TW201245215A - Composition for conductive film of solar cell and conductive film - Google Patents

Abstract

The present invention relates to a composition for a conductive film of a thin film solar cell, including electro-conductive oxide particles, and binder that is hardened by heating, wherein the binder includes organo-trialkoxysilanerepresented by a general formula (1): R1Si(OR2)3 (R1 and R2 in the formula are specific hydrocarbon radicals) and/or hydrolysate of the organo-trialkoxysilane. The present invention also relates to a transparent conductive thin film including hydrolysate of organo-trialkoxysilane, a solar cell having the same conductive thin film, and a method for producing the same conductive thin film.

Description

201245215 VI. Description of the Invention: [Technical Field] The present invention relates to a composition for a transparent conductive film and a transparent conductive film. More specifically, the present invention relates to a composition for a transparent conductive film for a thin film solar cell, a transparent conductive film, a solar cell including the transparent conductive film, and a method for producing a transparent conductive film for use in a thin film solar cell. Technology] At present, based on the standpoint of environmental protection, the development and practical use of clean energy has progressed, and solar cells have attracted attention because of their inexhaustible sunlight as energy sources and pollution-free. In the past, solar cells used monocrystalline or polycrystalline silicon solar cells. However, since bulk solar cells have high manufacturing costs and low productivity, it is urgent to develop solar cells that can save as much as possible. Therefore, development of a thin film solar cell using a semiconductor such as amorphous germanium having a thickness of, for example, 0.3 to 2 μm is being actively carried out. Since the thin film solar battery has a structure in which a semiconductor layer is required to form a photoelectric conversion on a glass substrate or a heat-resistant plastic substrate, it is thin, light in weight, low in cost, and easy to have a large area. The thin-film solar cell has a super-straight-type structure and a sub-straight-type structure, and the ultra-straight structure is usually a substrate because it is incident on the light-transmitting substrate side. Transparent Electrode · Photoelectric conversion layer - The structure in which the back electrodes are formed in order. 201245215 The thin film solar cell was formed by a vacuum film formation method such as sputtering in the past, but generally, a large cost is required for introduction, maintenance, and operation of a large vacuum film forming apparatus. In order to improve this, a technique of forming a transparent conductive film and a conductive reflective film by a wet coating method using a composition for a transparent conductive film and a composition for a conductive reflective film by a cheaper manufacturing method has been disclosed (Patent Document 1) ). [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 2 0 0 9 - 8 8 4 8 9 SUMMARY OF THE INVENTION An object of the present invention is to improve a transparent conductive film produced by the above wet coating method. The present inventors have found that the composition for a transparent conductive film can be improved, and the transparent conductive film-photoelectric conversion can be increased by increasing the difference between the refractive index of the transparent conductive film used in the wet coating method and the refractive index of the photoelectric conversion layer. The reflected light at the layer interface, and by the increased return of the light to the photoelectric conversion layer, can increase the power generation efficiency of the thin film solar cell. The same technique can be applied to a sub-straight solar cell or a bulk solar cell. The present invention relates to a composition for a transparent conductive film used in a thin film solar cell and a transparent conductive film, which solve the above problems by the configuration shown below. The first aspect of the present invention is a composition for a transparent conductive film for a thin film solar cell, characterized by comprising conductive oxide particles and a binder which is hardened by heating, and the binder comprises the general formula (1) : WSi(OR2) 3 (wherein R1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms 'R2 is a linear or branched alkyl group having 1 to 4 carbon atoms) and/or 201245215 Hydrolyzate. The second aspect of the present invention is the composition for a transparent conductive film for a thin film solar cell according to the above-mentioned first aspect, wherein the monomer is contained in an amount of 50 to 95 parts by mass with respect to the binder: 100 parts by mass Formula (1): an