WO2012056774A1 - 透明導電性フィルム、電子デバイス及び電子デバイスの製造方法 - Google Patents
透明導電性フィルム、電子デバイス及び電子デバイスの製造方法 Download PDFInfo
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- FGGAOQTXQHKQOW-UHFFFAOYSA-N n,n-diphenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1 FGGAOQTXQHKQOW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- CDZOGLJOFWFVOZ-UHFFFAOYSA-N n-propylaniline Chemical compound CCCNC1=CC=CC=C1 CDZOGLJOFWFVOZ-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000552 poly[2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylenevinylene] polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- QYUMESOEHIJKHV-UHFFFAOYSA-M prop-2-enamide;trimethyl(propyl)azanium;chloride Chemical compound [Cl-].NC(=O)C=C.CCC[N+](C)(C)C QYUMESOEHIJKHV-UHFFFAOYSA-M 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/02—Presence of polyamine or polyimide polyamine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2481/00—Presence of sulfur containing polymers
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
Definitions
- the present invention relates to a transparent conductive film, an electronic device, and an electronic device manufacturing method. More specifically, the present invention is excellent in the balance between transparency and low resistivity, and has an excellent adhesiveness itself, so that a transparent conductive film capable of manufacturing an electronic device by a laminate process, The present invention relates to an electronic device used and a method for manufacturing an electronic device by a laminating process.
- transparent electrodes using a transparent conductive film have been actively studied in organic electroluminescence, various solar cells, touch panels, mobile phones, electronic papers, and the like.
- organic photoelectric conversion or electro-optic conversion devices represented by electronic solar cells are usually produced by laminating materials on electrodes made of a transparent conductive film.
- Various conductive films such as metal thin films, metal oxide thin films, and conductive nitride thin films have been studied as transparent conductive films, but at present, it is possible to achieve both light transmission and conductivity, and it is also durable.
- Metal oxide thin films are the mainstream because of their superiority.
- ITO indium oxide
- tin is well-balanced between light transmittance and conductivity, and is widely used (see Patent Document 1).
- Patent Document 2 there is a sheet in which a fine metal mesh or grid is formed on a transparent substrate such as PET (see Patent Document 2). These sheets can be used as transparent electrodes because the translucency and conductivity can be controlled depending on the mesh design (opening ratio determined by pitch and line width).
- a transparent conductive film having a conductive metal mesh layer and a transparent conductive layer made of a conductive polymer compound such as polythiophene on at least one surface of a transparent base sheet is disclosed (Patent Document 3, etc.) reference).
- electronic devices are conventionally manufactured by a vacuum deposition method, a dry process or similar wet process represented by coating, or a laminating process via an adhesive layer when laminating layers made of organic element materials.
- a laminating process a transparent electrode film and a transparent conductive film having adhesiveness are desired.
- balance of transparency, adhesiveness and surface resistivity is an issue. Yes. Therefore, it has been proposed to use a conductive organic polymer compound such as polythiophene or a derivative thereof as a conductive component in the conductive adhesive composition, and more specifically, a conductive organic polymer compound.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a transparent conductive film, an electronic device, and a method for manufacturing the electronic device that have solved the above-described problems.
- the present invention provides the following (1) a transparent conductive film having an adhesive conductive layer at an opening of a conductive metal mesh layer provided on at least one surface of a transparent substrate, wherein the conductive layer is ( A) comprising a conductive adhesive composition comprising a water-soluble vinyl polymer, (B) an organic additive, and (C) a conductive organic polymer compound, (B)
- the organic additive is at least one selected from water-soluble polyhydric alcohols, water-soluble pyrrolidones or hydrophilic aprotic solvents, and (C) conductive organic polymer compounds include polyanilines and polypyrroles.
- a transparent conductive film (2) When the glass transition temperature of (A) the water-soluble vinyl polymer is T1, (B) the melting point of the organic additive is T2, and the boiling point of the organic additive at 0.101 MPa (760 mmHg) is T3, T2 ⁇ The transparent conductive film according to (1), which satisfies a relationship of T1 ⁇ T3, (3) (A) The transparent conductive film according to (1), wherein the water-soluble vinyl polymer is polyvinyl alcohol, polyvinyl pyrrolidone, or an acrylic acid polymer, (4) An electronic device comprising the transparent conductive film according to (1) above, (5) The electronic device according to (4) above, wherein the transparent conductive film according to (1), the photoelectric conversion layer, and the cathode layer are arranged in this order, and (6) described in (4) above The method for producing an electronic device according to claim 1, wherein the photoelectric conversion layer is formed on the cathode layer, and the conductive
- the transparent conductive film of the present invention has high transparency and low surface resistivity, it has an excellent balance between transparency and conductivity, and itself has excellent adhesiveness. Electronic devices can be manufactured.
- the transparent conductive film of the present invention is a transparent conductive film having a conductive layer in an opening of a conductive metal mesh layer provided on at least one surface of a transparent substrate, and the conductive layer has a specific conductivity. It consists of an adhesive composition.
- the constituent material of the transparent conductive film of this invention is demonstrated using FIG.
- 1 is a conductive layer
- 2 is a conductive metal mesh layer
- 3 is a transparent substrate
- 7 is a transparent conductive film
- 9 is an opening of the conductive metal mesh layer.
- the transparent conductive film of the present invention is formed by providing a conductive metal mesh layer 2 on at least one surface of a transparent substrate 3 and filling the conductive layer 1 in the opening of the conductive metal mesh layer 2. Has been.
- the transparent substrate preferably has a total light transmittance of 70% or more from the viewpoint of transparency, and as such a transparent substrate, a plastic film is generally preferable from the viewpoint of flexibility.
- the plastic film include polyethylene terephthalate, polyethylene naphthalate, tetraacetylcellulose, syndiotactic polystyrene, polyphenylene sulfide, polycarbonate, polyarylate, polysulfone, polyestersulfone, polyetherimide, and cyclic polyolefin. Can be mentioned. Among them, those excellent in mechanical strength, durability and the like are preferable.
- the thickness of the transparent substrate is preferably 3 ⁇ m to 5 mm, more preferably 5 ⁇ m to 1 mm, and particularly preferably 10 ⁇ m to 300 ⁇ m from the viewpoint of the balance of mechanical strength, durability, and transparency.
- the conductive metal mesh layer 2 is provided on at least one surface of the transparent substrate 3.
- the conductive metal mesh layer 2 include a layer having a fine mesh structure with a metal grid pattern such as an electromagnetic wave shielding film of a plasma display.
- the thickness of the conductive metal mesh layer 2 is preferably 20 nm to 100 ⁇ m, and particularly preferably 30 to 200 nm. By setting the thickness to 20 nm or more, the conductivity is improved. By setting the thickness to 100 ⁇ m or less, the thickness of the entire transparent conductive film can be reduced, and the desired total light transmittance can be maintained. it can.
- the conductive metal mesh layer 2 Since the conductive metal mesh layer 2 has a fine mesh structure with a metal grid pattern, it has an opening 9 as shown in FIG.
- the opening ratio of the opening 9 is preferably 80% or more from the viewpoint of transparency, more preferably 90% or more, and still more preferably 95% or more.
- the pitch of the openings is preferably 1 to 3000 ⁇ m, more preferably 1 to 1500 ⁇ m. When the pitch of the openings is 1 ⁇ m or less, the transparency may be lowered. When the pitch is 3000 ⁇ m or more, it is difficult to obtain the effect of improving the conductivity.
- the line width of the conductive metal mesh layer 2 is preferably 100 nm to 1000 ⁇ m, and more preferably 1 ⁇ m to 100 ⁇ m. When the line width exceeds 1000 ⁇ m, the transparency may decrease, and when it is less than 100 nm, the effect of improving the conductivity may be difficult to obtain.
- Examples of the material for forming the conductive metal mesh layer 2 include metals and alloys.
- simple metals such as gold, silver, copper, aluminum, titanium, chromium, iron, cobalt, nickel, zinc, tin, iridium, indium, tungsten, molybdenum, platinum, iridium, hafnium, niobium, tantalum, tungsten, magnesium
- an alloy mainly composed of at least one metal selected from these groups can be used.
- gold, silver, copper, and platinum metals are preferable from the viewpoint of low corrosivity and high conductivity.
- Alloys include stainless steel, nickel-chromium, inconel (trade name), bronze, phosphor bronze, brass, duralumin, white phosphorus, invar, monel, metal phosphorous compounds such as nickel phosphorous alloys, metal boron compounds such as nickel boron, titanium nitride Nitride such as can be selected as appropriate.
- metal phosphorous compounds such as nickel phosphorous alloys
- metal boron compounds such as nickel boron, titanium nitride Nitride
- copper and copper-based alloys, nickel and nickel-based alloys, cobalt and cobalt-based alloys, chromium and chromium-based alloys, aluminum and aluminum-based alloys are electrically conductive. It is preferably used because of its excellent properties and good workability.
- the conductive metal mesh layer 2 may be a single layer made of metal or alloy, or may be a multilayer structure in which layers made of at least two kinds of metals or alloys are laminated.
- a method for providing the conductive metal mesh layer 2 will be described.
- PVD physical vapor deposition
- CVD thermal CVD
- atomic layer deposition ALD
- CVD chemical Vapor Deposition
- other dry processes or various processes such as dip coating, spin coating, spray coating, gravure coating, die coating, doctor blade, and electrochemical deposition, photolithographic methods, silver salts Method, ink-jet method, and screen printing method, which are appropriately selected according to the material of the conductive metal mesh layer 2.
- a conventionally known easy adhesion layer is formed between the conductive metal mesh layer 2 and the transparent substrate 3. Also good. Moreover, you may provide a transparent conductive layer between the conductive metal mesh layer 2 and the transparent base material 3 for the purpose of improving the electroconductivity of a transparent conductive film. As such a transparent conductive layer, a conductive metal oxide or the like can be used.
- the conductive metal oxide examples include tin-doped indium oxide (ITO), iridium oxide (IrO 2 ), indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), fluorine-doped tin oxide (FTO), and oxide.
- ITO indium oxide
- IrO 2 iridium oxide
- IrO 2 indium oxide
- SnO 2 tin oxide
- FTO fluorine-doped tin oxide
- oxide Indium-zinc oxide
- IZO zinc oxide
- ZnO gallium-doped zinc oxide
- AZO aluminum-doped zinc oxide
- MoO 3 molybdenum oxide
- TiO 2 titanium oxide
- These conductive metal oxides are used for dry deposition such as PVD (physical vapor deposition) such as vacuum deposition, sputtering, ion plating, or CVD (chemical vapor deposition) such as thermal CVD or atomic layer deposition (ALD). It can be formed by a known method such as a process.
- the thickness of such a transparent conductive layer is usually 10 to 1000 nm, preferably 10 to 500 nm, particularly preferably 30 to 300 nm, from the viewpoints of transparency and conductivity.
- the transparent conductive film of the present invention has the conductive layer 1 in the opening 9 of the conductive metal mesh layer 2 provided on at least one surface of the transparent substrate 3.
- the conductive layer 1 is composed of a conductive adhesive composition.
- the conductive adhesive composition includes (A) a water-soluble vinyl polymer, (B) an organic additive, and (C) a conductive organic polymer compound, and (B) the organic additive includes a water-soluble polyhydric alcohol, It is at least one selected from water-soluble pyrrolidones or hydrophilic aprotic solvents, and (C) the conductive organic polymer compound is at least one selected from polyanilines, polypyrroles or polythiophenes and derivatives thereof. is there.
- One water-soluble vinyl polymer of component (A) is for imparting adhesiveness to a conductive layer made of a conductive adhesive composition.
- the water-soluble vinyl polymer also includes a hot water-soluble vinyl polymer.
- the glass transition temperature (Tg) of the water-soluble polyvinyl polymer is preferably in the range of ⁇ 50 to 150 ° C., preferably 20 to 140 ° C., more preferably 30 from the viewpoints of film formability, adhesion, and handling. -130 ° C, more preferably 40-120 ° C.
- the water-soluble polyvinyl polymer has a structural unit of —CH 2 —CH (R) — in the polymer.
- the structure unit is not particularly limited as long as it has at least 30 mol% or more in the polymer.
