CN111009336B - Flexible and transparent conductive film and preparation method thereof - Google Patents
Flexible and transparent conductive film and preparation method thereof Download PDFInfo
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- CN111009336B CN111009336B CN201911256555.1A CN201911256555A CN111009336B CN 111009336 B CN111009336 B CN 111009336B CN 201911256555 A CN201911256555 A CN 201911256555A CN 111009336 B CN111009336 B CN 111009336B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 53
- 239000004038 photonic crystal Substances 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002077 nanosphere Substances 0.000 claims description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- 239000000377 silicon dioxide Substances 0.000 description 21
- 235000019441 ethanol Nutrition 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001230 polyarylate Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 description 2
- 230000006355 external stress Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920006135 semi-crystalline thermoplastic polymer Polymers 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The invention belongs to the field of materials, and discloses a flexible and transparent conductive film. The conductive film comprises a substrate and silver nanowires; the silver nanowires form a network structure, and the conductive film further comprises photonic crystals and/or conductive polymers, wherein the photonic crystals are arranged in the network holes of the network structure formed by the silver nanowires. The preparation method of the conductive film comprises the following steps: (1) depositing a photonic crystal on the surface of the substrate; (2) mixing soluble salt of silver, a reducing agent, a surfactant and a solvent to obtain a mixed solution, and then coating the mixed solution on the surface of the photonic crystal prepared in the step (1) in a constant-temperature vacuum environment; then standing and washing to obtain the conductive film. The conductive film prepared by the invention has good flexibility, transmittance and conductivity, wherein the transmittance can exceed 97%, and the square resistance value can be lower than 20 omega/□.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a flexible and transparent conductive film and a preparation method thereof.
Background
The flexible and transparent conductive film is widely applied to the fields of flexible displays, flexible touch screens, flexible OLEDs, expandable solar cells and the like due to high light transmittance, high conductivity and flexibility.
At present, the commercial transparent conductive film is mainly an ITO (indium tin oxide) conductive film, but the ITO conductive film has the defects of poor flexibility, indium resource shortage, easy diffusion of metal ions, no acid and alkali resistance and the like, and the application of the ITO conductive film in flexible electronic products is limited to a great extent. Common flexible electrode materials mainly include: carbon nanotubes, conductive polymers, graphene, silver nanowires, and the like. Wherein, the flexibility of the carbon nano tube is high, but the square resistance is large; the conductive polymer has high flexibility, low cost and poor chemical stability, and the blue light wave band has strong absorption; the conductivity and flexibility of the graphene are excellent, but the process is difficult, the square resistance is large, and the actual requirements of electronic products cannot be met; the silver nanowires are paid much attention from the market due to their ultra-strong flexibility, thermal conductivity and electrical conductivity, but the silver nanowires used in the preparation of the transparent conductive film at present are easy to agglomerate, and influence the electrical conductivity and light transmittance.
In the prior art, the silver nanowires are mostly dispersed in an organic solvent or an inorganic solvent to form a film through self-sedimentation, so more silver nanowires are required to be arranged in cluster aggregation to ensure the conductivity of the silver nanowire film, but the light transmittance of the film is not facilitated, and the silver nanowires are required to be distributed more sparsely to ensure the light transmittance of the film, but the conductivity of the film is just greatly reduced. In addition, the film has a large number of pores, and the surface roughness of local areas is too large, so that large leakage current and even short circuit of the device are easily caused.
Accordingly, it is desirable to provide a flexible, transparent conductive film that has both good light transmission and conductivity while maintaining the flexibility of the conductive film.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a flexible and transparent conductive film which can simultaneously have good light transmission and conductivity, and the conductive film can simultaneously keep good flexibility.
In addition, the invention also provides a preparation method of the flexible and transparent conductive film.
A flexible, transparent conductive film comprising a substrate, silver nanowires; the silver nanowires are arranged on the substrate and form a net structure.
The substrate is a flexible glass substrate or a flexible plastic substrate.
Preferably, the substrate is a semi-crystalline thermoplastic polymer or an amorphous polymer.