organotrialkoxydecane represented by R1 Si (OR2) 3 and/or a hydrolyzate thereof. The third aspect of the present invention is the composition for a transparent conductive film for a thin film solar cell according to the first or second aspect described above, wherein the binder is contained by the above formula (1): R>Si (OR2) 3 is an adhesive component formed by using an organic trialkoxysilane, water and an organic solvent, and a mixture of two or a mixture of an acid and a base as a catalyst. The fourth aspect of the present invention is the composition for a transparent conductive film for a thin film solar cell, wherein the binder further comprises a polymer type which is hardened by heating, as in any of the first to third aspects described above. Either or both of a binder or a non-polymeric binder. According to a fifth aspect of the invention, the composition for a transparent conductive film of a thin film solar cell, wherein the binder comprises sesquiterpene oxide, in any of the first to fourth aspects described above. The sixth aspect of the invention is a composition for a transparent conductive film for a thin film solar cell, which further comprises a coupling agent, as in any of the first to fifth aspects described above. The seventh aspect of the invention is the composition for a transparent conductive film for a thin film solar cell according to the sixth aspect described above, wherein the coupling agent is a decane coupling agent. The composition for a conductive film for use in a thin film solar cell of the present invention in any of the above aspects may further comprise a low-resistance agent or a water-soluble cellulose derivative. Further, the composition for a transparent conductive film may contain 65 to 99 parts by mass of a dispersion medium in an amount of 100 parts by mass. The eighth aspect of the present invention is a transparent conductive film for use in a thin film solar cell, characterized in that it contains conductive oxide particles and a hardened adhesive, and the hardened adhesive comprises the general formula (1): Wsi (OR2) 3 (wherein, R1 is a hydrocarbon having 1 to 12 carbon atoms; and R2 is a linear or branched alkyl group having 1 to 4 carbon atoms) is a hydrolyzate of an organic trialkoxysilane. The ninth aspect of the present invention is the transparent conductive film for use in a thin film solar cell according to the eighth aspect described above, wherein the hardened adhesive comprises a sesquifer. A tenth aspect of the present invention is the transparent conductive film for a thin film solar cell according to the eighth or ninth aspect, wherein the hardened adhesive further comprises a hardening of a polymer type adhesive or a non-polymer type adhesive. Adhesive 〇 The transparent conductive film used in the thin film solar cell of the present invention described above can be produced by using the above-described composition for a transparent conductive film. A tenth aspect of the invention is a thin film solar cell comprising a transparent conductive film as in any of the eighth to tenth aspects described above. The thin film solar cell may be provided with a substrate, a transparent electrode layer, a light conversion layer, and a transparent conductive film of the present invention. The method for producing a transparent conductive film for a thin film solar cell of the present invention is a method for producing a transparent conductive film of a thin film solar cell comprising a substrate, a transparent electrode layer, a photoelectric conversion layer and a transparent conductive film, which is characterized by In the wet coating method, the transparent conductive film of the present invention is formed on the photoelectric conversion layer formed on the transparent electrode layer of the substrate, and after electrocoating, the film is fired at 130 to 400 ° C to have a transparent conductive coating. Film thickness: 0.03~0.5 μηι transparent conductive film. That is, the twelfth aspect of the present invention is a method for producing a transparent conductive film for a thin battery, which is a method for manufacturing a thin film solar light conductive film having a base electrode layer, a photoelectric conversion layer, and a transparent conductive film. It is characterized by a wet coating method, an electrical oxide particle and a binder hardened by heating, and is contained in the formula (1) zRiSiCOR2), wherein R1 is a carbon number monovalent hydrocarbon group, and R2 is a transparent conductive film having a carbon number of 1 to 4 or a linear alkyl group or a hydrolyzate thereof, which is formed on a photoelectric conversion layer formed on a transparent electrode layer of a substrate, and is coated with a conductive coating. After the film, a transparent conductive film having a thickness of 〇_〇3 to 0.5 μm is formed by firing a transparent