- the water-soluble polyvinyl polymer may be a homopolymer containing this structural unit or a copolymer. Among these, those in which R is any one of a hydroxyl group, a carboxyl group, a pyrrolidone group, and an acrylamide group are preferable.
- R is a hydroxyl group have a structural unit of —CH 2 —CH (OH) —
- specific examples of the water-soluble vinyl polymer having a hydroxyl group include, for example, polyvinyl alcohol (PVA), polyvinyl alcohol -Ethylene copolymer, polyvinyl alcohol- (N-vinylformamide) copolymer, polyvinyl alcohol-vinyl acetate copolymer and the like.
- the water-soluble polyvinyl polymer having a hydroxyl group may be partially saponified or may be completely saponified.
- the degree of saponification is preferably 20 to 100 mol%, more preferably 35 to 100 mol%, still more preferably 40 to 100 mol%.
- Those having a carboxyl group in the polymer have a structural unit of —CH 2 —CH (COOH) —.
- Specific examples of the water-soluble polyvinyl polymer having a carboxyl group include polyacrylic acid (PAA).
- PAA polyacrylic acid
- the water-soluble vinyl polymer in which R is a pyrrolidone group has a structural unit of —CH 2 —CH (NC 4 O) —.
- polyvinylpyrrolidone PVP
- N-vinyl-2 -Pyrrolidone-ethylene copolymer N-vinyl-2-pyrrolidone-vinyl acetate copolymer and the like.
- the water-soluble vinyl polymer in which R is an acrylamide group has a structural unit of —CH 2 —CH (CONH 2 ) —, and specific examples thereof include polyacrylamide and the like.
- the water-soluble vinyl polymer has a functional group such as a hydrophobic group, a cationic group, an anionic group including a sulfonic acid group, a thiol group, a carbonyl group, and a silanol group other than the above structural units for the purpose of imparting various functions. You may contain in.
- these water-soluble polyvinyl polymers those in which R is any one of a hydroxyl group, a pyrrolidone group, and a carboxyl group from the viewpoints of film forming properties, adhesiveness, and handling, because the electronic device described later can be easily manufactured.
- PVA, PVP or PAA is preferable.
- the weight average molecular weight (Mw) of the water-soluble polyvinyl polymer is usually 500 to 500,000, preferably 500 to 300,000, more preferably 1,000 to 200,000, and 3,000 to 15 More preferably, it is 10,000. When the weight average molecular weight Mw of the water-soluble vinyl polymer is within this range, sufficient film formability and adhesiveness are exhibited in the transparent conductive film and the electronic device of the present invention.
- the weight average molecular weight Mw is a numerical value in terms of standard polystyrene measured by gel permeation chromatography (GPC).
- the other ethylenically unsaturated monomer which can be copolymerized may be copolymerized 1 type (s) or 2 or more types. .
- Examples of other copolymerizable ethylenically unsaturated monomers include: Carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, isopropenyl acetate, vinyl valelate, vinyl caprate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl versatate, vinyl pivalate Vinyl ester monomers; olefins such as ethylene, propylene, butylene; aromatic vinyls such as styrene and ⁇ -methylstyrene; methacrylic acid, fumaric acid, maleic acid, itaconic acid, monoethyl fumarate, maleic anhydride, anhydrous Ethylenically unsaturated carboxylic acid monomers such as itaconic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate
- the organic additive of component (B) is at least one selected from water-soluble polyhydric alcohols, water-soluble pyrrolidones, and hydrophilic aprotic solvents.
- the organic additive of component (B) is added for the purpose of improving conductivity. Although details are unknown, by adding such an organic additive, the orientation of the conductive organic polymer compound of the component (C) described later is improved, so that the conductivity is improved.
- the organic additive of component (B) those having a boiling point of 100 ° C. or higher at 1.101 MPa (760 mmHg) are preferable.
- boiling point is below 100 ° C.
- the organic additive volatilizes and scatters during the mixing process of the conductive adhesive composition, during storage, and in various heating processes when manufacturing electronic devices described later, resulting in a reduction in the blending ratio. Since the effect which improves electroconductivity falls, it is not preferable.
- a more preferred boiling point is in the range of 120 to 300 ° C., more preferably 140 to 300 ° C.
- water-soluble polyhydric alcohols that are one of the organic additives of component (B) include glycerin, diglycerin, polyglycerin, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol.
- alkylene oxide derivatives and the like may be used alone or in combinations of two or more thereof.
- Water-soluble pyrrolidones that are one of the organic additives of component (B) include N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-isopropylpyrrolidone, N-butylpyrrolidone, Nt-butyl Pyrrolidone, N-pentylpyrrolidone, N-hexylpyrrolidone, N-heptylpyrrolidone, N-cyclohexylpyrrolidone, N-octylpyrrolidone, N- (2-ethylhexyl) pyrrolidone, N-phenylpyrrolidone, N-benzylpyrrolidone, phenethylpyrrolidone, 2 -Methoxyethyl pyrrolidone, 2-methoxypropyl pyrrolidone, 2-hydroxypropyl pyrrolidone, vinyl
- an aprotic solvent is added as one of the component (B) organic additives.
- the aprotic solvent is blended in the conductive adhesive composition without volatilization / scattering.
- the hydrophilic aprotic solvent which is one of the organic additives of the component (B) include dimethyl sulfoxide and N, N-dimethylformamide.
- the component (B) is preferably selected in combination with the component (A) so as to satisfy the following relationship. That is, the glass transition temperature (Tg) of the water-soluble polyvinyl polymer of component (A) is T1, the melting point of the organic additive of component (B) is T2, and the boiling point at 0.101 MPa (760 mmHg) of the organic additive is T3. In such a case, the combination satisfies T2 ⁇ T1 ⁇ T3.
- the glass transition temperature T1 of the water-soluble vinyl polymer of the component (A) is a value measured by a [differential scanning calorimetry (DSC) measuring instrument].
- water-soluble polyhydric alcohol satisfying the relationship of T2 ⁇ T1 ⁇ T3 with the component (A) include, for example, glycerin [melting point T2: 18 ° C., boiling point T3: 290 ° C.], ethylene glycol [melting point T2 : -11.5 ° C, boiling point T3: 197 ° C], diethylene glycol [melting point T2: -6.5 ° C, boiling point T3: 245 ° C], propylene glycol [melting point T2: -59 ° C, boiling point T3: 188.2 ° C] Dipropylene glycol [melting point T2: ⁇ 40 ° C., boiling point T3: 232 ° C.], 1,3-butanediol [melting point T2: ⁇ 50 ° C., boiling point T3: 207.5 ° C.], 1,4-butanediol [melting point T2: 19 ° C., boiling point T3:
- glycerin and 1,4-butanediol are preferable from the viewpoint of improving conductivity.
- water-soluble pyrrolidone derivatives of component (B) that satisfy the relationship of T2 ⁇ T1 ⁇ T3 include N-methylpyrrolidone [melting point T2: ⁇ 24 ° C., boiling point T3: 202 ° C.], vinylpyrrolidone [melting point T2: 13. 5 ° C, boiling point T3: 214.5 ° C], 2-pyrrolidone [melting point T2: 24.6 ° C, boiling point T3: 245 ° C], and the like.
- hydrophilic aprotic solvent of component (B) that satisfies the relationship of T2 ⁇ T1 ⁇ T3 include dimethyl sulfoxide (DMSO) [melting point T2: 19 ° C., boiling point T3: 189 ° C.], N, N-dimethyl. And formamide (DMF) [melting point T2: -61 ° C, boiling point T3: 153 ° C].
- DMSO dimethyl sulfoxide
- DMF formamide
- the conductive organic polymer compound of component (C) is at least one selected from polyanilines, polypyrroles or polythiophenes, and derivatives thereof.
- Polyanilines, polypyrroles or polythiophenes, and derivatives thereof are conductive polymers having conductivity through ⁇ -electron conjugation.
- Polyanilines are high molecular weight compounds of compounds in which the 2-position, 3-position or N-position of aniline is substituted with an alkyl group having 1 to 18 carbon atoms, an alkoxy group, an aryl group, a sulfonic acid group or the like.
- Methyl aniline poly 3-methyl aniline, poly 2-ethyl aniline, poly 3-ethyl aniline, poly 2-methoxy aniline, poly 3-methoxy aniline, poly 2-ethoxy aniline, poly 3-ethoxy aniline, poly N-methyl aniline Poly N-propyl aniline, poly N-phenyl-1-naphthyl aniline, poly 8-anilino-1-naphthalene sulfonic acid, poly 2-aminobenzene sulfonic acid, poly 7-anilino-4-hydroxy-2-naphthalene sulfonic acid Etc.
- Examples of the derivatives of polyanilines include the dopants of the polyanilines.
- halide ions such as chloride ion, bromide ion and iodide ion; perchlorate ion; tetrafluoroborate ion; hexafluoroarsenate ion; sulfate ion; nitrate ion; thiocyanate ion; hexafluoride Silicate ion; Phosphate ion such as phosphate ion, phenyl phosphate ion, hexafluorophosphate ion; trifluoroacetate ion; alkylbenzenesulfonate ion such as tosylate ion, ethylbenzenesulfonate ion, dodecylbenzenesulfonate ion; methylsulfone Alkyl sulfonate ions such as acid ions and ethyl sulfonate ions; or poly
- Polypyrroles are high molecular weight compounds of compounds in which 1-position, 3-position or 4-position of pyrrole is substituted with an alkyl group or alkoxy group having 1 to 18 carbon atoms, such as poly 1-methyl pyrrole, poly 3-pyrrole. Examples thereof include methyl pyrrole, poly 1-ethyl pyrrole, poly 3-ethyl pyrrole, poly 1-methoxy pyrrole, 3-methoxy pyrrole, poly 1-ethoxy pyrrole, poly 3-ethoxy pyrrole and the like. Examples of the derivatives of polypyrroles include the dopants of the polypyrroles. As a dopant, what was illustrated as a dopant body of the above-mentioned polyaniline can be used.
- Polythiophenes are high molecular weight compounds of compounds in which the 3-position or 4-position of thiophene is substituted with an alkyl group or alkoxy group having 1 to 18 carbon atoms, such as poly-3-methylthiophene, poly-3-ethylthiophene, poly Examples thereof include polymers such as 3-methoxythiophene, poly-3-ethoxythiophene, and poly3,4-ethylenedioxythiophene (PEDOT).
- Examples of the derivatives of polythiophenes include the dopants of the polythiophenes. As a dopant, what was illustrated as a dopant body of the above-mentioned polyaniline can be used.
- the conductive organic polymer compound it is possible to easily adjust high conductivity in a very small amount, and since it has a hydrophilic skeleton useful for easy dispersion in an aqueous solution, poly ( 3,4-ethylene oxide thiophene) and a mixture of polystyrene sulfonate ions (hereinafter sometimes referred to as “PEDOT: PSS”) and the like are preferable.
- the conductive adhesive composition for forming a conductive layer in the transparent conductive film of the present invention comprises (A) a water-soluble vinyl polymer, (B) an organic additive, and (C) a conductive organic polymer compound.
- the compounding quantity of each component is as follows.
- the component (A) is 1 to 60 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass. It is.
- Component (B) is 0.1 to 90 parts by weight, preferably 10 to 70 parts by weight, more preferably 20 to 65 parts by weight.
- Component (C) is 0.1 to 90 parts by weight, preferably 0.5 to 75 parts by weight, more preferably 5 to 55 parts by weight.
- the adhesiveness is not expressed, and when it exceeds 60 parts by mass, the transparency and conductivity are lowered, which is not preferable.
- the component (B) is less than 0.1 parts by mass, the conductivity is low, and when it exceeds 90 parts by mass, the adhesiveness is lowered, which is not preferable.
- component (C) is less than 0.1 parts by mass, the conductivity is low, and when it exceeds 90 parts by mass, the adhesiveness is not exhibited, which is not preferable.
- the conductive adhesive composition may be a solution containing components (A), (B), and (C) and a solvent such as water, toluene, ethyl acetate, and methyl ethyl ketone. .
- a solvent such as water, toluene, ethyl acetate, and methyl ethyl ketone.
- the active ingredient concentration is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass.
- a tackifier in addition to the components (A), (B), (C) and the solvent, a tackifier, a plasticizer, a thickener, a wetting agent Agents, antifoaming agents, film-forming aids, preservatives, rust inhibitors, freeze-thaw stabilizers, pigments, colorants, fillers, metal powders, antioxidants, light stabilizers, UV absorbers, etc. are added as appropriate. be able to.
