shows excellent photoelectric characteristic simultaneously.Metal porphyrinses simultaneously
There is big conjugated molecule structure it is easy to be self-assembled into nanocrystalline and by the nanocrystalline thin film forming by non-covalent bond effect,
But above-mentioned nanostructured preparation process is complicated, degree of crystallinity is not high, specific surface area is less, so that being light based on above-mentioned nanostructured
The detector of detecting layer is relatively costly, dark current is more relatively low than larger, sensitivity, and is not suitable for the large-area life of industrialization
Produce.
Content of the invention
For solving the above problems, the present invention provides a kind of crosslink metallic porphyrin nano crystalline substance and its preparation method and application.Will
This crosslink metallic porphyrin nano crystalline substance is applied in the making of photo-detector as organic detecting layer, has highly sensitive, high stable
The feature of property, and manufacture method is simple and convenient, applied widely.
This crosslink metallic porphyrin nano crystal structure, metalloporphyrin nano wire is cross-linked with each other into one-dimensional netted or dendritic knot
Structure.
Wherein, described metalloporphyrin nanowire diameter is 10～2000nm；Length is 5～1000 μm.
The present invention also provides this crosslink metallic porphyrin nano brilliant preparation method, and its step is by metal porphyrinses
The mixed solution being formed with organic solvent is transferred on receiver board, then is made annealing treatment；Metalloporphyrin in described mixed solution
The concentration of compound is 0.05～10mg/ml.
Wherein, described annealing is to control 50～150 DEG C of temperature, keeps 10～60 minutes.
Wherein, described organic solvent includes chloroform, chlorobenzene, dimethylbenzene, o-dichlorohenzene, propylene glycol methyl ether acetate, second two
At least one of alcohol methyl ether acetate, octane.
Further, the central metal element of described metal porphyrinses is zinc, cobalt, nickel, indium, copper, magnesium or platinum.
Further, described transfer method includes spin coating, drop film, immersion, roller coat, Electrospun, aerosol spray printing, ink-jet print
One of brush, intaglio printing or silk screen printing.
The present invention also provides another kind of described crosslink metallic porphyrin nano brilliant manufacture method, different from above-mentioned manufacture method
, described metal porphyrinses are used in the metal porphyrin derivative replacement of the substituted base of porphyrin ring upper band.
Wherein, described substituent group be ester group, hydroxyl or at least one less than the alkyl of 4 carbon atoms.
The present invention also provides this crosslink metallic porphyrin nano brilliant purposes in preparing bottom gate type organic photodetector.This
The manufacture method planting bottom gate type photo-detector, including substrate, light detector layer, grid and source, drain electrode, the system of described light detector layer
It is that metal porphyrinses are substantially dissolved in formation mixed solution in organic solvent as step, described mixed solution is transferred to
On receiver board, it is brilliant that annealing forms crosslink metallic porphyrin nano.
Wherein, in described mixed solution, the concentration of metal porphyrinses is 0.05～10mg/ml.
Wherein, described annealing is to control 50～150 DEG C of temperature, keeps 10～60 minutes.
Wherein, described organic solvent includes chloroform, chlorobenzene, dimethylbenzene, o-dichlorohenzene, propylene glycol methyl ether acetate, second two
At least one of alcohol methyl ether acetate, octane.
Further, the central metal element of described metal porphyrinses is zinc, cobalt, nickel, indium, copper, magnesium or platinum.
Further, described transfer method includes spin coating, drop film, immersion, roller coat, Electrospun, aerosol spray printing, ink-jet print
One of brush, intaglio printing or silk screen printing.
Further, described receiver board is insulating barrier or at least one of source, drain electrode.
Beneficial effect:
The preparation method of photo-detector provided by the present invention, using crosslink metallic porphyrin nano crystalline substance have one-dimensional netted
Or dendritic morphology, prepare the organic detecting layer having good photoelectric characteristic.The manufacture method of this organic detecting layer is easy to operate, becomes
This is cheap, not high to environmental requirement.The photo-detector prepared have solvable liquefaction preparation, flexibility, high sensitivity, low cost,
It is easy to the features such as large area preparation, have therefore in flexibility, large area, low cost, the preparation of high sensitivity organic photodetector
There is important using value.
Brief description
Fig. 1 is the optical microscopy map of the crosslinked porphyrin zinc nanocrystalline of the embodiment of the present invention 1.
Fig. 2 is the photoelectric characteristic test chart of the organic detecting layer of the embodiment of the present invention 1.
Specific embodiment
With reference to the accompanying drawings, in conjunction with specific embodiments, the present invention is described in more detail.