conductive coating film at 130 to 400 ft. A thirteenth aspect of the invention is the method for producing a transparent conductive film of a film solar cell according to the twelfth aspect, wherein the composition for the front electrode film contains 50 parts by mass based on 10 parts by mass of the binder. The above formula (1): an organic decane represented by WSi (OR2) 3 and/or a hydrolyzate thereof. The fourteenth aspect of the invention is the method for producing a film according to the thirteenth aspect, wherein the agent for the composition for a transparent conductive film is contained by the above formula (1): RlSi (〇R2) 3 The oxygen sand chamber, water and organic solvent, and the acid and alkali as the catalyst are coated on the transparent conductive substrate, and the transparent film of the solar material and the transparent battery will contain the conductive adhesive package 1~12. The coating is applied to form a transparent substrate, and is used as a binder component which is formed by using a mixture of a transparent conductive material of 9.5 masses of a trialkoxy transparent conductive or the above-mentioned bonded organic trioxane or -9-201245215. The above binder component can be formed by reacting the above mixture at a temperature of 〇 60 ° C for 30 to 360 minutes. A fifteenth aspect of the invention is the method for producing a transparent conductive film for a thin film solar cell according to the twelfth to fourteenth aspects, wherein the composition for a transparent conductive film further comprises hardening by heating Either or both of a polymeric binder or a non-polymeric binder. The sixteenth aspect of the invention is the method for producing a transparent conductive film for a thin film solar cell according to any of the twelfth to fifteenth aspects, wherein the binder comprises sesquiterpene oxide. The seventeenth aspect of the present invention is the method for producing a transparent conductive film for a thin film solar cell according to any of the twelfth to sixteenth aspects, wherein the composition for the transparent conductive film further comprises a coupling agent . The eighteenth aspect of the invention is the method for producing a transparent conductive film for a thin film solar cell according to the seventeenth aspect, wherein the coupling agent is a decane coupling agent. The nineteenth aspect of the present invention is the method for producing a transparent conductive film for a thin film solar cell according to any of the twelfth to eighteenth aspects, wherein the wet coating method is a spray coating method. , a coater coating method, a spin coating method, a knife coating method, a slit coating method, an inkjet coating method, a die coating method, a screen printing method, a lithography method, or a gravure printing method. [Effect of the Invention] The composition for a transparent conductive film of the present invention can be applied onto a photoelectric conversion layer of -10-201245215 by a wet coating method and fired. The transparent conductive film after hardening is considered to have a microporous structure, and the refractive index of the transparent conductive film is lowered by the microporous structure. Therefore, the difference between the refractive index of the transparent conductive film and the refractive index of the photoelectric conversion layer becomes large, and the reflected light at the interface of the transparent conductive film-photoelectric conversion layer is increased, and the light returned to the photoelectric conversion layer with the increase can improve the film. Solar cell power generation efficiency. Therefore, when the composition for a transparent conductive film of the present invention is used, a transparent conductive film which improves the power generation efficiency of the thin film solar cell can be easily obtained. According to the transparent conductive film for a thin film solar cell of the present invention, it is possible to obtain a film in which the transparent conductive film-reflecting light at the interface of the photoelectric conversion layer is increased, and the light which is returned to the photoelectric conversion layer by the increase, thereby improving power generation efficiency Solar battery. According to the method for producing a transparent conductive film for a thin film solar cell of the present invention, a transparent conductive film can be formed without using a high-priced vacuum device, and a thin film solar cell having high power generation efficiency can be manufactured simply and at low cost. [Embodiment] Hereinafter, the present invention will be specifically described based on embodiments. Further, % is % by mass unless otherwise specified. [Composition for a transparent conductive film for a super-straight-type thin film solar cell] The composition for a transparent conductive