- Examples of the method for forming the conductive layer 1 include various processes such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade, and wet processes such as electrochemical deposition. Is done.
- the conductive adhesive composition provided on the transparent substrate 3 by applying a solution (coating solution) obtained by dissolving or dispersing the conductive adhesive composition in an appropriate solvent such as purified water to the above-described various coatings.
- the conductive layer is formed by applying to the opening of the conductive metal mesh layer 2 and drying the resulting coating, and optionally heating the organic adhesive in the conductive adhesive composition so as not to evaporate. 1 is preferably formed. According to such a method, the conductive layer 1 can be easily formed in the opening 9 of the conductive metal mesh layer 2.
- the thickness of the conductive layer 1 made of the conductive adhesive composition is preferably 5 to 10,000 nm, more preferably 30 to 3,000 nm. If it is less than 5 nm, the adhesiveness is not expressed, and if it exceeds 10,000 nm, the conductivity is lowered.
- the conductive layer has high conductivity applicable as an electronic device.
- the surface resistivity of the conductive layer 1 is preferably 1 to 1.0 ⁇ 10 10 ⁇ / ⁇ , more preferably 1 to 1.0 ⁇ 10 9 , and more preferably 1 to 1.0 ⁇ 10 8 ⁇ / ⁇ . Further preferred. When it exceeds 1.0 ⁇ 10 10 ⁇ / ⁇ , the electrical conductivity is low, and the performance deteriorates when used in an electronic device.
- the total light transmittance of the conductive layer 1 is preferably 80% or more and as close to 100% as possible. When the total light transmittance is 80% or more, the transparency is sufficient when it is used for various electronic devices such as solar cells, and it is preferably used.
- the transparent conductive film of the present invention has the conductive metal mesh layer 2 and the conductive layer 1 on at least one surface of the transparent substrate 3. As shown in FIG. 1, the conductive metal mesh layer 2 and the conductive layer 1 are provided on one surface of the transparent substrate 3, and the conductive layer 1 is filled in the opening 9 of the conductive metal mesh layer 2. Preferably it is formed.
- the conductive layer 1 may be formed so as to fill the opening of the conductive metal mesh layer 2 and may be formed so that the upper part of the conductive metal mesh layer 2 is hidden (7 in FIG. 3). reference). That is, the transparent conductive film 7 of the present invention has the conductive metal mesh layer 2 and the conductive layer 1 on at least one surface of the transparent base material 3, and the conductive metal mesh layer 2 is electrically connected to the opening 9.
- the conductivity is improved by filling the layer 1.
- the transparent conductive film of the present invention since the transparent conductive film of the present invention has high transparency and low surface resistivity, it has an excellent balance between transparency and conductivity, and itself has excellent adhesiveness. Therefore, it is possible to manufacture an electronic device by a laminating process.
- the surface resistivity on the side of the transparent conductive film of the present invention provided with the conductive layer and the metal mesh layer is preferably 1 to 1.0 ⁇ 10 9 ⁇ / ⁇ . When it exceeds 1.0 ⁇ 10 9 ⁇ / ⁇ , the electrical conductivity is low, and the performance deteriorates when used in an electronic device.
- the electronic device of the present invention has the above-described transparent conductive film.
- Electronic devices include organic devices such as organic transistors, organic memories, and organic EL; liquid crystal displays; electronic paper; thin film transistors; electrochromic; electrochemiluminescence devices; touch panels; displays; solar cells; Device; and the like.
- FIG. 2 is an example of an electronic device having the transparent conductive film of the present invention.
- 1 is a conductive layer
- 2 is a conductive metal mesh layer
- 3 is a transparent substrate
- 4 is a photoelectric conversion layer
- 5 is an electrode
- 6 is a substrate
- 7 is a transparent conductive film
- 8 is an electronic device. .
- a photoelectric conversion layer is a layer which receives a photoelectric effect, may consist of a single layer, and may consist of multiple layers.
- the photoelectric conversion layer is usually formed from an intrinsic semiconductor layer (i-type semiconductor).
- the photoelectric conversion layer is a layer that performs photoelectric conversion, and is preferably an organic semiconductor from the viewpoint of cost reduction, flexibility, ease of formation, high extinction coefficient, weight reduction, impact resistance, and the like of the raw material. .
- a stack of (p-type semiconductor layer / n-type semiconductor layer) or (p-type semiconductor layer / intrinsic semiconductor layer / n-type semiconductor layer) is used.
- the thickness of the photoelectric conversion layer varies depending on whether it is a single layer or a plurality of layers, but it is generally preferably 30 nm to 2 ⁇ m, particularly 40 nm to 300 nm from the viewpoint of conductivity and exciton diffusion distance. Is preferred.
- Intrinsic Semiconductor As an intrinsic semiconductor material, for example, a fullerene, a fullerene derivative, a first material composed of at least one of carbon nanotubes (CNT) and CNT compounds having semiconductivity, and a derivative of polyphenylene vinylene (PPV) Alternatively, it is possible to use a mixture in which a second material made of a polythiophene polymer material is mixed so that the obtained semiconductor becomes an intrinsic semiconductor.
- fullerene derivative for example, [6,6] -phenyl-C61-methyl butyrate (PCBM) and the like can be used, and fullerene into which a dimer of fullerene or an alkali metal or an alkaline earth metal is introduced. Compounds and the like can also be used. Further, as the CNT, carbon nanotubes or the like including fullerene or metal-encapsulated fullerene can be used. Furthermore, a CNT compound in which various molecules are added to the side wall or tip of the CNT can also be used.
- polyphenylene vinylene poly [2-methoxy, 5- (2′-ethyl-hexyloxy) -p-phenylene-vinylene] (MEH-PPV) or the like can be used.
- polythiophene polymer material Poly (3-alkylthiophene) such as poly-3-hexylthiophene (P3HT), dioctylfluorene-bithiophene copolymer (F8T2), and the like can be used.
- a particularly preferable intrinsic semiconductor is a mixture of PCBM and P3HT mixed at a mass ratio of 1: 0.3 to 1: 4.
- polyalkylthiophene such as poly-3-hexylthiophene (P3HT) and derivatives thereof; polyphenylene and derivatives thereof, poly [2-methoxy-5- (2 ′ -Ethyl-hexyloxy) -p-phenylene-vinylene] (MEH-PPV) and the like, polyphenylene vinylene and derivatives thereof, polysilane and derivatives thereof, porphyrin derivatives, phthalocyanine derivatives, polyalkylthiophenes and derivatives thereof, organometallic polymers, etc. .
- polyalkylthiophene and derivatives thereof are preferred.
- the mixture of these organic materials may be sufficient.
- the conductive polymer poly (3,4) -ethylenedioxythiophene / polystyrene sulfonate (PEDOT: PSS) can be preferably used.
- n-type semiconductor The material of the n-type semiconductor is not particularly limited, and 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTCDA), 3,4,9,10-perylene tetracarboxylic dian Hydride (PTCDA), 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), N, N′-dioctyl-3,4,9,10-naphthyltetracarboxydiimide (PTCDI-C8H), 2 -(4-Biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), 2,5-di (1-naphthyl) -1,3,4-oxadi Oxazole derivatives such as azole (BND), trizole such as 3- (4-biphenylyl) -4-phenyl-5- (4-t-
- fullerene compounds are particularly preferable because they are n-type semiconductors that are stable and have high carrier mobility.
- the fullerene compound for example, [6,6] -phenyl-C61-methyl butyrate (PCBM) can be used.
- PCBM is preferable from the viewpoint of having excellent electron acceptability.
- n-type semiconductors can be used alone or in combination of two or more.
- PVD physical vapor deposition
- CVD chemical vapor deposition
- thermal CVD thermal CVD
- atomic layer deposition ALD
- the electrode material is preferably a material having a relatively small work function.
- metals such as platinum, gold, aluminum, iridium, chromium, and zinc oxide, metal oxides or alloys, carbon nanotubes, or composites of carbon nanotubes and the above metals, metal oxides, or alloys can be given.
- the thickness of the electrode is preferably 20 nm to 1 ⁇ m, and particularly preferably 30 to 200 nm.
- a dry process such as PVD (physical vapor deposition) such as vacuum deposition, sputtering or ion plating, or CVD (chemical vapor deposition) such as thermal CVD or atomic layer deposition (ALD).
- the plastic film include polyethylene terephthalate, polyethylene naphthalate, tetraacetylcellulose, syndiotactic polystyrene, polyphenylene sulfide, polycarbonate, polyarylate, polysulfone, polyestersulfone, polyetherimide, and cyclic polyolefin.
- the thickness of the base material layer 6 is preferably 3 ⁇ m to 5 mm, more preferably 5 ⁇ m to 1 mm, and particularly preferably 10 ⁇ m to 300 ⁇ m, from the viewpoint of the balance between mechanical strength and transparency.
- the method for producing an electronic device of the present invention is characterized in that the conductive layer of the transparent conductive film and the surface of the photoelectric conversion layer are bonded together. That is, it is characterized in that the conductive layer of the transparent conductive film and the surface of the photoelectric conversion layer are bonded together at a temperature higher than the temperature at which the conductive adhesive composition is softened.
- the manufacturing method of the electronic device of this invention is demonstrated using FIG. In FIG. 3, the downward arrow indicates that the photoelectric conversion layer 4 and the conductive layer 1 are bonded to each other at a temperature higher than the temperature at which the conductive adhesive composition is softened to form an electronic device.
- the electrode 5 is formed on the base material layer 6, and the photoelectric conversion layer 4 is formed on the electrode 5.
- an electronic device is manufactured by bonding the conductive layer 1 of the transparent conductive film and the surface of the photoelectric conversion layer 4 at a temperature equal to or higher than the temperature at which the conductive adhesive composition is softened.
- the temperature at which the conductive adhesive composition is softened is a temperature equal to or higher than the glass transition temperature (Tg) of the water-soluble vinyl polymer. Specifically, it is about 60 to 140 ° C. from the viewpoint of easy production.
- the electronic device since the surface of the conductive layer 1 and the surface of the photoelectric conversion layer 4 of the transparent conductive film are bonded together, the electronic device can be easily manufactured by a laminating process. Moreover, according to this method, since the electrode 5 is formed on the base material layer 6 and the photoelectric conversion layer 4 is formed on the electrode 5, there is a step of forming the electrode 5 on the light conversion layer 4. do not do. Therefore, the electrode 5 does not become non-uniform, and the photoelectric conversion layer 4 is not damaged by the energy at the time of forming the electrode 5, and the performance of the electronic device does not deteriorate.
- ⁇ Example 1> [Preparation of conductive adhesive composition]
- a water-soluble vinyl polymer of component (A) polyvinyl alcohol [manufactured by Sigma-Aldrich, product name “polyvinyl alcohol”, weight average molecular weight 9100, Tg (T1): 50 ° C., described as PVA in Table 1] 50 mass Part was used.
- an organic additive of component (B) 50 parts by mass of glycerin [manufactured by Sigma Aldrich, product name “glycerin”, melting point (T2): 18 ° C., boiling point (T3): 290 ° C.] was used.
- a conductive organic polymer compound of component (C) a mixture of poly (3,4-ethylene oxide thiophene) (PEDOT) and polystyrene sulfonic acid (PSS), which is a derivative of polythiophenes (PEDOT: PSS) (H. C. Starck, product name “CleviousP VP.AI4083”, 1% by mass of active ingredient (solvent: purified water), described in Table 1 as polythiophenes], 10,000 parts by mass. 200 parts by mass of purified water was added to the components (A), (B) and (C) to prepare a coating liquid for the conductive adhesive composition (active ingredient: 1.9% by mass).
- solvent purified water
- a copper film having a thickness of 100 nm is formed by depositing copper on one surface of a transparent substrate (product name “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) under a reduced pressure of 1 ⁇ 10 ⁇ 3 Pa or less by a vapor deposition method. A layer was formed. Next, resist treatment and etching treatment were performed to produce a conductive metal mesh layer (opening pitch: 1200 ⁇ m / line width 20 ⁇ m, total light transmittance 89%, surface resistivity 2 ⁇ / ⁇ ).
