CN114411089A - Composite transparent conductive film and amino acid anchoring method preparation process and application thereof - Google Patents
Composite transparent conductive film and amino acid anchoring method preparation process and application thereof Download PDFInfo
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004873 anchoring Methods 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 230000001939 inductive effect Effects 0.000 claims abstract description 11
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004472 Lysine Substances 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 17
- 239000004475 Arginine Substances 0.000 claims description 16
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 16
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 9
- -1 polyethylene terephthalate Polymers 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 238000003618 dip coating Methods 0.000 claims description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims 1
- 229920000144 PEDOT:PSS Polymers 0.000 claims 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 40
- 238000002834 transmittance Methods 0.000 description 17
- 238000005452 bending Methods 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
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- 230000002401 inhibitory effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910015711 MoOx Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a composite transparent conductive film and an amino acid anchoring method preparation process and application thereof. The composite conductive film has a three-layer structure of amino acid/metal/anti-reflection layer, the amino acid is used as an inducing layer for the growth of the metal film, the high-refractive-index material is used as the anti-reflection layer, and the preparation process comprises the following steps: cleaning the substrate and performing hydrophilic treatment; coating an amino acid solution on a substrate to prepare an inducing layer, and fully volatilizing the solvent through a thermal annealing process; and depositing a metal film by vacuum evaporation, and then depositing an anti-reflection layer material to obtain the composite transparent conductive film. The composite transparent conductive film and the preparation method thereof provided by the invention have the characteristics of simple preparation process and low cost, and are suitable for various substrate materials. Has important prospect and value in the application of large-area photoelectronic devices.
Description
Technical Field
The invention relates to a composite transparent conductive film and an amino acid anchoring method preparation process and application thereof, belonging to the technical field of electronic devices.
Background
Organic optoelectronics has been rapidly developed in recent years, and is widely applied to the fields of organic solar cells, wearable sensors, touch screens, smart windows, organic light emitting diodes and the like. The organic optoelectronic device has the advantages of light weight, thinness, low manufacturing cost and the like, and has wide application prospect in the field of flexible electronics. In order to obtain a high-performance flexible photoelectric device, the preparation of the transparent electrode is a key step, and the electrode is required to have the characteristics of good mechanical bending property, high light transmittance and low sheet resistance. Currently, an Indium Tin Oxide (ITO) electrode is difficult to integrate into a highly flexible substrate due to a high deposition temperature and poor mechanical bending performance, which greatly limits the application of the ITO electrode in the field of flexible electronics. For this reason, researchers have been devoted to exploring transparent electrodes suitable for flexible devices, such as metal nanowires, ultra-thin metals, metal meshes, conductive polymers, and the like.
Among them, the ultra-thin metal has good mechanical stability, is convenient to manufacture, and is expected to be applied to large-area equipment. During the deposition of the ultrathin metal layer, the island-shaped growth mode is presented in the early stage of metal film formation due to the mismatch of the surface energies of the substrate and the metal. This results in a higher penetration thickness of the metal film (>10 nm) to reduce the light transmittance of the film. In order to obtain a transparent conductive film with good photoelectric properties, the key point is to inhibit the island-shaped growth mode of the metal layer. To this end, researchers have proposed solutions to incorporate an inducing layer between the base material and the conductive metal. The induction layer material can improve the surface energy of the substrate and reduce the surface energy difference between the metal and the substrate; and induces the function of forming bonds between the layer material and the metal atoms,effectively inhibiting the random migration and aggregation of metal atoms. Metal oxides as inducing layer materials have been reported many times, e.g., Kim et al using ZnS, WO3、MoO3The metal film is used as a seed layer to improve the surface energy of the substrate and effectively reduce the threshold thickness of the metal film (adv. Funct. Mater. 2015, 25, 7145-7153); sylvio Schubert et al utilize thermal deposition of MoO3、WO3、V2O5The form of the ultrathin silver layer is improved by being used as a seed layer, and the transmittance of the film is further improved by using an oxide or an organic multilayer as a covering layer (adv. Funct. Mater. 