Further preferably, the substrate is selected from at least one of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polyetheretherketone (PEEK), polyethersulfone resin (PES), Polyarylate (PAR), Polycarbonate (PC), propyleneglycol butylether (PNB), and Polyimide (PI) (each of PAR, PC, PI can be used as a flexible substrate), and a textile substrate.
Preferably, the conductive film comprises a substrate, silver nanowires and photonic crystals; the photonic crystal and the silver nanowire are arranged on the substrate; the silver nanowires form a net structure (the photonic crystals and the silver nanowires form a two-dimensional-like structure, and the photonic crystals are arranged in the meshes of the net structure formed by the silver nanowires). The photonic crystal has the effect similar to a convex lens, and is beneficial to improving the light transmittance of the conductive film.
Preferably, the photonic crystal is a nanosphere.
Further preferably, the photonic crystal is selected from inorganic oxide nanospheres, carbon nanospheres, polystyrene nanospheres, polymethyl methacrylate (PMMA) nanospheres, Polycarbonate (PC) nanospheres, silicone nanospheres.
More preferably, the inorganic oxide nanospheres are selected from at least one of silica nanospheres, titanium dioxide nanospheres, or tin dioxide nanospheres.
Preferably, the particle size of the inorganic oxide nanospheres is 1-300 nm; further preferably, the particle size of the inorganic oxide nanospheres is 1-200 nm; more preferably, the inorganic oxide nanospheres have a particle size of 50-150 nm.
Preferably, the conductive film further comprises a conductive polymer, and the conductive polymer is arranged on the silver nanowire and plays a role in packaging the whole conductive film, so that the whole conductive film is protected, the flexibility of the conductive film and the surface smoothness of the conductive film are further improved, and the electric leakage condition is not easily caused.
Preferably, the conductive polymer may also be a conductive monomer capable of synthesizing a conductive polymer.
Preferably, the conductive polymer is poly (3-hexylthiophene) and a derivative thereof.
Preferably, the conductive monomer is selected from at least one of aniline, pyrrole and thiophene.
A method for preparing a flexible, transparent conductive film, comprising the steps of:
(1) depositing a photonic crystal on the surface of the substrate;
(2) mixing soluble salt of silver, a reducing agent, a surfactant and a solvent to obtain a mixed solution, and then coating the mixed solution on the surface of the photonic crystal prepared in the step (1) in a constant-temperature vacuum environment; then standing and washing to prepare the flexible and transparent conductive film.
Preferably, the specific process of depositing the photonic crystal on the substrate surface in the step (1) is as follows: the photonic crystal is dispersed with a solvent to obtain a dispersion of the photonic crystal, and then the substrate is immersed in the dispersion, and the solvent is evaporated.
Preferably, the solvent is an alcohol; further preferably, the alcohol is at least one selected from the group consisting of ethanol, propanol, and butanol.
Preferably, in the dispersion liquid of the photonic crystals, the concentration of the photonic crystals is 0.1-4 g/L; further preferably, the concentration of the photonic crystal in the dispersion of the photonic crystal is 0.1 to 2 g/L.
Preferably, the temperature at which the solvent is evaporated is from 25 to 100 ℃.
Preferably, the process of immersing the substrate in the dispersion and then evaporating the solvent is repeated 1 to 5 times.
Preferably, the thickness of the photonic crystal deposited on the substrate is 100-800 nm; it is further preferred that the thickness of the photonic crystal deposited on the substrate is 200-500 nm.
Preferably, the soluble salt of silver in step (2) is nitrate.
Preferably, the reducing agent in step (2) is selected from at least one of citric acid, sodium borohydride or ascorbic acid.
Preferably, the surfactant in step (2) is a quaternary ammonium salt, such as cetyltrimethylammonium bromide, tetradecyltrimethylammonium chloride or hexadecylpyridinium bromide; further preferably, in the step (2), the surfactant is cetyl trimethyl ammonium bromide.
Preferably, the solvent is an organic solvent; further preferably, the solvent is an alcohol.
Preferably, the concentration of the soluble salt of silver in the mixed solution in the step (2) is 0.1-8 g/L; further preferably, the concentration of the soluble salt of silver in the mixed solution in the step (2) is 0.5 to 5 g/L.