film for a thin film solar cell (hereinafter referred to as a composition for a transparent conductive film) is characterized by containing conductive oxidation. The particles and the adhesive which is hardened by heating, and the binder comprises the formula (1): 11^(01^2) 3 (wherein R1 is a hydrocarbon number of 1 to 12 carbon atoms in the formula) R2 is an organic trialkoxy sand garden represented by a carbon number·1 to 4 linear or branched alkyl group and/or a hydrolyzate thereof. The conductive oxide particles impart conductivity to the cured product of the transparent conductive film composition, i.e., the transparent conductive film. The conductive oxide particles are preferably tin oxide powders of ITO (Indium Tin Oxide), antimony Tin Oxide (or antimony tin oxide) or contain Al, Co, Fe, In, Sn. And at least one metal zinc oxide powder selected from the group consisting of Ti, more preferably IT0, ΑΤΟ, AZO (Aluminum Zinc Oxide), IZO (Indium Zinc Oxide) Zinc oxide), TZO (tin Zinc Oxide: zinc oxide doped with tin). Further, the average particle diameter of the conductive oxide fine particles is preferably in the range of 10 to 100 nm, more preferably in the range of 20 to 60 nm, in order to maintain stability in the dispersion medium. Here, the average particle diameter is measured by the BET method using the specific surface area measurement. For example, specific surface area measurements can be made using QUANTACHROME AUTOSORB·1 from Quantachrome Instruments. The binder comprises the general formula (1): 1^5丨(0112)3 (wherein R1 is a hydrocarbon group having a carbon number of 1 to 12, and R2 is a linear or branched alkyl group having a carbon number of 1 to 4) An organic trialkoxysilane and/or a hydrolyzate thereof. The organic trialkoxy decane and/or its hydrolyzate are considered to form a microporous structure in the transparent conductive film, and the refractive index of the transparent conductive film can be lowered by the microporous structure. R1 preferably comprises an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl or dodecyl; cyclohex-12-.201245215 a functional group in which at least one selected from the group consisting of a cycloalkyl group such as a 2-cyclopropyl group; an arylalkyl group such as a 2-phenylpropyl group; an aryl group such as a phenyl group or a tolyl group; and the like, wherein the hydrolysis reaction is controlled to form a microporous structure. More preferably, it is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a phenyl group. Further, since R1 imparts stress relaxation to the transparent conductive film, it is possible to provide a thin film solar cell which is resistant to a decrease in conversion efficiency in a heat cycle test and which is stable for a long period of time. R2 is exemplified by a methyl group, an ethyl group, a propyl group, a butyl group or the like, and more preferably a methyl group, an ethyl group or a methylethyl group from the viewpoint of controlling the hydrolysis reaction. The organotrialkoxydecanes are exemplified by methyltrimethoxydecane, methyltriethoxydecane, methyltriisopropoxydecane, methylstilbene (methoxyethoxy)decane, ethyltrimethoxy. From the viewpoint of controlling the hydrolysis reaction, decane, phenyltrimethoxydecane, and phenyltriethoxydecane are preferably methyltrimethoxydecane, methyltriethoxydecane, and phenyltrimethoxydecane. , phenyl triethoxy decane. The binder further comprises, as a material, an organic trialkoxy decane represented by the above formula (1): WSi (OR2) 3, water and an organic solvent, and a mixture of one or a combination of an acid and a base as a catalyst. The binder component formed. The above mixture can produce hydrolysis and polycondensation reaction of the organotrialkoxydecane. The binder containing the component becomes the organic trialkoxysilane and/or the hydrolyzate thereof. 1 mole, the catalyst is preferably used as a catalyst, and the acid used as hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, etc. is preferably nitric acid or formic acid from the viewpoint of controlling the hydrolysis reaction. , acetic acid. Ion exchange water and pure water are preferably used in the hydrolysis. It is preferably from 1 to 10 mol%, more preferably from 2 to 10 mols, based on the organotrialkoxydecane-13-201245215. As for the acid/base used as a medium, it is preferred to slowly add a very low concentration, and slowly hydrolyze and polycondense. The base for promoting the polycondensation of the hydrolyzate is exemplified by potassium hydroxide hydroxide, ammonia, monomethylamine, monoethylamine, etc., and ammonia, monoethylamine is preferred from the viewpoint of controlling polycondensation and anti-low residual impurities. . Addition of a base The mixture of water and water and an organic solvent is 100 parts by mass, preferably about 3 to 5 parts by weight. For example, when