2012, 22(23), 4993-4999); Tzu-Wei Lin et al obtained MoO by sputtering systemsx/Ag/MoOxConducting thin film and passing through in-situ O2The light transmittance of the material is further improved by the modification of the/Ar plasma (Ceramics International, 2017, 43(1, Part A), 308-315); the Mihalea Girtan obtains ITO/metal/ITO and ZnO/metal/ZnO electrodes by using a continuous sputtering method, and applies the electrodes to Solar cells (Solar Energy Materials)&Solar cells, 2012, 100(none), 153-. The deposition temperature of the metal oxide is high, which may cause damage to the flexible substrate. In addition, the N-containing organic small molecule can also be used as a metal induction layer, which inhibits the random migration of metal atoms by forming an N-Ag chemical bond, such as Bae and the like, so that a transparent conductive film p-bPPhen/Ag/HAT-CN (adv. electron. mater. 2019, 1900620) which is efficient, bending-resistant and has thermal stability is prepared; subin Lee et al prepared conductive thin films HAT-CN/Ag/HAT-CN and applied them as transparent anodes to OLED devices (ACS applied. Electron. mater. 2020, 2, 1538-. The deposition temperature of the organic micromolecules is lower than that of the metal oxide, and the organic micromolecules are compatible with the vacuum evaporation process. The polymer material containing N, S, O atoms is also reported many times as an inducing layer, and the coordination bond is formed between the lone pair electrons provided by N, S, O and the metal, so that the random migration of the metal atoms is effectively inhibited. Li and the like prepare electrode PAI/Ag/MoO3It has good photoelectric property and good bending resistance (nanophotonics 2020, 9(11), 3567-; Yan-Gang B et al prepared SU-8/Au electrodes with metal atoms fixed by chemical bonding between Au and SU-8 films to inhibit island growth mode (Nano)scale, 2016, 8(19), 10010-; the Hongkyu Kang and the like prepare a PEI/Ag/PEDOT/PSS composite electrode which has good mechanical bending property and excellent photoelectric property (sheet resistance)<10 Ω/sq, light transmittance>95% @550 nm) (Nature communications. 2015, 6, 6503); jeong uses PEI, PAA, PVP and the like as inducing layers and MoO3PSs, PVK as anti-reflection layers, with high transmittance, low sheet resistance, excellent mechanical flexibility, with light transmittance exceeding 80% in the visible range, and can also be applied to large-scale devices (adv. funct. mater. 2017, 27(22), 1606842). Therefore, in order to realize the conductive film with high light transmittance and low sheet resistance, it is key to explore an induction layer material and an electrode structure which are more beneficial to metal film formation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a composite transparent conductive film and an amino acid anchoring method preparation process and application thereof. Arginine (arginine), lysine (lysine), and histidine (histidine) are used as inducing layers, and amino group (-NH) contained in the material2) The carboxyl group (-COOH) and the N atom of the side chain provide anchoring sites for the silver atoms, thereby inhibiting random aggregation and migration of the silver atoms and facilitating the formation of a flat continuous silver film at a relatively low thickness. And combining the anti-reflection layer with high light transmittance and high refractive index to obtain the flexible transparent conductive film with high light transmittance and low sheet resistance.
In order to solve the technical problems, the invention adopts the technical scheme that:
the method for preparing the composite transparent conductive film by using the amino acid anchored metal atoms comprises the following steps:
Adding amino acid into a methanol solvent to prepare a solution with the concentration of 0.5-5 mg/mL, and oscillating the solution in an ultrasonic cleaning machine for 40 min-1 h to fully dissolve the amino acid;
Cleaning and drying the substrate, and treating the substrate for 1-10 min by using an ultraviolet ozone cleaning instrument or a plasma cleaning machine to enhance the surface hydrophilicity of the substrate;
Coating an amino acid solution on the substrate, and annealing to fully volatilize the solvent;
and 5, preparing the anti-reflection layer material by vacuum evaporation or spin coating.
The amino acid in step 1 may be arginine (arginine), lysine (lysine), or histidine (histidine).
As a modification, the substrate in step 2 is glass, Polyethylene Terephthalate (PET), Polyimide (PI), Polyethylene Naphthalate (PEN), or UV-curable glue NOA63 (NORLAND OPTICAL ADHESIVE).
The coating mode in the step 3 is spin coating, dip coating or blade coating.
The metal layer in step 4 is made of silver, gold or copper.
The improvement is that the material of the anti-reflection layer in the step 5 is molybdenum oxide, HAT-CN, cuprous thiocyanate, PEDOT PSS, polystyrene, polyvinyl carbazole or zinc oxide.
The composite transparent conductive film prepared by any one of the preparation methods.
The composite transparent conductive film can be applied to light-emitting diodes, solar cells, photodetectors, touch screens, sensors, capacitors or electronic skins.
Has the advantages that:
compared with the prior art, the composite transparent conductive film and the amino acid anchoring method preparation process and application thereof have the following advantages:
1) the preparation process is simple in flow, low in cost and operable at normal temperature and normal pressure;
2) the application range is wide, and amino acid materials can be deposited on most rigid or flexible substrates in ways of dip coating, spin coating and the like to serve as a modification layer, so that subsequent metal and anti-reflection layer deposition is facilitated, and the application range is very wide;
3) can be applied to large-size equipment.