- the coating solution of the conductive adhesive composition prepared as described above is applied to the opening of the conductive metal mesh layer using a Meyer bar (20 mil), and the drying is performed at 120 ° C. for 10 minutes. Dried. In this way, a transparent conductive film having a conductive layer (thickness: 500 nm) made of a conductive adhesive composition at the opening of the conductive metal mesh layer was produced.
- an aluminum film is deposited on a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”) under a reduced pressure of 1 ⁇ 10 ⁇ 3 Pa or less by a vapor deposition method.
- a 100 nm thick aluminum layer (electrode) was formed.
- the solution (concentration: 2% by mass) was applied by spin casting, and dried at 120 ° C. for 10 minutes to form a 100 nm-thick photoelectric conversion layer.
- the surface of the photoelectric conversion layer and the surface of the conductive layer of the transparent conductive film are bonded together by heating the pressure of a roll laminator (product name “RSL-328S” manufactured by Royal Sovereign Co., Ltd.) to 120 ° C. Got a device.
- a roll laminator product name “RSL-328S” manufactured by Royal Sovereign Co., Ltd.
- Examples 2 and 3 A transparent conductive film and an electronic device were produced in the same manner as in Example 1 except that the conductive adhesive composition prepared at the blending ratio shown in Table 1 (parts by mass, the same applies hereinafter) was used.
- Example 4 The amount of PVA of component (A) is 25 parts by mass, and N-methylpyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd., T2: melting point ⁇ 24 ° C., T3: A boiling point 202 ° C.] A transparent conductive film and an electronic device were produced in the same manner as in Example 1 except that 80 parts by mass was used.
- Example 5 Using the water-soluble vinyl polymer of component (A), 50 parts by mass of polyvinylpyrrolidone (manufactured by Sigma-Aldrich, Tg (T1): 80 ° C., described as PVP in Table 1) is used instead of PVA. As the organic additive of B), a transparent conductive film and an electronic device were produced in the same manner as in Example 1 except that the amount of glycerin was 100 parts by mass.
- Example 6 Example except that 100 parts by mass of N-methylpyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd., T2: melting point ⁇ 24 ° C., T3: boiling point 202 ° C.] was used as the organic additive of component (B) instead of glycerin In the same manner as in Example 5, a transparent conductive film and an electronic device were produced.
- N-methylpyrrolidone manufactured by Wako Pure Chemical Industries, Ltd., T2: melting point ⁇ 24 ° C., T3: boiling point 202 ° C.
- Example 7 As an organic additive of component (B), 100 mass of dimethyl sulfoxide [manufactured by Wako Pure Chemical Industries, Ltd., description in Table 1 is DMSO, T2: melting point 19 ° C., T3: boiling point 189 ° C.] instead of glycerol A transparent conductive film and an electronic device were produced in the same manner as in Example 1 except for using a part.
- Example 8 As an organic additive of component (B), 100 mass of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., description in Table 1 is DMF, T2: melting point ⁇ 61 ° C., T3: boiling point 153 ° C.) instead of glycerin A transparent conductive film and an electronic device were produced in the same manner as in Example 1 except for using a part.
- dimethylformamide manufactured by Wako Pure Chemical Industries, Ltd., description in Table 1 is DMF, T2: melting point ⁇ 61 ° C., T3: boiling point 153 ° C.
- Example 9 A transparent conductive film in the same manner as in Example 1 except that the derivative of polythiophene, which is a conductive organic polymer compound of component (C), is changed to PEDOT: PSS [manufactured by Nippon Agfa Materials, product name “S305”] And electronic devices were fabricated.
- Example 10 As a conductive organic polymer compound of component (C), 100 parts by mass of polyaniline (manufactured by Sigma Alidrich, described as polyaniline in Table 1) instead of polythiophene derivatives, glycerin of component (B) A transparent conductive film and an electronic device were produced in the same manner as in Example 1 except that the amount of was changed to 100 parts by mass.
- polyaniline manufactured by Sigma Alidrich, described as polyaniline in Table 1
- glycerin of component (B) A transparent conductive film and an electronic device were produced in the same manner as in Example 1 except that the amount of was changed to 100 parts by mass.
- Example 11 As a conductive organic polymer compound of component (C), 10,000 parts by mass of polypyrrole (manufactured by Sigma-Alidrich, described as polypyrroles in Table 1) instead of polythiophene derivatives A transparent conductive film and an electronic device were produced in the same manner as in Example 1 except that the amount of glycerin of component (B) was changed to 100 parts by mass.
- polypyrrole manufactured by Sigma-Alidrich, described as polypyrroles in Table 1
- ⁇ Comparative example 4> A comparative transparent conductive film and an electronic device were produced in the same manner as in Example 1 except that the conductive layer made of the conductive adhesive composition was not provided. That is, an electronic device was produced using only the conductive metal mesh layer as a comparative transparent conductive film.
- ⁇ Comparative Examples 7 to 10> A transparent base material in which a conductive metal mesh layer is not formed using the conductive adhesive composition prepared by blending the component (A), (B) or (C) with the compounding ratio shown in Table 1 A conductive layer was directly formed, and a comparative transparent conductive film and an electronic device were produced in the same manner as in Example 1.
- Examples 1 to 4 and 7 to 11 and Comparative Examples 1, 2, 5, 7, 8, and 10 are examples in which PVA is used as the water-soluble vinyl polymer of component (A).
- Table 1 shows the compounding ratio of each component in the conductive adhesive composition used in each example and the characteristics of the obtained transparent conductive film and electronic device.
- the compounding amounts of components (A), (B), and (C) all indicate parts by mass of the active ingredient. Numerical values in parentheses represent parts by mass or mass% of each component when the total of components (A), (B), and (C) is 100.
- Examples 5 and 6 are examples in which PVP was used as the water-soluble vinyl polymer of component (A).
- Example 12 [Preparation of conductive adhesive composition]
- acrylic acid polymer manufactured by Sigma-Aldrich, “polyacrylic acid”, weight average molecular weight 100,000, Tg 102 ° C., active ingredient 40 mass%, described as PAA in Table 2] 113 parts by mass, component ( As an organic additive of B), 90 parts by mass of glycerin [manufactured by Sigma Aldrich, product name “glycerin”, melting point (T2): 18 ° C., boiling point (T3): 290 ° C.] was used.
- a conductive organic polymer compound of component (C) As a conductive organic polymer compound of component (C), a mixture of poly (3,4-ethylene oxide thiophene) (PEDOT) and polystyrene sulfonic acid (PSS), which is a derivative of polythiophenes (PEDOT: PSS) [H. 1500 parts by mass of C. Starck, product name “CleviousP VP.AI4083”, 1% by mass of active ingredient (solvent: purified water), described as polythiophenes in Table 2) were used. 200 parts by mass of purified water was added to the components (A), (B), and (C) to prepare a coating liquid for the conductive adhesive composition (active ingredient: 7.9% by mass). In the same manner as in Example 1, a transparent conductive film and an electronic device were produced.
- PEDOT poly (3,4-ethylene oxide thiophene)
- PSS polystyrene sulfonic acid
- solvent purified water
- Example 12 except that a conductive adhesive composition prepared with a blending ratio of components (A), (B) and (C) shown in Table 2 (parts by mass of active ingredient, the same applies hereinafter) was used. In the same manner, a transparent conductive film and an electronic device were produced.
- Example 12 A transparent conductive material for comparison was prepared in the same manner as in Example 12 except that the component (A), (B) or (C) was prepared using the conductive adhesive composition prepared at the blending ratio shown in Table 2. A film and the same electronic device were produced.
- Table 2 shows the compounding ratio of each component in the conductive adhesive composition used in each example and the characteristics of the obtained transparent conductive film and electronic device.
- the compounding amounts of components (A), (B), and (C) all indicate parts by mass of the active ingredient. Numerical values in parentheses represent parts by mass or mass% of each component when the total of components (A), (B), and (C) is 100.
- the characteristics described in Table 1 and Table 2 were measured as follows. (1) Thickness of conductive layer and conductive metal mesh layer The thickness of the conductive layer and conductive metal mesh layer made of the conductive adhesive composition is determined by the stylus type surface shape measuring device (product name “Dektak 150, manufactured by Veeco”). )). (2) Surface resistivity The surface resistivity was measured by a four-terminal method using a surface resistance measuring device [manufactured by Mitsubishi Chemical Corporation, product name “Loresta GP MCP-T600”]. In the Example, the surface provided with the conductive layer and metal mesh layer of the transparent conductive film was measured. In Comparative Examples 4 and 14, the surface of the conductive metal mesh layer (copper layer) was measured.
- Adhesive strength The adhesive strength described in Table 2 is obtained by applying a coating solution of the conductive adhesive composition obtained in Examples 12 to 19 and Comparative Examples 11 to 20 to a polyethylene terephthalate film [manufactured by Toyobo Co., Ltd. , Product name “Cosmo Shine A4100”, thickness 100 ⁇ m], dried at 100 ° C. for 10 minutes to form a conductive layer composed of a conductive adhesive composition having a thickness of (500) nm, and a measurement sample. Was made. The measurement sample obtained was cut into 25 mm ⁇ 300 mm in a 23 ° C.
- the glass transition temperature T1 of the water-soluble vinyl polymer of the component (A) is based on JIS K 7121, and is an input compensated differential scanning calorimeter (manufactured by PerkinElmer, apparatus name “Pyrisl DSG”). Was used to measure the external glass transition start temperature in the temperature range of ⁇ 80 ° C. to 250 ° C.
- Table 1 confirms the following. (1) In Comparative Examples 1 and 2 using the components (A) and (C) without using the component (B), the surface resistivity is high, and the obtained electronic device does not show rectification, Did not function as a device. (2) In Comparative Example 3 containing only component (C), the adhesion was poor. Moreover, the obtained electronic device did not function as a device due to poor bonding. (3) In Comparative Example 4 having no conductive layer, there was no adhesive property and an electronic device could not be produced. (4) In Comparative Example 5 containing only the component (A), the surface resistivity was high, and the obtained electronic device did not show rectification and did not function as a device.
- Comparative Example 6 containing only component (B), the film-forming property was poor, the conductive layer could not be formed, and there was no adhesiveness.
- Comparative Examples 7 to 10 in which the conductive metal mesh layer was not provided, the surface resistivity was high, and the obtained electronic device did not show rectification and did not function as a device.
- Examples 1 to 11 had low surface resistivity, high transparency, and good adhesion. Moreover, since the obtained electronic device was also rectifying, it turned out that it is effective also as a device.
- Comparative Example 16 containing only component (B), the film formability was poor, the conductive layer could not be formed, and there was no adhesion.
- Comparative Examples 17 to 20 in which the conductive metal mesh layer was not provided, the surface resistivity was high, and the obtained electronic device did not show rectification and did not function as a device.
- the surface resistivity of the conductive layer was low, the transparency was high, and the adhesiveness was good.
- the obtained electronic device was also rectifying, it turned out that it is effective also as a device.
- the transparent conductive film of the present invention has excellent adhesion, low surface resistivity, and high transparency, so organic devices such as organic transistors, organic memories, and organic ELs; liquid crystal displays; electronic paper; thin film transistors Electrochromic; Electrochemiluminescence device; Touch panel; Display; Solar cell; Thermoelectric conversion device; Piezoelectric conversion device; Power storage device; Can be used in electronic devices such as power storage device; This is useful in the field of electronic devices.