The present invention provides a kind of crosslink metallic porphyrin nano brilliant, as shown in figure 1, every described metalloporphyrin nanocrystalline in line
Shape, and it is cross-linked with each other into one-dimensional netted or dendritic morphology.Above-mentioned cross-linked structure is intermolecular by metal porphyrinses
Active force is formed.By selecting the concentration of solvent of different nature and adjustment metal porphyrinses, size can be produced not
The crosslink metallic porphyrin nano same, crosslinking degree is different, performance is different is brilliant.
The present invention provides the nanocrystalline a diameter of 10～2000nm of this crosslink metallic Porphyrin and its derivative；Length be 5～
1000μm.This metalloporphyrin and its derivates nanometer crystalline substance can be applied in the making of organic light detector layer.
The manufacture method of this crosslink metallic porphyrin compound, is that metalloporphyrin or derivatives thereof is abundant with organic solvent
Dissolve each other, the mixed solution of formation is transferred in substrate, then is made annealing treatment；Metal porphyrinses in described mixed solution
Concentration is 0.05～10mg/ml.Wherein, metalloporphyrin or derivatives thereof should be substantially dissolved in organic solvent, such ability
Ensure this metalloporphyrin or its derivative can disperse in the solution, nano wire and network structure are formed with intermolecular force.
Below, in conjunction with the making embodiment of photo-detector, introduce the nanocrystalline work of this crosslink metallic Porphyrin and its derivative
Manufacture method for organic detecting layer.
Embodiment 1
The photo-detector of the present embodiment is bottom gate-top contact type, and its manufacture method is as follows:
Step one, prepares the thick gate electrode of one layer of 100nm with the method for sputtering, this gate electrode is made up of si in substrate.
Wherein, the manufacture method of substrate will be used acetone, ethanol, ultrasonic 40 minutes of pure water, then use n as substrate successively for pei2
Air-blowing is done, and puts in 100 ° of c vacuum drying ovens and places 10 minutes, forms substrate.
Step 2, on gate electrode, plates the thick sio of last layer 300nm using the method for thermal oxide2As insulating barrier.
Step 3, prepares crosslink metallic porphyrin nano crystalline substance, wherein insulating barrier is as receiver board on the insulating layer.
Step 4, in substrate and crosslink metallic porphyrin nano crystalline substance, thermal evaporation is for the source electricity of a layer thickness 100nm gold material
Pole and drain electrode.Source, the width of drain electrode are 20 μm, and length is 200 μm, and the distance between two electrodes are 20 μm.
Wherein, adopt crosslink metallic porphyrin nano brilliant as follows as the manufacture method of organic detecting layer in step 3:
Zinc porphyrin is mixed with chloroform, octane and is made into mixed solution, wherein porphyrin zinc concentration is 3mg/ml.Then pass through
The method of drop film transfers to described mixed solution on gate electrode and insulating barrier, places 40 minutes.Through 100 ° of c thermal anneal process
10 minutes, that is, obtain the organic detecting layer being formed by one-dimensional crosslinking porphyrin zinc nanocrystalline.
The photo-detector that to adopt said method to obtain be organic detecting layer with crosslinked one-dimensional porphyrin zinc nanocrystalline.
Photoelectric characteristic test is carried out to above-mentioned organic photodetector, result is shown in Fig. 2.In figure can draw the present embodiment institute
The susceptiveness that the organic photodetector of preparation has had, and preferably repeatability.
Embodiment 2
The photo-detector of the present embodiment is bottom gate-top contact type, and its manufacture method is as follows:
Step one, uses the method for thermal evaporation to prepare the thick gate electrode of one layer of 100nm, this gate electrode is by golden structure in substrate
Become.Wherein, the preparation method of substrate is as described in Example 1.
Step 2, on gate electrode, plates the thick dielectric film such as polyvinylpyrrolidine of last layer 500nm using the method for rotation
Ketone (pvp) is as insulating barrier.
Step 3, prepares crosslink metallic porphyrin nano crystalline substance, wherein insulating barrier is as receiver board on the insulating layer.
Step 4, in substrate and on one-dimensional crosslink metallic porphyrin nano crystalline substance, the method for thermal evaporation is for one layer of 100nm gold structure
Become source electrode and drain electrode.Wherein, the parameter of source-drain electrode is as described in Example 1.
Wherein, adopt crosslink metallic porphyrin nano brilliant as follows as the manufacture method of organic detecting layer in step 3:
8 methyl porphyrin cobalt is mixed with chlorobenzene and is made into mixed solution, wherein the concentration of 8 methyl porphyrin cobalt is 10mg/ml.