Drawings
FIG. 1 shows the sheet resistance of the electrodes of the different amino acid modification layers of example 1;
FIG. 2 is a schematic representation of a silver film with different amino acid modification layers on a PET substrate according to example 2;
FIG. 3 is the light transmittance of the front and rear electrodes of the HAT-CN anti-reflection layer evaporated on the conductive film in example 2;
table 1 shows the mean sheet resistance of the front and rear electrodes of the conductive film evaporated HAT-CN anti-reflection layer in example 2;
FIG. 4 is a bending property test of the transparent conductive film in example 2;
FIG. 5 is a pictorial representation (a) showing the electrodes (his/Ag/HAT-CN) illuminating the flexible OLED; (b) for electrode (his/Ag/HAT-CN) bending test, bending radius r =2.5mm, and the substrates were all Polyethylene Terephthalate (PET, 0.125 mm).
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
the method for preparing the composite transparent conductive film by using the amino acid anchored metal atoms comprises the following steps:
Adding amino acid into a methanol solvent to prepare a solution with the concentration of 0.5-5 mg/mL, and oscillating the solution in an ultrasonic cleaning machine for 40 min-1 h to fully dissolve the amino acid;
Cleaning and drying the substrate, and treating the substrate for 1-10 min by using an ultraviolet ozone cleaning instrument or a plasma cleaning machine to enhance the surface hydrophilicity of the substrate;
Coating an amino acid solution on the substrate, and annealing to fully volatilize the solvent;
and 5, preparing the anti-reflection layer material by vacuum evaporation or spin coating.
The amino acid in step 1 may be arginine (arginine), lysine (lysine), or histidine (histidine).
As a modification, the substrate in step 2 is glass, Polyethylene Terephthalate (PET), Polyimide (PI), Polyethylene Naphthalate (PEN), or UV-curable glue NOA63 (NORLAND OPTICAL ADHESIVE).
The coating mode in the step 3 is spin coating, dip coating or blade coating.
The metal layer in step 4 is made of silver, gold or copper.
The improvement is that the material of the anti-reflection layer in the step 5 is molybdenum oxide, HAT-CN, cuprous thiocyanate, PEDOT PSS, polystyrene, polyvinyl carbazole or zinc oxide.
The composite transparent conductive film prepared by any one of the preparation methods.
The composite transparent conductive film can be applied to light-emitting diodes, solar cells, photodetectors, touch screens, sensors, capacitors or electronic skins.
Example 1
The method for preparing the composite transparent conductive film by using the amino acid anchored metal atoms sequentially comprises the following steps:
1) and preparing an amino acid solution:
respectively preparing methanol solutions of arginine (arginine), lysine (lysine) and histidine (histidine) at a concentration of 2mg/mL, and placing the methanol solutions in an ultrasonic cleaning machine for oscillation for 40min to fully dissolve amino acids;
2) preparing and pretreating a glass substrate:
sequentially cleaning white glass in a detergent, ethanol, acetone and deionized water for 10min, transferring the white glass to a drying oven at 120 ℃ for drying for 1h, and treating the surface of the white glass for 10min under the power of 45W by using an ultraviolet ozone cleaning instrument to increase the surface hydrophilicity of the white glass;
3) and deposition of the amino acid modification layer:
respectively spin coating arginine (arginine), lysine (lysine) and histidine (histidine) solutions on a glass substrate at a rotation speed of 2000rpm for 30s, and baking on a hot bench at a temperature of 60 ℃ for 10min to fully volatilize the solvents;
4) vacuum evaporation of a conductive metal (silver) layer material:
placing 3 samples in a vacuum evaporation machine, and evaporating the silver for 7nm at a rate of 0.3 nm/s;
5) vacuum evaporation for preparing anti-reflection layer material
Vapor-depositing 20nm anti-reflection layer MoO3Obtaining transparent metal electrodes with 3 different amino acids;
for comparison, the following were: silver thin film (7 nm) deposited directly on glass substrate.
6) Characterization test of the film:
testing the sheet resistance of the film by using an ST-2258C type multifunctional digital four-probe tester (ST-2258C multifunctional four-probe tester); the transmittance of the film was measured using an ultraviolet/visible spectrophotometer (LAMBDA 35), wavelength range: 300nm to 800nm, and the light transmittance of the glass substrate is used as a base line.