- conductive layer 2 conductive metal mesh layer 3: transparent substrate 4: photoelectric conversion layer 5: electrode 6: substrate layer 7: transparent conductive film 8: electronic device 9: opening of conductive metal mesh layer
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Abstract
Description
例えば、電子太陽電池に代表される有機光電変換あるいは電光変換デバイスは、通常、透明導電膜よりなる電極に材料を積層して作製される。透明導電膜としては金属薄膜、金属酸化物薄膜、導電性窒化物薄膜等の各種導電膜が検討されているが、現在は主に光透過性と導電性との両立が可能で耐久性にも優れるため金属酸化物薄膜が主流である。
中でも特に錫をドープした酸化インジウム(ITO)は、光透過性と導電性とのバランスが良く、広く使用されている(特許文献1等参照)。しかしながら、透明電極の大面積化に伴い、更なる低抵抗化が求められており、ITOでは導電性としてまだ不十分である。
一方、PET等の透明基材に金属製の微細なメッシュあるいはグリッドを形成させたシートがある(特許文献2等参照)。これらのシートは透光性および導電性がメッシュの設計(ピッチ、線幅で決まる開口率)次第で制御できるので、透明電極としての利用可能性がある。例えば、透明な基材シートの少なくとも一方の面に導電性金属メッシュ層とポリチオフェンのような導電性高分子化合物からなる透明導電性層を有する透明導電性フィルムが開示されている(特許文献3等参照)。
ところで、従来から電子デバイスは、有機素子材料からなる層を積層する場合には、真空蒸着法およびそれに類するドライプロセスあるいは塗布に代表されるウェットプロセスや、粘接着層を介したラミネートプロセスにより製造されてきた(特許文献4等参照)。
このようなラミネートプロセスにおいては、接着性を有する透明電極膜および透明導電フィルムが望まれているが、従来の透明導電性フィルムでは、透明性、接着性及び表面抵抗率のバランスが課題となっている。
そこで、導電性接着剤組成物中の導電性成分として、ポリチオフェンやその誘導体のような導電性有機高分子化合物を使用することが提案されており、より具体的には、導電性有機高分子化合物を含む粘接着層を介したラミネートプロセス(特許文献5等参照)により電子デバイスを製造することが提案されている。
しかしながら、導電性有機高分子化合物を含む粘接着層を介したラミネートプロセスは、界面の清浄性、均一性が重要な素子用途では利用が限られていた。また、粘接着層の導電性が低く、ラミネート界面でのキャリア注入効率が低下したり、界面の接着力が低かったりする等、電子デバイスの性能が低下するという問題があった。
すなわち、本発明は、下記
(1)透明基材の少なくとも一方の面に設けられた導電性金属メッシュ層の開口部に、接着性の導電層を有する透明導電性フィルムにおいて、導電層が、(A)水溶性ビニル重合体、(B)有機添加剤及び(C)導電性有機高分子化合物を含む導電性接着剤組成物からなり、
(B)有機添加剤は、水溶性多価アルコール、水溶性ピロリドン類または親水性の非プロトン性溶媒から選ばれる少なくとも一種であり、(C)導電性有機高分子化合物は、ポリアニリン類、ポリピロール類またはポリチオフェン類及びそれらの誘導体から選ばれる少なくとも1種であることを特徴とする透明導電性フィルム、
(2)(A)水溶性ビニル重合体のガラス転移温度をT1、(B)有機添加剤の融点をT2、有機添加剤の0.101MPa(760mmHg)における沸点をT3としたときに、T2<T1<T3の関係を満たす上記(1)に記載の透明導電性フィルム、
(3)(A)水溶性ビニル重合体が、ポリビニルアルコール、ポリビニルピロリドン、またはアクリル酸重合体である上記(1)に記載の透明導電性フィルム、
(4)上記(1)に記載の透明導電性フィルムを有することを特徴とする電子デバイス、
(5)上記(1)に記載の透明導電性フィルムと、光電変換層と、陰極層をこの順に配置してなる上記(4)に記載の電子デバイス、および
(6)上記(4)に記載の電子デバイスの製造方法であって、陰極層上に前記光電変換層を形成させ、前記導電性接着剤組成物が軟化する温度以上で、透明導電性フィルムの導電層と光電変換層表面を貼り合わせることを特徴とする電子デバイスの製造方法を提供する。
<透明導電性フィルム>
本発明の透明導電性フィルムは、透明基材の少なくとも一方の面に設けられた導電性金属メッシュ層の開口部に、導電層を有する透明導電性フィルムであって、前記導電層が特定の導電性接着剤組成物からなるものである。
本発明の透明導電性フィルムの構成材料について図1を用いて説明する。図1において1が導電層、2が導電性金属メッシュ層、3が透明基材、7が透明導電性フィルム、9が導電性金属メッシュ層の開口部である。
本発明の透明導電性フィルムは、透明基材3の少なくとも一方の面に、導電性金属メッシュ層2が設けられ、前記導電性金属メッシュ層2の開口部に、導電層1が充填されて形成されている。
透明基材としては、透明性の観点から、全光線透過率が70%以上のものが好ましく、このような透明基材としては、一般的には、柔軟性の観点からプラスチックフィルムが好ましい。
プラスチックフィルムの種類としては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、テトラアセチルセルロース、シンジオタクチックポリスチレン、ポリフェニレンスルフィド、ポリカーボネート、ポリアリレート、ポリスルホン、ポリエステルスルホン、ポリエーテルイミド、環状ポリオレフィン等からなるプラスチックフィルムが挙げられる。中でも機械的強度、耐久性等に優れたものが好ましい。
透明基材の厚さは、機械強度、耐久性、及び透明性のバランスの観点から、3μm~5mmが好ましく、より好ましくは5μm~1mmであり、特に好ましくは10μm~300μmである。
本発明の透明導電性フィルムにおいて、導電性金属メッシュ層2は透明基材3の少なくとも一方の面に設けられている。
導電性金属メッシュ層2としては、プラズマディスプレイの電磁波シールド膜のような金属グリッドパターンによる微細メッシュ構造の層が挙げられる。
導電性金属メッシュ層2の厚さは、20nm~100μmであることが好ましく、特に30~200nmであることが好ましい。
厚さを20nm以上とすることにより、導電性が向上することとなり、100μm以下とすることにより、透明導電性フィルム全体の厚みを薄くすることができ、所望の全光線透過率を維持することができる。
開口部9の開口率としては、透明性の観点から80%以上であることが好ましく、より好ましくは90%以上であり、さらに好ましくは95%以上である。
開口部のピッチは、1~3000μmが好ましく、より好ましく1~1500μmである。開口部のピッチが1μm以下の場合、透明性が低下する場合があり、3000μm以上の場合、導電性が向上する効果が得られにくい。導電性金属メッシュ層2の線幅は、100nm~1000μmが好ましく、1μ~100μmがより好ましい。線幅が1000μmを超えると、透明性が低下する場合があり、100nm未満だと、導電性が向上する効果が得られにくくなる可能性がある。
合金としては、ステンレス、ニッケル-クロム、インコネル(商品名)、青銅、リン青銅、黄銅、ジュラルミン、白銅、インバール、モネル、ニッケルリン合金などの金属リン化合物、ニッケルボロンなどの金属ホウ素化合物、窒化チタンなどの窒化物など適宜選択可能である。とりわけ、銅および銅を主体とする合金や、ニッケルやニッケルを主体とする合金、コバルトやコバルトを主体とする合金、クロムやクロムを主体とする合金、アルミニウム及びアルミニウムを主体とする合金は、導電性に優れ、加工性も良好なので、好ましく用いられる。
導電性金属メッシュ層2は、金属や合金からなる単層であってもよく、少なくとも2種類以上の金属や合金からなる層を積層した多層構造であってもよい。
透明基材3上に前記導電性金属メッシュ層2を設ける方法としては、真空蒸着、スパッタリング、イオンプレーティング等のPVD(物理気相蒸着)、もしくは熱CVD、原子層蒸着(ALD)等のCVD(化学気相蒸着)などのドライプロセス、またはディップコーティング、スピンコーティング、スプレーコーティング、グラビアコーティング、ダイコーティング、ドクターブレード等の各種コーティングや電気化学的ディポジションなどのウェットプロセス、フォトリソグラフィー法、銀塩法、インクジェット法やスクリーン印刷法が挙げられ、導電性金属メッシュ層2の材料に応じて適宜選択される。
また、透明導電性フィルムの導電性を向上させる目的で、導電性金属メッシュ層2と透明基材3の間に、透明導電層を設けてもよい。
このような透明導電層としては、導電性の金属酸化物等を使用することができる。
導電性の金属酸化物としては、例えば、スズドープ酸化インジウム(ITO)、酸化イリジウム(IrO2)、酸化インジウム(In2O3)、酸化スズ(SnO2)、フッ素ドープ酸化スズ(FTO)、酸化インジウム-酸化亜鉛(IZO)、酸化亜鉛(ZnO)、ガリウムドープ酸化亜鉛(GZO)、アルミニウムドープ酸化亜鉛(AZO)、酸化モリブデン(MoO3)、酸化チタン(TiO2)等が挙げられる。これらの導電性の金属酸化物は、真空蒸着、スパッタリング、イオンプレーティング等のPVD(物理気相蒸着)、もしくは熱CVD、原子層蒸着(ALD)等のCVD(化学気相蒸着)などのドライプロセス等の公知の方法により形成することができる。このような透明導電層の厚さは、透明性と導電性の点から、通常10~1000nm、好ましくは10~500nm、特に30~300nmであることが好ましい。
本発明の透明導電性フィルムは、透明基材3の少なくとも一方の面に設けられた導電性金属メッシュ層2の開口部9に、導電層1を有する。
導電層1は、導電性接着剤組成物からなるものである。
導電性接着剤組成物は、(A)水溶性ビニル重合体、(B)有機添加剤及び(C)導電性有機高分子化合物を含み、(B)有機添加剤は、水溶性多価アルコール、水溶性ピロリドン類または親水性の非プロトン性溶媒から選ばれる少なくとも一種であり、(C)導電性有機高分子化合物は、ポリアニリン類、ポリピロール類またはポリチオフェン類及びそれらの誘導体から選ばれる少なくとも1種である。
<成分(A)>
成分(A)の一方の水溶性ビニル重合体は、導電性接着剤組成物からなる導電層に接着性を付与するためのものである。水溶性ビニル重合体は温水可溶性ビニル重合体も含む。
水溶性ポリビニル重合体のガラス転移温度(Tg)は、成膜性、接着性、取り扱いの点から、-50~150℃の範囲が好ましく、20~140℃であることが好ましく、より好ましくは30~130℃、さらに好ましくは、40~120℃である。
水溶性ポリビニル重合体は、重合体中に-CH2-CH(R)-の構造単位を有するものである。この構造単位を重合体中に少なくとも30モル%以上有していれば、特に限定されない。水溶性ポリビニル重合体は、この構造単位を含む単独重合体であってもよく、共重合体であってもよい。これらのなかでもRが水酸基、カルボキシル基、ピロリドン基、アクリルアミド基のいずれかであるものが好ましい。
Rが水酸基であるものは、-CH2-CH(OH)-の構造単位を有するものであり、水酸基を有する水溶性ビニル重合体の具体例としては、例えば、ポリビニルアルコール(PVA)、ポリビニルアルコール-エチレン共重合体、ポリビニルアルコール-(N-ビニルホルムアミド)共重合体、ポリビニルアルコール-酢酸ビニル共重合体等が挙げられる。
水酸基を有する水溶性ポリビニル重合体重合体は、部分的にケン化されてなるものでもよく、完全にケン化されたものであってもよい。
ケン化度は、20~100モル%が好ましく、より好ましくは35~100モル%、さらに好ましくは40~100モル%である。ケン化度が20モル%未満の場合には、溶解性が低下する。
重合体中にカルボキシル基を有するものは、-CH2-CH(COOH)-の構造単位を有するものである。カルボキシル基を有する水溶性ポリビニル重合体の具体例としては、例えば、ポリアクリル酸(PAA)等が挙げられる。