Then by the method for spin coating, described mixed solution is transferred on gate electrode and insulating barrier, place 40 minutes.Through 130 ° of c heat
Annealing 20 minutes.Organic detecting layer that the one-dimensional crosslinking 8 methyl porphyrin cobalt nanocrystal that the present embodiment obtains is formed, with
The structure of the porphyrin zinc nanocrystalline of embodiment 1 is similar with performance.
Embodiment 3
The photo-detector of the present embodiment is bottom gate-bottom contact-type, and its manufacture method is as follows:
Step one, uses the method for thermal evaporation to prepare the thick gate electrode of one layer of 200nm, this gate electrode is by silver-colored structure in substrate
Become.Wherein, the preparation method of substrate is as described in Example 1.
Step 2, on gate electrode, the method by the use of atomic layer plates last layer 100nm thickness aluminium oxide as insulating barrier.
Step 3, on substrate, gate electrode and insulating barrier by the use of thermal evaporation method prepare the thick silver of one layer of 100nm as
Source, drain electrode.Wherein, the parameter of source-drain electrode is as described in Example 1.
Step 4, using insulating barrier and source, drain electrode as receiver sheet, prepares one-dimensional crosslinking using the method for aerosol spray printing
Metalloporphyrin is nanocrystalline.
Wherein, adopt crosslink metallic porphyrin nano brilliant as follows as the manufacture method of organic detecting layer in step 4:
Eight hydroxy-porphyrin nickel are mixed with chlorobenzene and propylene glycol methyl ether acetate and is made into mixed solution, wherein eight hydroxy-porphyrin
The concentration of nickel is 3mg/ml.Then described mixed solution is transferred to by substrate and source, drain electrode by the method for aerosol spray printing
On, place 30 minutes.Through 50 ° of c thermal anneal process 60 minutes.The one-dimensional crosslinked eight hydroxy-porphyrin nickel that the present embodiment obtains are received
Organic detecting layer that rice crystalline substance is formed, similar to the structure of the porphyrin zinc nanocrystalline of embodiment 1 and performance.
Embodiment 4
The photo-detector of the present embodiment is bottom gate-bottom contact-type, and its manufacture method is as follows:
Step one, uses the method for magnetron sputtering to prepare the thick gate electrode of one layer of 80nm, this gate electrode is by ta structure in substrate
Become.Wherein, the preparation method of substrate is as described in Example 1.The condition of magnetron sputtering is: base vacuum 2 × 10-3pa；It is passed through ar
Gas makes the vacuum of sputtering reach 1pa；Sputtering power 500w；100 ° of c of underlayer temperature.
Step 2, in substrate and gate electrode, the method using magnetically controlled DC sputtering plates last layer tio2As insulating barrier.
The condition of reactive sputtering is: base vacuum is 2 × 10-3pa；It is passed through o2Gas makes sputtering vacuum reach 1pa；Sputtering power 500w；Lining
100 ° of c of bottom temperature.
Step 3, on substrate, gate electrode and insulating barrier, the method for upper utilization thermal evaporation prepares the thick gold of one layer of 60nm
As source, drain electrode.The parameter of wherein source, drain electrode is referring to shown in embodiment 1.
Step 4, using insulating barrier and source, drain electrode as receiver sheet, prepares one-dimensional crosslinked gold using the method for ink jet printing
Belong to porphyrin nano brilliant.
Wherein, in step 4, the brilliant manufacture method of one-dimensional crosslink metallic porphyrin nano is as follows:
Octaethylporphyrin platinum and toluene, chloroform, octane are mixed into mixed solution, the concentration of wherein octaethylporphyrin platinum is
0.05mg/ml.The addition one side of octane can dissolve metalloporphyrin platinum, can adjust the volatility of solvent, consumption one simultaneously again
As account for the 1/5-1/2 of total solvent.By the method for ink jet printing, above-mentioned mixed solution is shifted on source electrode and drain electrode, put
Put 20 minutes.It is then passed through 150 DEG C of thermal anneal process 10 minutes.The one-dimensional crosslinking octaethylporphyrin platinum nanometer that the present embodiment obtains
Organic detecting layer that crystalline substance is formed, similar to the structure of the porphyrin zinc nanocrystalline of embodiment 1 and performance.
Wherein, the material of gate electrode, source electrode and drain electrode and preparation method include above example, but be not limited to
Upper embodiment.
Wherein one-dimensional crosslink metallic porphyrin nano crystalline substance transfers to receiver board method not only can be according in embodiment 1 to 4 point
Not using spin coating, drop film, the method such as aerosol spray printing and ink jet printing realize real it is also possible to by immersion, intaglio printing,
The method of silk screen printing, roller coat and Electrospun is realized, and annealing can also be the annealing in atmosphere of inert gases.Gold
Belong to the compound that porphyrin compound can also be the Porphyrin and its derivative of indium, copper, magnesium or other metals in addition to the implementation.