Example 2
The method for preparing the composite transparent conductive film by using the amino acid anchored metal atoms sequentially comprises the following steps:
1) and preparing an amino acid solution:
preparing a methanol solution of arginine (arginine), lysine (lysine) and histidine (histidine) at a concentration of 2mg/mL, and placing the methanol solution in an ultrasonic cleaning machine for oscillation for 40min to fully dissolve amino acid;
2) pretreatment of the PET substrate:
the PET (0.125 mm) substrate was ultrasonically cleaned with ethanol for 30 min and dried in an oven at 60 ℃ for 10 min. Then, the surface is treated for 10min under the power of 45W by using an ultraviolet ozone cleaning instrument to increase the hydrophilicity;
3) and deposition of the amino acid modification layer:
respectively spin coating arginine (argine), lysine (lysine) and histidine (histidine) on a PET substrate at the rotating speed of 2000rpm for 30s, and baking on a hot bench at the temperature of 60 ℃ for 10min to fully volatilize a solvent;
4) vacuum evaporation of a conductive metal (silver) layer material:
placing 3 samples in a vacuum evaporation machine, and evaporating the silver for 7nm at a rate of 0.3 nm/s;
5) vacuum evaporation for preparing anti-reflection layer material
35nm anti-reflection layer HAT-CN vapor depositionObtaining transparent metal electrodes with 3 different amino acids;
for comparison, the following were: a thin film of silver (7 nm) deposited directly on a Polyethylene Terephthalate (PET, 0.125 mm) substrate.
6) Characterization test of the film:
testing the sheet resistance of the film by using an ST-2258C type multifunctional digital four-probe tester (ST-2258C multifunctional four-probe tester); the transmittance of the film was measured using an ultraviolet/visible spectrophotometer (LAMBDA 35), wavelength range: 300 nm-800 nm, and taking the light transmittance of the PET substrate as a base line, as shown in figure 3; the surface topography of the film was characterized using a field emission scanning electron microscope (hitachi S4800), as shown in fig. 2; the film was subjected to a bending performance test using a slide table, and the bending radius of the conductive film was set to 2.5mm as shown in fig. 4 and 5.
TABLE 1
The invention uses arginine (arginine), lysine (lysine) and histidine (histidine) as inducing layers, and the amino (-NH) contained in the materials2) The carboxyl group (-COOH) and the N atom of the side chain provide anchoring sites for the silver atoms, thereby inhibiting random aggregation and migration of the silver atoms and facilitating the formation of a flat continuous silver film at a relatively low thickness. And combining the anti-reflection layer with high light transmittance and high refractive index to obtain the flexible transparent conductive film with high light transmittance and low sheet resistance.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (8)
1. The method for preparing the composite transparent conductive film by using the amino acid anchored metal atoms is characterized by comprising the following steps of:
step 1, preparing an amino acid solution
Adding amino acid into a methanol solvent to prepare a solution with the concentration of 0.5-5 mg/mL, and oscillating the solution in an ultrasonic cleaning machine for 40 min-1 h to fully dissolve the amino acid;
step 2, cleaning the substrate and performing hydrophilic treatment
Cleaning and drying the substrate, and treating the substrate for 1-10 min by using an ultraviolet ozone cleaning instrument or a plasma cleaning machine to enhance the surface hydrophilicity of the substrate;
step 3, coating an amino acid inducing layer on the substrate
Coating an amino acid solution on the substrate, and annealing to fully volatilize the solvent;
step 4, evaporating a conductive metal layer material in vacuum;
and 5, preparing the anti-reflection layer material by vacuum evaporation or spin coating.
2. The method for preparing a composite transparent conductive film by anchoring metal atoms with amino acids according to claim 1, wherein the amino acids in step 1 are arginine, lysine, or histidine.
3. The preparation of the composite transparent conductive film by anchoring metal atoms with amino acids according to claim 1, wherein the substrate in step 2 is glass, polyethylene terephthalate, polyimide, polyethylene naphthalate or UV curable glue NOA 63.
4. The method for preparing a composite transparent conductive film by using amino acid anchored metal atoms as claimed in claim 1, wherein the coating in step 3 is spin coating, dip coating or blade coating.
5. The method for preparing a composite transparent conductive film by using amino acid anchored metal atoms as claimed in claim 1, wherein the metal layer in step 4 is made of silver, gold or copper.
6. The method for preparing a composite transparent conductive film by using amino acid anchored metal atoms as claimed in claim 1, wherein the material of the anti-reflection layer in step 5 is molybdenum oxide, HAT-CN, cuprous thiocyanate, PEDOT: PSS, polystyrene, polyvinylcarbazole or zinc oxide.
7. The composite transparent conductive film prepared by the method according to any one of claims 1 to 6.
8. Use of the composite transparent conductive film according to claim 1 or claim 7 in light emitting diodes, solar cells, photodetectors, touch screens, sensors, capacitors, or electronic skins.
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