Rがピロリドン基である水溶性ビニル重合体は-CH2-CH(NC4O)-の構造単位を有するものであり、具体例としては、例えば、ポリビニルピロリドン(PVP)、N-ビニル-2-ピロリドン-エチレン共重合体、N-ビニル-2-ピロリドン-酢酸ビニル共重合体等が挙げられる。
Rがアクリルアミド基である水溶性ビニル重合体は、-CH2-CH(CONH2)-の構造単位を有するものであり、具体例としては、例えば、ポリアクリルアミド等が挙げられる。
水溶性ビニル重合体は、種々の機能を付与することを目的として疎水基やカチオン性基、スルホン酸基を含むアニオン性基、チオール基、カルボニル基、シラノール基などの官能基を上記構造単位以外に含有しても良い。
これら水溶性ポリビニル重合体の中でも、成膜性、接着性、取り扱いの点から、後述する電子デバイスの製造が容易に出来るという点から、Rが水酸基、ピロリドン基、カルボキシル基のいずれかであるものが好ましく、PVA、PVPまたはPAAが好ましい。これらの中でも、得られる導電層の導電性と接着性の点から、Rがカルボキシル基であるPAAであることがさらに好ましい。
水溶性ポリビニル重合体の重量平均分子量(Mw)は、通常500~50万であり、500~30万であることが好ましく、1,000~20万であることがより好ましく、3,000~15万であることがさらに好ましい。
水溶性ビニル重合体の重量平均分子量Mwがこの範囲であれば、本発明の透明導電性フィルムや電子デバイスにおいて十分な成膜性及び接着性が発現する。
なお、前記重量平均分子量Mwはゲルパーミエイションクロマトグラフィー(GPC)で測定された標準ポリスチレン換算の数値である。
共重合可能なその他のエチレン性不飽和単量体としては、例えば、
蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、酢酸イソプロペニル、バレリン酸ビニル、カプリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、バーサティック酸ビニル、ピバリン酸ビニル等のカルボン酸ビニルエステル単量体;エチレン、プロピレン、ブチレン等のオレフィン類;スチレン、α-メチルスチレン等の芳香族ビニル類;メタクリル酸、フマル酸、マレイン酸、イタコン酸、フマル酸モノエチル、無水マレイン酸、無水イタコン酸等のエチレン性不飽和カルボン酸単量体;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸2-エチルヘキシル、フマル酸ジメチル、マレイン酸ジメチル、マレイン酸ジエチル、イタコン酸ジイソプロピル等のエチレン性不飽和カルボン酸アルキルエステル単量体;メチルビニルエーテル、n-プロピルビニルエーテル、イソブチルビニルエーテル、ドデシルビニルエーテル等のビニルエーテル単量体;(メタ)アクリロニトリル等のエチレン性不飽和ニトリル単量体;塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン等のハロゲン化ビニル単量体またはビニリデン単量体;酢酸アリル、塩化アリル等のアリル化合物;エチレンスルホン酸、(メタ)アリルスルホン酸、2-アクリルアミド-2-メチルプロパンスルホン酸等のスルホン酸基含有単量体;3-(メタ)アクリルアミドプロピルトリメチルアンモニウムクロライド等の第四級アンモニウム基含有単量体;ビニルトリメトキシシラン、N-ビニルホルムアミド、メタアクリルアミド等が挙げられ、これらの1種または2種以上を使用することができる。
次に、成分(B)の有機添加剤について説明する。
本発明において、成分(B)の有機添加剤は水溶性多価アルコール、水溶性ピロリドン類および親水性の非プロトン性溶媒から選ばれる少なくとも一種であることを特徴としている。
成分(B)の有機添加剤は、導電性の向上を目的として添加される。詳細は不明であるが、このような有機添加剤を添加することで、後述する成分(C)の導電性有機高分子化合物の配向性が向上するため、導電性が向上する。
成分(B)の有機添加剤としては、1.101MPa(760mmHg)における沸点が100℃以上のものが好ましい。沸点が100℃を下回ると導電性接着剤組成物の混合過程、保存中や後述する電子デバイスを製造する際の種々の加熱過程において有機添加剤が揮発・飛散してその配合比率が低下するため導電性を向上させる効果が低下するので好ましくない。
より好ましい沸点は120~300℃、さらに好ましくは140~300℃の範囲である。
成分(B)の有機添加剤の一つである水溶性ピロリドン類としては、N-メチルピロリドン、N-エチルピロリドン、N-プロピルピロリドン、N-イソプロピルピロリドン、N-ブチルピロリドン、N-t-ブチルピロリドン、N-ペンチルピロリドン、N-ヘキシルピロリドン、N-ヘプチルピロリドン、N-シクロヘキシルピロリドン、N-オクチルピロリドン、N-(2-エチルヘキシル)ピロリドン、N-フェニルピロリドン、N-ベンジルピロリドン、フェネチルピロリドン、2-メトキシエチルピロリドン、2-メトキシプロピルピロリドン、2-ヒドロキシプロピルピロリドン、ビニルピロリドン、2-ピロリドン等が挙げられ、これらの1種または2種以上を用いてもよい。
本発明において、成分(B)有機添加剤の一つとして、非プロトン性溶媒が添加されている。本発明においては、非プロトン性溶媒は、導電性接着剤組成物中で、揮発・飛散せずに配合されているものである。このような成分(B)の有機添加剤の一つである親水性の非プロトン性溶媒としては、ジメチルスルホキシドおよびN,N-ジメチルホルムアミドが挙げられる。
すなわち、成分(A)の水溶性ポリビニル重合体のガラス転移温度(Tg)をT1、成分(B)の有機添加剤の融点をT2、有機添加剤の0.101MPa(760mmHg)における沸点をT3としたときに、T2<T1<T3を満たす組み合わせである。
ここで、成分(A)の水溶性ビニル重合体のガラス転移温度T1は、〔示差走査熱量測定(DSC)測定器〕で測定された値である。
成分(A)との間でT2<T1<T3の関係を満たす水溶性多価アルコールの具体例としては、例えば、グリセリン〔融点T2:18℃、沸点T3:290℃〕、エチレングリコール〔融点T2:-11.5℃、沸点T3:197℃〕、ジエチレングリコール〔融点T2:-6.5℃、沸点T3:245℃〕、プロピレングリコール〔融点T2:-59℃、沸点T3:188.2℃〕、ジプロピレングリコール〔融点T2:-40℃、沸点T3:232℃〕、1,3-ブタンジオール〔融点T2:-50℃、沸点T3:207.5℃〕、1,4-ブタンジオール〔融点T2:19℃、沸点T3:235℃〕等が挙げられる。中でも、導電性の向上という観点からグリセリン、1,4-ブタンジオールが好ましい。
T2<T1<T3の関係を満たすような成分(B)の水溶性ピロリドン誘導体としては、N-メチルピロリドン〔融点T2:-24℃、沸点T3:202℃〕、ビニルピロリドン〔融点T2:13.5℃、沸点T3:214.5℃〕、2-ピロリドン〔融点T2:24.6℃、沸点T3:245℃〕等が挙げられる。
T2<T1<T3の関係を満たすような成分(B)の親水性の非プロトン性溶媒としては、ジメチルスルホキシド(DMSO)〔融点T2:19℃、沸点T3:189℃〕、N,N-ジメチルホルムアミド(DMF)〔融点T2:-61℃、沸点T3:153℃〕等が挙げられる。
次に、成分(C)の導電性有機高分子化合物について説明する。
本発明において、成分(C)の導電性有機高分子化合物はポリアニリン類、ポリピロール類またはポリチオフェン類、及びそれらの誘導体から選ばれる少なくとも1種であることを特徴としている。
ポリアニリン類、ポリピロール類またはポリチオフェン類、及びそれらの誘導体は、π電子共役により導電性を有する導電性高分子である。
ポリアニリン類は、アニリンの2位または3位あるいはN位を炭素数1~18のアルキル基、アルコキシ基、アリール基、スルホン酸基等で置換した化合物の高分子量体であり、例えば、ポリ2-メチルアニリン、ポリ3-メチルアニリン、ポリ2-エチルアニリン、ポリ3-エチルアニリン、ポリ2-メトキシアニリン、ポリ3-メトキシアニリン、ポリ2-エトキシアニリン、ポリ3-エトキシアニリン、ポリN-メチルアニリン、ポリN-プロピルアニリン、ポリN-フェニル-1-ナフチルアニリン、ポリ8-アニリノ-1-ナフタレンスルホン酸、ポリ2-アミノベンゼンスルホン酸、ポリ7-アニリノ-4-ヒドロキシ-2-ナフタレンスルホン酸等が挙げられる。
ポリアニリン類の誘導体としては、前記ポリアニリン類のドーパント体等が挙げられる。ドーパントとしては、塩化物イオン、臭化物イオン、ヨウ化物イオンなどのハロゲン化物イオン;過塩素酸イオン;テトラフルオロ硼酸イオン;六フッ化ヒ酸イオン;硫酸イオン;硝酸イオン;チオシアン酸イオン;六フッ化ケイ酸イオン;燐酸イオン、フェニル燐酸イオン、六フッ化燐酸イオンなどの燐酸系イオン;トリフルオロ酢酸イオン;トシレートイオン、エチルベンゼンスルホン酸イオン、ドデシルベンゼンスルホン酸イオンなどのアルキルベンゼンスルホン酸イオン;メチルスルホン酸イオン、エチルスルホン酸イオンなどのアルキルスルホン酸イオン;または、ポリアクリル酸イオン、ポリビニルスルホン酸イオン、ポリスチレンスルホン酸イオン(PSS)、ポリ(2-アクリルアミド-2-メチルプロパンスルホン酸)イオンなどの高分子イオン;挙げられ、これらは単独でもまたは2種以上組み合わせて用いてもよい。
これらの中でも、高い導電性を容易に調整でき、かつ、水溶液にした場合に、容易に分散するために有用な親水骨格を有することから、ドーパントとしては、ポリアクリル酸イオン、ポリビニルスルホン酸イオン、ポリスチレンスルホン酸イオン(PSS)、ポリ(2-アクリルアミド-2-メチルプロパンスルホン酸)イオンなどの高分子イオンが好ましく、ポリスチレンスルホン酸イオン(PSS)がより好ましい。
ポリピロール類の誘導体としては、前記ポリピロール類のドーパント体等が挙げられる。ドーパントとしては、前述のポリアニリン類のドーパント体として例示したものが使用できる。
ポリチオフェン類の誘導体としては、前記ポリチオフェン類のドーパント体等が挙げられる。ドーパントとしては、前述のポリアニリン類のドーパント体として例示したものが使用できる。
これらの中でも、導電性有機高分子化合物としては、極めて少量で高い導電性を容易に調整でき、かつ、水溶液にした場合に、容易に分散するために有用な親水骨格を有することから、ポリ(3,4-エチレンオキサイドチオフェン)と、ドーパントとして、ポリスチレンスルホン酸イオンの混合物(以下、「PEDOT:PSS」と記載することがある)等が好ましい。
成分(A)、(B)および(C)の総量を100質量部とした時、成分(A)は1~60質量部、好ましくは、5~50質量部、より好ましくは10~40質量部である。成分(B)は0.1~90質量部、好ましくは10~70質量部、より好ましくは20~65質量部である。成分(C)は0.1~90質量部、好ましくは、0.5~75質量部、より好ましくは5~55質量部である。
成分(A)が1質量部未満の場合は、接着性が発現しなくなり、逆に60質量部を超える場合は、透明性及び導電性が低くなるので好ましくない。
成分(B)が0.1質量部未満の場合は、導電性が低くなり、逆に90質量部を超える場合は接着性が低下するので好ましくない。
成分(C)が0.1質量部未満の場合は導電性が低くなり、逆に90質量部を超える場合は接着性が発現しなくなるので好ましくない。
さらに、本発明において、導電性接着剤組成物中には前記成分(A)、(B)、(C)および溶媒以外にも必要に応じて、粘着付与剤、可塑剤、増粘剤、濡れ剤、消泡剤、造膜助剤、防腐剤、防錆剤、凍結溶融安定剤、顔料、着色剤、充填剤、金属粉末、酸化防止剤、光安定剤、紫外線吸収剤等を適宜添加することができる。
なかでも、前記導電性接着剤組成物を、精製水等の適当な溶剤に溶解又は分散してなる溶液(塗工液)を、上記各種コーティングにより、透明基材3上に設けられた前記導電性金属メッシュ層2の開口部に塗布し、得られた塗膜を乾燥させ、所望により、導電性接着剤組成物中の有機添加剤が揮発しない程度で加熱することより形成することにより導電層1を形成することが好ましい。このような方法によれば、容易に前記導電性金属メッシュ層2の開口部9に、導電層1を形成させることができる。
導電層1の全光線透過率は、80%以上、可能な限り100%に近いことが好ましい。全光線透過率が80%以上であれば、太陽電池等種々の電子デバイスに用いた場合に、透明性が十分であり、好適に用いられる。