Preferably, the concentration of the reducing agent in the mixed solution in the step (2) is 0.1-8 g/L; further preferably, the concentration of the reducing agent in the mixed solution in the step (2) is 0.1 to 5 g/L.
Preferably, the concentration of the surfactant in the mixed solution in the step (2) is 0.05-15 g/L; further preferably, the concentration of the surfactant in the mixed solution in the step (2) is 0.1 to 10 g/L.
Preferably, the constant-temperature vacuum environment in the step (2) is an environment with the temperature of 90-120 ℃ and the vacuum degree of 1-100 Pa; further preferably, the constant-temperature vacuum environment in the step (2) is an environment with the temperature of 100 ℃ and the vacuum degree of 10 Pa.
Preferably, the coating amount of the mixed solution coated on the surface of the photonic crystal prepared in the step (1) in the step (2) is 1-40mL/cm2(ii) a Further preferably, the coating amount of the mixed solution coated on the surface of the photonic crystal prepared in the step (1) in the step (2) is 1-20mL/cm2。
Preferably, the standing in the step (2) is carried out at 20 to 100 ℃ under normal pressure for 5 to 30 hours.
Preferably, the washing process in the step (2) is washing for 1 to 6 times by alternately using water and absolute ethyl alcohol; further preferably, the water is deionized water.
Optionally, step (2) is followed by a process of removing the photonic crystal, for example, when the photonic crystal is a silica nanosphere, soaking the photonic crystal in an alkali solution, such as sodium hydroxide.
Preferably, after the step (2), the method further comprises the following steps: and (3) spraying a solution of a conductive polymer or a monomer capable of reacting to generate the conductive polymer on the surface of the conductive film prepared in the step (2), and then drying.
Specifically, for example, a solution of a conductive polymer, which is poly (3-hexylthiophene) and a derivative thereof, is coated on the prepared conductive thin film, and then dried under vacuum.
Preferably, the concentration of the conductive polymer is 1 to 20 g/L.
Preferably, the coating amount of the conductive polymer is 1 to 40mL/cm2(ii) a Further preferably, the coating amount of the conductive polymer in the step (2) is 1 to 20mL/cm2。
Preferably, the drying condition under vacuum is that the vacuum degree is 50-200Pa and the temperature is 50-105 ℃; further preferably, the drying under vacuum is carried out under conditions of a vacuum degree of 50 to 100Pa and a temperature of 60 to 105 ℃.
The conductive polymer plays a role in packaging the whole conductive film, so that the whole conductive film is protected, particularly silver nanowires of a formed net structure are protected, the flexibility of the conductive film and the surface smoothness of the conductive film are further improved, and the electric leakage condition is not easy to cause.
The conductive polymer may be a dispersion of monomers capable of forming a conductive polymer.
The conductive film is applied to the field of semiconductors.
The semiconductor field includes the display field, the touch screen field, the OLED field and the battery field.
A display comprises the conductive film.
A touch screen comprises the conductive film.
An OLED comprises the conductive film.
A solar cell comprises the conductive film.
The conductive film prepared by the invention forms the final silver nanowire with a net structure by utilizing the in-situ growth mode of the silver nanowire (completely different from the mode of directly adding the silver nanowire, and the silver nanowire with the net structure is generated by utilizing the reaction between substances under the action of the template), so that the contact resistance of the substance interface can be obviously reduced. The size of the mesh of the silver nanowire with the shape structure can be controlled by regulating the size of the photonic crystal serving as the template, and further the light transmittance of the conductive film can be regulated.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the preparation process of the conductive film, the photonic crystal is used as a template and is deposited on the surface of the flexible substrate, and then the mixed solution is sprayed under the action of the photonic crystal template to form the silver nanowire with a net structure. Wherein the mesh size of the silver nanowires of the mesh structure can be adjusted by controlling the size of the photonic crystal (e.g., silica nanosphere). When the size of the photonic crystal silicon dioxide nanosphere is increased, the porosity of the silver nanowire self-assembled grid structure prepared by using the photonic crystal silicon dioxide nanosphere as a template is higher, and the light transmission uniformity of the grid is obviously enhanced. The silver nanowires have special 'quasi-two-dimensional' grid structures, so that free electrons can freely migrate in the 'quasi-two-dimensional' direction to the maximum extent, the conductive dimensions and paths of the network structures are greatly expanded, and compared with a silver nanowire film formed in a traditional 'self-deposition' mode, the conductive film prepared by the method has excellent conductivity. Moreover, when the local area of the grid structure formed by the silver nanowires is stressed, the micro-area relative sliding or stretching can be generated to relieve the external stress. The estimated transmittance of the conductive film prepared by the invention can exceed 97 percent, and the square resistance value can be lower than 20 omega/□.