Organic solvent used is also not necessarily limited to described in the present embodiment, and those skilled in the art are should well know that can be conducive to dissolving
Dispersed metal porphyrin chemical combination, and the organic solvent of the volatilization that is easy to be heated is all applicable.Control metal porphin in described mixed solution
The concentration of quinoline compound is 0.05～10mg/ml, and described annealing is to control 50～150 DEG C of temperature, keeps 10～60 minutes,
All can reach similar implementation result.In addition, metal porphyrinses can also be derived using the substituent group metalloporphyrin carrying
Thing replaces, and substituent group, in addition to above-described embodiment is related to, can also be ester group, hydroxyl, short-chain alkyl etc..
Organic photodetector prepared by the present invention, its organic detecting layer is by the one-dimensional crosslinked nanocrystalline structure of metalloporphyrin
Become.Based on the device architecture of transistor, gate electrode voltage be zero diode structure can also using the inventive method make, should
This is included within the present invention.The preparation method of organic photodetector provided by the present invention have solvable liquefaction preparation, flexible,
High sensitivity, low cost, be easy to large area preparation etc. feature, therefore in flexibility, large area, low cost, the organic light of high sensitivity
There is in the preparation of detector important using value.
Claims (7)
1. a kind of brilliant manufacture method of crosslink metallic porphyrin nano is it is characterised in that comprise the steps: metalloporphyrin chemical combination
Thing is completely dissolved in formation mixed solution in organic solvent；Described mixed solution is transferred on receiver board, then carries out annealing treatment
Reason；In described mixed solution, the concentration of metal porphyrinses is 0.05～10mg/ml；Described annealing is to control temperature 50
～150 DEG C, keep 10～60 minutes；Described organic solvent includes chloroform, chlorobenzene, dimethylbenzene, o-dichlorohenzene, propylene glycol monomethyl ether vinegar
At least one of acid esters, glycol methyl ether acetate, octane；The central metal element of described metal porphyrinses be zinc, cobalt,
Nickel, indium, copper, magnesium or platinum；
Described crosslink metallic porphyrin nano crystal structure, the nanocrystalline one-tenth wire of every metalloporphyrin, and it is cross-linked with each other into one-dimensional netted
Or dendritic morphology.
2. according to claim 1 the brilliant manufacture method of crosslink metallic porphyrin nano it is characterised in that described transfer method bag
Include one of spin coating, drop film, immersion, roller coat, Electrospun, aerosol spray printing, ink jet printing, intaglio printing or silk screen printing.
3. a kind of brilliant manufacture method of crosslink metallic porphyrin nano is it is characterised in that comprise the steps: to derive metalloporphyrin
Thing is completely dissolved in formation mixed solution in organic solvent；Described mixed solution is transferred on receiver board, then carries out annealing treatment
Reason；In described mixed solution, the concentration of metal porphyrin derivative is 0.05～10mg/ml；Described annealing is to control temperature 50
～150 DEG C, keep 10～60 minutes；Described organic solvent includes chloroform, chlorobenzene, dimethylbenzene, o-dichlorohenzene, propylene glycol monomethyl ether vinegar
At least one of acid esters, glycol methyl ether acetate, octane；The central metal element of described metal porphyrin derivative be zinc, cobalt,
Nickel, indium, copper, magnesium or platinum；
Described crosslink metallic porphyrin nano crystal structure, the nanocrystalline one-tenth wire of every metal porphyrin derivative, and it is cross-linked with each other into one
Tie up netted or dendritic morphology；
Wherein, described metal porphyrin derivative is the substituted base of porphyrin ring upper band in metal porphyrinses.
4. according to claim 3 the brilliant manufacture method of crosslink metallic porphyrin nano it is characterised in that described substituent group is ester
Base, hydroxyl or at least one less than the alkyl of 4 carbon atoms.
5. a kind of manufacture method of bottom gate type photo-detector, including substrate, light detector layer, grid and source, drain electrode, its feature exists
In the making step of described light detector layer is the system brilliant using described crosslink metallic porphyrin nano as arbitrary in claim 1 or 3
Make method, form crosslink metallic porphyrin nano crystalline substance as described light detector layer.
6. according to claim 5 photo-detector manufacture method it is characterised in that described transfer method include spin coating, drip
One of film, immersion, roller coat, Electrospun, aerosol spray printing, ink jet printing, intaglio printing or silk screen printing.
7. according to claim 5 photo-detector manufacture method it is characterised in that described receiver board be insulating barrier or source,
At least one of drain electrode.
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