図1に示すように、透明基材3の一方の面に、導電性金属メッシュ層2と導電層1を有し、導電性金属メッシュ層2の開口部9に、導電層1が充填されて形成されていることが好ましい。
また、導電層1は、導電性金属メッシュ層2の開口部に充填されて形成されていればよく、導電性金属メッシュ層2の上部が隠れるように形成されていてもよい(図3の7参照)。
すなわち、本発明の透明導電性フィルム7は、透明基材3の少なくとも一方の面に、導電性金属メッシュ層2と導電層1を有し、導電性金属メッシュ層2の開口部9に、導電層1が充填されて形成されていることで、導電性が向上する。
このように、本発明の透明導電性フィルムは、透明性が高く、表面抵抗率が低いため、透明性と導電性のバランスに優れており、また、それ自体が優れた接着性を有しているため、ラミネートプロセスによる電子デバイスの製造が可能である。
以下、本発明の電子デバイスについて説明する。
本発明の電子デバイスは、前述の透明導電性フィルムを有しているものである。
電子デバイスとしては、有機トランジスタ、有機メモリー、有機EL等の有機デバイス;液晶ディスプレイ;電子ペーパー;薄膜トランジスタ;エレクトロクロミック;電気化学発光デバイス;タッチパネル;ディスプレイ;太陽電池;熱電変換デバイス;圧電変換デバイス;蓄電デバイス;等が挙げられる。
図2は、本発明の透明導電性フィルムを有する電子デバイスの一例である。図2において1が導電層、2が導電性金属メッシュ層、3が透明基材、4は光電変換層、5は電極、6は基材、7は透明導電性フィルム、8は電子デバイスである。
光電変換層は光電効果を受ける層であり、単層からなっていても良いし、複数層からなっていても良い。単層の場合には、光電変換層は、通常、真性半導体層(i型半導体)から形成される。
光電変換層は、光電変換を行う層であり、原料の低コスト化、柔軟性、形成の容易性、吸光係数の高さ、軽量化、耐衝撃性等の観点から有機半導体であることが好ましい。
また、複数層の場合、(p型半導体層/n型半導体層)の積層、または、(p型半導体層/真性半導体層/n型半導体層)等である。
光電変換層の厚さは、単層または複数層の場合で異なるが導電性、励起子拡散距離という観点から、一般的には、30nm~2μmであることが好ましく、特に40nm~300nmであることが好ましい。
(1)真性半導体
真性半導体の材料としては、例えば、フラーレン、フラーレン誘導体、半導体性を有するカーボンナノチューブ(CNT)およびCNT化合物の少なくとも1種類からなる第1の材料と、ポリフェニレンビニレン(PPV)の誘導体またはポリチオフェン系高分子材料からなる第2の材料とを、得られる半導体が真性半導体となるように混合した混合物を使用することができる。
フラーレン誘導体としては、例えば、[6,6]-フェニル-C61-酪酸メチル(PCBM)等を用いることができ、また、フラーレンの二量体、またはアルカリ金属もしくはアルカリ土類金属等を導入したフラーレン化合物なども用いることができる。また、CNTとしては、フラーレンまたは金属内包フラーレンを内包したカーボンナノチューブ等を用いることができる。さらに、CNTの側壁や先端に、種々の分子を付加したCNT化合物等も用いることができる。
ポリフェニレンビニレンの誘導体としては、ポリ[2-メトキシ,5-(2’-エチル-ヘキシロキシ)-p-フェニレン-ビニレン](MEH-PPV)等を用いることができ、ポリチオフェン系高分子材料としては、ポリ-3-ヘキシルチオフェン(P3HT)などのポリ(3-アルキルチオフェン),ジオクチルフルオレンエン-ビチオフェン共重合体(F8T2)、等を用いることができる。
特に好ましい真性半導体としては、PCBMとP3HTとを質量比で1:0.3~1:4で混合した混合物が挙げられる。
p型半導体の材料としては、例えば、ポリ-3-ヘキシルチオフェン(P3HT)等のポリアルキルチオフェンおよびその誘導体;ポリフェニレンおよびその誘導体、ポリ[2-メトキシ-5-(2′-エチル-ヘキシロキシ)-p-フェニレン-ビニレン](MEH-PPV)等のポリフェニレンビニレンおよびその誘導体、ポリシランおよびその誘導体、ポルフィリン誘導体、フタロシアニン誘導体、ポリアルキルチオフェンおよびその誘導体、有機金属ポリマー等が挙げられる。中でもポリアルキルチオフェンおよびその誘導体が好ましい。また、それら有機材料の混合物であってもよい。導電性高分子としては、ポリ(3,4)-エチレンジオキシチオフェン/ポリスチレンスルフォネート(PEDOT:PSS)を好ましく使用することができる。
n型半導体の材料としては、特に限定されず、1,4,5,8-ナフタレンテトラカルボキシリックジアンハイドライド(NTCDA)、3,4,9,10-ペリレンテトラカルボキシリックジアンハイドライド(PTCDA)、3,4,9,10-ペリレンテトラカルボキシリックビスベンズイミダゾール(PTCBI)、N,N′-ジオクチル-3,4,9,10-ナフチルテトラカルボキシジイミド(PTCDI-C8H)、2-(4-ビフェニリル)-5-(4-t-ブチルフェニル)-1,3,4-オキサジアゾール(PBD)、2,5-ジ(1-ナフチル)-1,3,4-オキサジアゾール(BND)等のオキサアゾール誘導体、3-(4-ビフェニリル)-4-フェニル-5-(4-t-ブチルフェニル)-1,2,4-トリアゾール(TAZ)等のトリゾール誘導体、フェナントロリン誘導体、ホスフィンオキサイド誘導体、フラーレン化合物、カーボンナノチューブ(CNT)、CNTの側壁や先端に種々の分子を付加したCNT化合物、ポリ-p-フェニレンビニレン系重合体にシアノ基を導入した誘導体(CN-PPV)等が挙げられる。
これらの中でも、安定でキャリア移動度の高いn型半導体であることから特にフラーレン化合物が好ましい。
フラーレン化合物としては、例えば、[6,6]-フェニル-C61-酪酸メチル(PCBM)等を用いることができる。また、フラーレンの二量体、またはアルカリ金属もしくはアルカリ土類金属を導入したフラーレン化合物等が挙げられる。これらの中でも優れた電子受容性を有する観点からPCBMが好ましい。
なお、これらのn型半導体は、単独でまたは2種以上組み合わせて用いることができる。
電極の材料としては、仕事関数が比較的小さいものが好ましい。例えば、白金、金、アルミニウム、イリジウム、クロム、酸化亜鉛等の金属、金属酸化物もしくは合金の他、カーボンナノチューブ、またはカーボンナノチューブと上記金属、金属酸化物もしくは合金との複合体が挙げられる。
電極の厚さは、20nm~1μmであることが好ましく、特に30~200nmであることが好ましい。
電極5を形成する方法としては、真空蒸着、スパッタリング、イオンプレーティング等のPVD(物理気相蒸着)、もしくは熱CVD、原子層蒸着(ALD)等のCVD(化学気相蒸着)などのドライプロセス、またはディップコーティング、スピンコーティング、スプレーコーティング、バーコーティング、グラビアコーティング、ダイコーティング、ドクターブレード等の各種コーティングや電気化学的ディポジションなどのウェットプロセスが挙げられ、電極5の材料に応じて適宜選択される。
<基材層>
基材層6としては、一般的にガラス(板)またはプラスチックフィルムが挙げられ、電子デバイスの用途に応じて適宜される。プラスチックフィルムとしては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、テトラアセチルセルロース、シンジオタクチックポリスチレン、ポリフェニレンスルフィド、ポリカーボネート、ポリアリレート、ポリスルホン、ポリエステルスルホン、ポリエーテルイミド、環状ポリオレフィン等のフィルムが挙げられ、機械的強度、耐久性等に優れたものが好ましい。これらの中でも、透明性が高いものが好ましい。
基材層6の厚さは、機械強度及び透明性のバランスの観点から、3μm~5mmが好ましく、より好ましくは5μm~1mmであり、特に好ましくは10μm~300μmである。
本発明の電子デバイスの製造方法は、透明導電性フィルムの導電層と光電変換層表面とを貼りあわせることを特徴とするものである。すなわち、前記導電性接着剤組成物が軟化する温度以上で、透明導電性フィルムの導電層と、前記光電変換層表面を貼り合わせることを特徴とする。
以下、図3を用いて本発明の電子デバイスの製造方法について説明する。図3において、下向きの矢印は光電変換層4と導電層1を、導電性接着剤組成物が軟化する温度以上で圧着して貼り合わせて、電子デバイスとすることを表わしている。
前記導電性接着剤組成物が軟化する温度は、水溶性ビニル重合体のガラス転移温度(Tg)以上の温度である。製造しやすいという点から、具体的には60~140℃程度である。
本発明の電子デバイスの製造方法によれば、透明導電性フィルムの導電層1表面と光電変換層4表面を貼り合わせるため、ラミネートプロセスにより容易に電子デバイスを製造することができる。
また、この方法によれば、基材層6上に電極5を形成し、この電極5上に光電変換層4を形成させているため、光変換層4上に電極5を形成させる工程が存在しない。
したがって、電極5が不均一になったり、電極5の形成時のエネルギーによって光電変換層4がダメージを受けることがなく、電子デバイスの性能が低下することがない。
[導電性接着剤組成物の調製]
成分(A)の水溶性ビニル重合体として、ポリビニルアルコール〔シグマアルドリッチ社製、製品名「ポリビニルアルコール」、重量平均分子量9100、Tg(T1):50℃、表1中ではPVAと記載〕50質量部を使用した。成分(B)の有機添加剤として、グリセリン〔シグマアルドリッチ社製、製品名「グリセリン」、融点(T2):18℃、沸点(T3):290℃〕50質量部を使用した。成分(C)の導電性有機高分子化合物として、ポリチオフェン類の誘導体である、ポリ(3,4-エチレンオキサイドチオフェン)(PEDOT)とポリスチレンスルホン酸(PSS)の混合物(PEDOT:PSS)(H.C.Starck社製、製品名「CleviousP VP.AI4083」、有効成分1質量%(溶剤:精製水)、表1中ではポリチオフェン類と記載〕10,000質量部を使用した。
前記成分(A)、(B)および(C)に精製水200質量部を添加して、導電性接着剤組成物の塗工液(有効成分:1.9質量%)を調製した。
透明基材〔東洋紡績社製、製品名「コスモシャインA4100」〕の一方の面に、1×10-3Pa以下の減圧下、銅を蒸着法で製膜することにより、厚さ100nmの銅層を形成した。次いで、レジスト処理とエッチング処理を行ない、導電性金属メッシュ層(開口部ピッチ:1200μm/線幅20μm、全光線透過率89%、表面抵抗率2Ω/□)を作製した。
次いで、導電性金属メッシュ層の開口部に、上記のように調製した導電性接着剤組成物の塗工液を、マイヤーバー(20ミル)を用いて塗布し、120℃の乾燥機で10分間乾燥させた。
このようにして、導電性金属メッシュ層の開口部に導電性接着剤組成物からなる導電層(厚さ500nm)を有する透明導電性フィルムを作製した。
次いで、上記で得られた電極上にポリ-3-ヘキシルチオフェン(P3HT)と[6,6]-フェニル-C61-酪酸メチル(PCBM)とを質量比1:0.8で混合した混合物のクロロベンゼン溶液(濃度:2質量%)を、スピンキャスト法により塗布し、120℃で10分間乾燥して、厚さ100nmの光電変換層を形成させた。
光電変換層表面と、透明導電性フィルムの導電層表面とをロールラミネーター〔ロイヤルソブリン社製、製品名「RSL-328S」〕のローラーの温度を120℃に加熱し圧着して貼り合わせることにより電子デバイスを得た。
表1に示されている配合比(質量部、以下同様)で調製された導電性接着剤組成物を用いた以外は実施例1と同様にして、透明導電性フィルムおよび電子デバイスを作製した。
成分(A)のPVAの量を25質量部とし、成分(B)の有機添加剤として、グリセリンの替わりにN-メチルピロリドン〔和光純薬工業株式会社製、T2:融点-24℃、T3:沸点202℃〕80質量部を使用した以外は実施例1と同様にして、透明導電性フィルムおよび電子デバイスを作製した。
成分(A)の水溶性ビニル重合体をとして、PVAの替わりにポリビニルピロリドン〔シグマアルドリッチ社製、Tg(T1):80℃、表1中ではPVPと記載〕を50質量部使用し、成分(B)の有機添加剤として、グリセリンの量を100質量部とした以外は実施例1と同様にして、透明導電性フィルムおよび電子デバイスを作製した。