(2) In the conductive film, the photonic crystal not only plays a role of a template, but also plays a role similar to a convex lens, and is favorable for improving the light transmittance of the conductive film.
(3) The conductive polymer is used for packaging the conductive film, so that bridging between the flexible substrate and the silver nanowires of the net structure is greatly strengthened, the activity of the silver nanowires of the net structure is guaranteed to the maximum degree, external stress can be relieved remarkably, the flexibility of the conductive film and the surface smoothness of the conductive film are improved remarkably, and the conductive polymer is further widely applied to the field of flexible display.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
Example 1
A method for preparing a flexible, transparent conductive film, comprising the steps of:
(1) depositing the photonic crystal on the surface of the substrate, which comprises the following specific steps: dispersing silica nanospheres (with the size of 140-150nm) by using ethanol to obtain a dispersion liquid of the silica nanospheres, wherein the concentration of the dispersion liquid is 0.1g/L, then soaking a polyethylene terephthalate flexible substrate in the dispersion liquid, evaporating the ethanol at 100 ℃, and forming a layer of silica nanospheres (namely forming a layer of photonic crystal film) on the surface of the flexible substrate;
(2) mixing silver nitrate, citric acid, cetyl trimethyl ammonium bromide and ethanol to obtain a mixed solution, wherein the concentration of the silver nitrate in the mixed solution is 1g/L, the concentration of the citric acid is 0.1g/L, and the concentration of the cetyl trimethyl ammonium bromide is 2g/L, and then coating the mixed solution on the surface of the silicon dioxide nanosphere prepared in the step (1) in an environment with the temperature of 100 ℃ and the vacuum degree of 10Pa, wherein the coating amount is 10mL/cm2(ii) a Then standing for 24 hours at the temperature of 20 ℃ and under normal pressure, and then alternately washing for 3 times by using deionized water and absolute ethyl alcohol;
(3) coating the solution of poly (3-hexylthiophene) with the concentration of 5g/L on the conductive film treated in the step (2) in an amount of 10mL/cm2Then keeping the film for 1 hour under the environment of 100Pa of vacuum degree and 100 ℃, and drying to obtain the conductive film containing the conductive polymer.
The prepared conductive film consists of a flexible substrate, silver nanowires, silicon dioxide nanospheres and poly (3-hexylthiophene); the silver nanowires form a net structure; the silicon dioxide nanospheres and the silver nanowires are arranged on the substrate; the silicon dioxide nanospheres are arranged in the mesh of the net structure formed by the silver nanowires, and the poly (3-hexylthiophene) is arranged on the silver nanowires to package and protect the whole conductive film.
Example 2
A method for preparing a flexible, transparent conductive film, comprising the steps of:
(1) depositing the photonic crystal on the surface of the substrate, which comprises the following specific steps: dispersing silica nanospheres (with the size of 130-135nm) by using ethanol to obtain a dispersion liquid of the silica nanospheres, wherein the concentration of the dispersion liquid is 2g/L, then soaking a polyethylene naphthalate flexible substrate in the dispersion liquid, evaporating the ethanol at the temperature of 25 ℃, and forming a layer of silica nanospheres (namely forming a layer of photonic crystal film) on the surface of the flexible substrate;
(2) mixing silver nitrate, citric acid, cetyl trimethyl ammonium bromide and ethanol to obtain a mixed solution, wherein the concentration of the silver nitrate in the mixed solution is 5g/L, the concentration of the citric acid is 5g/L, and the concentration of the cetyl trimethyl ammonium bromide is 0.1g/L, and then coating the mixed solution on the surface of the silicon dioxide nanosphere prepared in the step (1) in an environment with the temperature of 25 ℃ and the vacuum degree of 100Pa, wherein the coating amount is 15mL/cm2(ii) a Then standing for 5 hours at 100 ℃ and normal pressure, and then alternately washing for 4 times by using deionized water and absolute ethyl alcohol;
(3) coating the solution of poly (3-hexylthiophene) with the concentration of 10g/L on the conductive film treated by the step (2) in an amount of 8mL/cm2Then keeping the film for 5 hours in an environment with the vacuum degree of 20Pa and the temperature of 60 ℃, and drying the film to obtain the conductive film containing the conductive polymer.