成分(B)の有機添加剤として、グリセリンの替わりにN-メチルピロリドン〔和光純薬工業株式会社製、T2:融点-24℃、T3:沸点202℃〕を100質量部使用した以外は実施例5と同様にして、透明導電性フィルムおよび電子デバイスを作製した。
成分(B)の有機添加剤として、グリセリンの替わりにジメチルスルフォオキサイド〔和光純薬工業株式会社製、表1中の記載はDMSO、T2:融点19℃、T3:沸点189℃〕を100質量部使用した以外は実施例1と同様にして、透明導電性フィルムおよび電子デバイスを作製した。
成分(B)の有機添加剤として、グリセリンの替わりにジメチルフォルムアミド〔和光純薬工業株式会社製、表1中の記載はDMF、T2:融点-61℃、T3:沸点153℃〕を100質量部使用した以外は実施例1と同様にして、透明導電性フィルムおよび電子デバイスを作製した。
成分(C)の導電性有機高分子化合物であるポリチオフェン類の誘導体を、PEDOT:PSS〔日本アグファマテリアルズ製、製品名「S305」〕に変えて、実施例1と同様にして透明導電性フィルムおよび電子デバイスを作製した。
成分(C)の導電性有機高分子化合物として、ポリチオフェン類の誘導体の替わりに、ポリアニリン〔シグマアリドリッチ社製、表1中ではポリアニリン類と記載〕を100質量部、成分(B)のグリセリンの量を100質量部に変える以外は実施例1と同様にして透明導電性フィルムおよび電子デバイスを作製した。
成分(C)の導電性有機高分子化合物として、ポリチオフェン類の誘導体の替わりに、ポリピロール〔シグマアリドリッチ社製、有効成分1質量%表1中ではポリピロール類と記載〕を10,000質量部、成分(B)のグリセリンの量を100質量部に変える以外は実施例1と同様にして透明導電性フィルムおよび電子デバイスを作製した。
成分(A)、(B)または(C)を、表1に示されている配合比で調製された導電性接着剤組成物を用いて実施例1と同様にして、比較用の透明導電性フィルムおよび同電子デバイスを作製した。
導電性接着剤組成物からなる導電層を設けない以外は、実施例1と同様にして、比較用の透明導電性フィルムおよび電子デバイスを作製した。すなわち、導電性金属メッシュ層のみを比較用の透明導電性フィルムとして電子デバイスを作製した。
<比較例7~10>
成分(A)、(B)または(C)を、表1に示されている配合比で調製された導電性接着剤組成物を用いて、導電性金属メッシュ層を形成していない透明基材に直接、導電層を形成し、実施例1と同様にして比較用の透明導電性フィルムおよび電子デバイスを作製した。
各例で用いられた導電性接着剤組成物における各成分の配合比および得られた透明導電性フィルムおよび電子デバイスの特性を表1に示す。
表1において、成分(A)、(B)、(C)の配合量はいずれも有効成分の質量部を示す。カッコ内の数値は成分(A)、(B)、(C)の合計を100とした時の各成分の質量部または質量%を表わす。実施例5、6は成分(A)の水溶性ビニル重合体としてPVPを用いた例である。
[導電性接着剤組成物の調製]
成分(A)として、アクリル酸重合体〔シグマアルドリッチ製、″ポリアクリル酸″、重量平均分子量10万、Tg102℃、有効成分40質量%、表2中ではPAAと記載〕113質量部、成分(B)の有機添加剤として、グリセリン〔シグマアルドリッチ社製、製品名「グリセリン」、融点(T2):18℃、沸点(T3):290℃〕90質量部を使用した。成分(C)の導電性有機高分子化合物として、ポリチオフェン類の誘導体である、ポリ(3,4-エチレンオキサイドチオフェン)(PEDOT)とポリスチレンスルホン酸(PSS)の混合物(PEDOT:PSS)〔H.C.Starck社製、製品名「CleviousP VP.AI4083」、有効成分1質量%(溶剤:精製水)、表2中ではポリチオフェン類と記載〕1500質量部を使用した。
前記成分(A)、(B)および(C)に精製水200質量部を添加して導電性接着剤組成物の塗工液(有効成分:7.9質量%)を調製した。
実施例1と同じ方法で、透明導電性フィルムおよび電子デバイスの作製を行った。
表2に示されている成分(A)、(B)および(C)の配合比(質量部、以下同様)で調製された導電性接着剤組成物を用いた以外は実施例12と同様にして、透明導電性フィルムおよび電子デバイスを作製した。
表2に示されている成分(A)、(B)および(C)の配合比(有効成分の質量部、以下同様)で調製された導電性接着剤組成物を用いた以外は実施例12と同様にして、透明導電性フィルムおよび電子デバイスを作製した。
成分(A)、(B)または(C)を、表2に示されている配合比で調製された導電性接着剤組成物を用いて実施例12と同様にして、比較用の透明導電性フィルムおよび同電子デバイスを作製した。
(1)導電層及び導電性金属メッシュ層の厚み
導電性接着剤組成物からなる導電層及び導電性金属メッシュ層の厚みは、触針式表面形状測定装置(Veeco社製、製品名「Dektak 150」)により測定した。
(2)表面抵抗率
表面抵抗測定装置〔三菱化学社製、製品名「ロレスタGP MCP-T600」〕により、四端子法で表面抵抗率を測定した。実施例においては、透明導電性フィルムの導電層及び金属メッシュ層を備えた面を測定した。比較例4、14においては、導電性金属メッシュ層(銅層)表面を測定した。比較例7~10、17~20においては、導電層表面を測定した。
(3)全光線透過率
光線透過率測定装置〔日本電色工業社製、製品名「NDH-5000」〕を用いてJIS K7631-1に準じて、透明導電性フィルムの全光線透過率を測定した。
(4)貼り合わせ評価(接着性)
実施例および比較例で得られた透明導電性フィルム(5×5cm)を、ラミネーター〔ロイヤルソブリン社製、製品名「RSL-328J」〕を用いて、温度120℃でガラス板(25mm×25mm、厚み1mm)に貼り合わせた。その後、常温まで冷却後、透明導電性フィルムを垂直にし、接着しているか否かを調べた。
○:ガラス板が落ちずに接着している。
×:接着せずにガラス板が剥離した。
(5)電子デバイスの評価
実施例および比較例で得られた電子デバイスを、ソースメジャーユニット〔ワコム電創社製〕を用いて電流電圧特性を測定し、整流曲線を観察した。
○:整流性有
×:整流性無(貼り合せ不良により電子デバイスとして機能しない)
(6)接着力
表2に記載されている接着力は、実施例12~19および比較例11~20で得られた導電性接着剤組成物の塗工液をポリエチレンテレフタレートフィルム〔東洋紡績社製、製品名「コスモシャインA4100」、厚み100μm〕上に塗工し、100℃で10分間乾燥させ、膜厚(500)nmの導電性接着剤組成物からなる導電層を形成させ、測定用サンプルを作製した。
得られた測定用サンプルを、を用いてJIS Z0237(2009)に準じて、23℃50%RH(相対湿度)環境下で25mm×300mmにカットした測定用サンプルをラミネーター〔ロイヤルソブリン社製、製品名「RSL-328J」〕を用いて、温度100℃で被着体(ガラス板、800mm×1500mm、厚み3mm)に貼り合わせた。貼付後24時間後の粘着力を180°引き剥がし法によって、引っ張り速度300mm/分にて測定した。
(7)ガラス転移温度
成分(A)の水溶性ビニル重合体のガラス転移温度T1は、JIS K 7121に準拠し、入力補償示差走査熱量測定装置[パーキンエルマー社製、装置名「Pyrisl DSG」]を用いて、-80℃から250℃の温度範囲で、捕外ガラス転移開始温度を測定して求めた。
(1)成分(B)を使用せず、成分(A)と(C)を使用した比較例1、2においては、表面抵抗率が高く、得られた電子デバイスは整流性が見られず、デバイスとして機能しなかった。
(2)成分(C)のみを含む比較例3においては、接着性が悪かった。また、得られた電子デバイスは、貼り合せ不良によりデバイスとして機能しなかった。
(3)導電層を有さない比較例4においては、接着性が全くなく、電子デバイスが作成できなかった。
(4)成分(A)のみを含む比較例5においては、表面抵抗率が高く、得られた電子デバイスは整流性が見られず、デバイスとして機能しなかった。
(5)成分(B)のみを含む比較例6においては、成膜性が悪く、導電層を形成することが出来ず、接着性も全くなかった。
(6)導電性金属メッシュ層を設けない比較例7~10においては、表面抵抗率が高かった、また、得られた電子デバイスは整流性が見られず、デバイスとして機能しなかった。
一方、実施例1~11は、表面抵抗率が低く、透明性も高く、かつ接着性も良好であった。また、得られた電子デバイスも整流性があったことからデバイスとしても有効であることがわかった。
(1)成分(B)を使用せず、成分(A)と(C)を使用した比較例11、12においては、導電層の表面抵抗率が高く、得られた電子デバイスは整流性が見られず、デバイスとして機能しなかった。
(2)成分(C)のみを含む比較例13においては、接着力が低く、測定できなかった。また、得られた電子デバイスは、貼り合せ不良によりデバイスとして機能しなかった。
(3)導電層を有さない比較例14においては、接着力が全くなく、電子デバイスが作成できなかった。
(4)成分(A)のみを含む比較例15においては、導電層の表面抵抗率が高く、得られた電子デバイスは整流性が見られず、デバイスとして機能しなかった。
(5)成分(B)のみを含む比較例16においては、成膜性が悪く、導電層を形成することが出来ず、接着性も全くなかった。
(6)導電性金属メッシュ層を設けない比較例17~20においては、表面抵抗率が高かった、また、得られた電子デバイスは整流性が見られず、デバイスとして機能しなかった。
一方、成分(A)、(B)および(C)を使用した実施例12~19では、導電層の表面抵抗率が低く、透明性も高く、かつ接着性も良好であった。また、得られた電子デバイスも整流性があったことからデバイスとしても有効であることがわかった。
2:導電性金属メッシュ層
3:透明基材
4:光電変換層
5:電極
6:基材層
7:透明導電性フィルム
8:電子デバイス
9:導電性金属メッシュ層の開口部
Claims (6)
- 透明基材の少なくとも一方の面に設けられた導電性金属メッシュ層の開口部に、接着性の導電層を有する透明導電性フィルムにおいて、導電層が、(A)水溶性ビニル重合体、(B)有機添加剤及び(C)導電性有機高分子化合物を含む導電性接着剤組成物からなり、
(B)有機添加剤は、水溶性多価アルコール、水溶性ピロリドン類または親水性の非プロトン性溶媒から選ばれる少なくとも一種であり、(C)導電性有機高分子化合物は、ポリアニリン類、ポリピロール類またはポリチオフェン類及びそれらの誘導体から選ばれる少なくとも1種であることを特徴とする透明導電性フィルム。 - (A)水溶性ビニル重合体のガラス転移温度をT1、(B)有機添加剤の融点をT2、有機添加剤の0.101MPa(760mmHg)における沸点をT3としたときに、T2<T1<T3の関係を満たす請求項1に記載の透明導電性フィルム。
- (A)水溶性ビニル重合体が、ポリビニルアルコール、ポリビニルピロリドン、またはアクリル酸重合体である請求項1に記載の透明導電性フィルム。
- 請求項1に記載の透明導電性フィルムを有することを特徴とする電子デバイス。
- 請求項1に記載の透明導電性フィルムと、光電変換層と、陰極層をこの順に配置してなる請求項4に記載の電子デバイス。
- 請求項4に記載の電子デバイスの製造方法であって、陰極層上に前記光電変換層を形成させ、前記導電性接着剤組成物が軟化する温度以上で、透明導電性フィルムの導電層と光電変換層表面を貼り合わせることを特徴とする電子デバイスの製造方法。
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US13/881,952 US9401490B2 (en) | 2010-10-29 | 2011-07-20 | Transparent conductive film, electronic device, and method for manufacturing electronic device |
CN201180049913.7A CN103229251B (zh) | 2010-10-29 | 2011-07-20 | 透明导电性薄膜和电子装置以及电子装置的制备方法 |
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