The prepared conductive film consists of a flexible substrate, silver nanowires, silicon dioxide nanospheres and poly (3-hexylthiophene); the silver nanowires form a net structure; the silicon dioxide nanospheres and the silver nanowires are arranged on the substrate; the silicon dioxide nanospheres are arranged in the mesh of the net structure formed by the silver nanowires, and the poly (3-hexylthiophene) is arranged on the silver nanowires to package and protect the whole conductive film.
Example 3
A method for preparing a flexible, transparent conductive film, comprising the steps of:
(1) depositing the photonic crystal on the surface of the substrate, which comprises the following specific steps: dispersing silica nanospheres (with the size of 140-150nm) by using ethanol to obtain a dispersion liquid of the silica nanospheres, wherein the concentration of the dispersion liquid is 0.5g/L, then soaking a polyether sulfone resin flexible substrate in the dispersion liquid, evaporating the ethanol at the temperature of 60 ℃, and forming a layer of silica nanospheres (namely forming a layer of photonic crystal film) on the surface of the flexible substrate;
(2) mixing silver nitrate, citric acid, cetyl trimethyl ammonium bromide and ethanol to obtain a mixed solution, wherein the concentration of the silver nitrate in the mixed solution is 2g/L, the concentration of the citric acid is 2g/L, and the cetyl trimethyl ammonium bromide isIs 0.1g/L, and then the mixed solution is coated on the surface of the silicon dioxide nanosphere prepared in the step (1) in an amount of 20mL/cm in an environment of 60 ℃ and a vacuum degree of 1Pa2(ii) a Then standing for 10 hours at the temperature of 60 ℃ and under normal pressure, and then alternately washing for 2 times by using deionized water and absolute ethyl alcohol;
(3) coating the solution of poly (3-hexylthiophene) with the concentration of 20g/L on the conductive film treated by the step (2) in an amount of 12mL/cm2Then keeping the film for 12 hours in an environment with the vacuum degree of 1Pa and the temperature of 25 ℃, and drying the film to obtain the conductive film containing the conductive polymer.
The prepared conductive film consists of a flexible substrate, silver nanowires, silicon dioxide nanospheres and poly (3-hexylthiophene); the silver nanowires form a net structure; the silicon dioxide nanospheres and the silver nanowires are arranged on the substrate; the silicon dioxide nanospheres are arranged in the mesh of the net structure formed by the silver nanowires, and the poly (3-hexylthiophene) is arranged on the silver nanowires to package and protect the whole conductive film.
Example 4
In comparison with example 1, example 4 does not include step (3), and the rest of the procedure is the same as example 1.
The conductive thin film prepared in example 4 is composed of a flexible substrate, silver nanowires, and silica nanospheres; the silver nanowires form a net structure, and the silicon dioxide nanospheres and the silver nanowires are arranged on the substrate; the silicon dioxide nanospheres are arranged in the meshes of the net structure formed by the silver nanowires.
Example 5
Compared with the embodiment 1, in the embodiment 5, between the step (2) and the step (3), the conductive film treated by the step (2) is soaked by using NaOH solution with the concentration of 1mol/L to remove the silicon dioxide nanospheres, and the rest process is the same as the embodiment 1.
The conductive thin film prepared in example 5 was composed of a flexible substrate, silver nanowires, and poly (3-hexylthiophene); the silver nanowires form a network structure.
Example 6
In comparison with example 5, step (3) was not included in example 6, and the rest of the procedure was the same as in example 5.
The conductive film prepared in example 6 was composed of a flexible substrate and silver nanowires; the silver nanowires form a network structure.
Example 7
Compared with example 1, the silica nanospheres of example 1 are replaced with carbon nanospheres of example 7, and the rest of the process is the same as example 1.
Example 8
In comparison with example 1, the silica nanospheres of example 1 were replaced with polystyrene nanospheres of example 8, and the rest of the procedure was the same as example 1.
Other photonic crystals, such as polycarbonate nanospheres, organosilicon nanospheres, titanium dioxide nanospheres or tin dioxide nanospheres, can be used as templates of the photonic crystals, and can provide a template function for growing the reticular silver nanowires.
The use of other surfactants, such as tetradecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride or hexadecylpyridinium bromide, also has the same effect as hexadecyltrimethylammonium bromide.
Comparative example 1
Compared with example 1, the silver nanowires in comparative example 1 are directly dispersed with ethanol (the concentration of the silver nanowires is 1g/L), and then directly coated on the surface of the silica nanospheres prepared in step (1), and then left to stand and washed, i.e., comparative example 1 is different from example 1 only in that the silver nanowires are used instead of the mixed solution of step (2) in example 1.
Product effectiveness testing
The conductive films obtained in examples 1 to 8 and comparative example 1 were measured for natural light transmittance and sheet resistance, and the results are shown in table 1.
Table 1:
as can be seen from table 1, the conductive films prepared in examples 1 to 8 of the present invention have both good light transmittance and good conductivity (the smaller the sheet resistance, the better the conductivity of the conductive film), and the light transmittance and conductivity of the conductive film can be well balanced.
In addition, the light transmission uniformity of the conductive films prepared in examples 1 to 6 of the present invention was improved by 40 to 50% with respect to the light transmission uniformity of the conductive film prepared in comparative example 1.
The flexibility and the surface smoothness of the conductive film obtained in example 1 were improved by 30 to 40% relative to those of the conductive film obtained in example 6.
Application example 1
A flexible display comprising the conductive film prepared in example 1.
Application example 2
A flexible touch panel comprising the conductive film prepared in example 2.
Application example 3
A flexible OLED comprising the conductive film prepared in example 3.
Claims (4)
1. A conductive film, comprising a substrate, silver nanowires; the silver nanowires are arranged on the substrate and form a net structure;
the conductive film further comprises a photonic crystal; the photonic crystal is arranged in the mesh of the reticular structure formed by the silver nanowires; the conductive film further comprises a conductive polymer; the conductive polymer is poly (3-hexylthiophene) and derivatives thereof;
the preparation method of the conductive film comprises the following steps:
(1) depositing a photonic crystal on the surface of the substrate;
(2) mixing soluble salt of silver, a reducing agent, a surfactant and a solvent to obtain a mixed solution, coating the mixed solution on the surface of the photonic crystal prepared in the step (1), and standing to prepare the conductive film;
the process of depositing the photonic crystal on the surface of the substrate in the step (1) is as follows: firstly, dispersing the photonic crystal by using a solvent to obtain a dispersion liquid of the photonic crystal, then soaking the substrate in the dispersion liquid, and evaporating the solvent;
the soluble salt of silver in the step (2) is nitrate; the reducing agent in the step (2) is at least one selected from citric acid, sodium borohydride or ascorbic acid;
after the step (2), the method further comprises the following steps: and (3) spraying a solution of a conductive polymer or a monomer capable of reacting to generate the conductive polymer on the surface of the conductive film prepared in the step (2), and then drying.
2. The conductive film of claim 1, wherein the photonic crystal is selected from at least one of inorganic oxide nanospheres, carbon nanospheres, polystyrene nanospheres, polymethyl methacrylate nanospheres, polycarbonate nanospheres, or silicone nanospheres.
3. Use of the conductive film according to any one of claims 1 to 2 in the field of semiconductors.
4. A display comprising the conductive film according to any one of claims 1 to 2.
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