ammonia is used, it is preferably about 0.001 to 1 part by weight based on 100 parts by mass of the mixture of water and water and the organic agent. The organic solvent used in the reaction is exemplified by methanol, ethanol, n-propanol propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, ethylene glycol monoether, acetone, diethyl ether, tetrahydrofuran, diacetone alcohol. Preferred are ethanol, isopropanol 'acetone, diacetone alcohol. The organic solvent may be one or a mixture of two or more. The organic solvent is used as a diluent for adjusting the contrast. The amount of the organic solvent to be added is preferably adjusted so that the concentration of the cerium oxide in the alkoxide is about 3 to 30% by mass in the reaction system in which the organic solvent is added to the water and the catalyst. As for the hydrolysis conditions, in order to make the hydrolysis reaction and the polycondensation reaction rate extremely slow, in order to obtain the dissolved hydrolyzate in order not to generate particles, it is preferably 0 to 60 ° C, more preferably 0 to 50 ° C, and the time is good. For 30~3 60 points, it is better for 60~240 minutes. When the hydrolyzate of the organotrialkoxydecane contains sesquiterpene oxide, it is preferred from the viewpoint of forming a microporous structure. When the organotrialkoxydecane is reacted, it becomes a sesquioxane. Here, the sesquioxane is controlled by • Atm: sodium, the phase 1x10' is dissolved, and the isomethylmethanol is used. The second is the temperature clock, which is easy to make water and sand oxygen 201245215 A sand-containing polymer composed of a bond, which is represented by a general formula, wherein Ri is a hydrocarbon group having 1 to 12 carbon atoms, and a general formula of a polyoxane having the following chemical formula (!):

ο 1 R -S1 - ο I ο I In addition to the organic trialkoxy decane and/or its hydrolyzate, the binder contains a polymer-type binder or a non-polymer-type binder which is hardened by heating. The composition of one or both of them is preferable because the adhesion and workability of the transparent conductive film can be improved. As the polymer type adhesive, it is exemplified by acrylic resin, polycarbonate, polyester 'alkyd resin, polyurethane urethane, urethane acrylate, polystyrene, polyacetal, polyamine, polyethylene. Alcohol, polyvinyl acetate, cellulose, and siloxane polymers. Further, the polymer type binder preferably comprises a metal soap, a metal complex, a metal alkoxide or a metal of a wrong, sand, titanium, chromium, bell, iron, m, nickel, silver, copper, zinc, molybdenum or tin. A hydrolyzate of alkoxide. As the non-polymer type binder, there are mentioned metal soaps, metal complexes, metal alkoxides, haloximes, 2-alkoxyethanol, β-diketones, and alkyl acetates. Further, the metal contained in the metal, the metal complex or the metal alkoxide is preferably aluminum, lanthanum, lanthanum, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or recorded. More preferably, it is an alkoxide of cerium or aluminum (for example, tetraethoxy decane, tetramethoxy decane, acetonitrile, isopropyl alumina). These polymer type adhesive -15-201245215 agents and non-polymer type adhesives are hardened by heating, and can form a transparent conductive film having a low haze ratio and a volume resistivity at a low temperature. Further, the metal alkoxide may be a hydrolyzate or an anhydrate thereof. The binder is preferably added with a coupling agent depending on the other ingredients used. The addition of a coupling agent is to form a microporous structure with sesquiterpene oxide, improve bonding with conductive oxide particles or a binder, and improve formation of a transparent conductive film from a composition for a transparent conductive film and lamination on a substrate. The adhesion of the photoelectric conversion layer or the conductive reflective film. The coupling agent is exemplified by a decane coupling agent, an aluminum coupling agent, a titanium coupling agent, etc. As for the decane coupling agent, vinyl triethoxy decane (CH2 = CH[Si(OCH2CH3)3]), ethylene trimethoxy decane ( CH2 = CH[Si(OCH3)3]), ethylene ginseng (2-methoxyethoxy) litter (CH2 = CH[Si(OCH2CH2OCH3)3]), 3-(chemical formula (2)) Glycidoxypropyltrimethoxydecane, octa CH2—CHCH2OCH2CH2CH2Si(OCH3)3 (2) 3-glycidoxypropyltriethoxy oxime represented by the formula (3), Α Μ CH2—CHCH2OCH2CH2CH2Si ( OCH2CH3)3 (3) 3·mercaptopropyltrimethoxydecane (HSCH2CH2CH2Si(OCH3)3), 3-mercaptopropyltriethoxydecane (HSCH2CH2CH2Si(OCH2CH3)3), 3-aminopropyltri Ethoxy decane (H2NCH2CH2CH2Si(OCH2CH3)3) ' 3- -16- 201245215 Aminopropyltrimethoxydecane (112^1 <:112(:112(:1128丨(0(:113)3), 3-isocyanatepropyltriethoxydecane (0 = C = NCH2CH2CH2Si(0CH2CH3)3), 3-isocyanatepropyltrimethyl) Oxydecane (〇= C = NCH2CH2CH2Si(OCH3)3), 3-methylpropenyloxypropyltrimethoxydecane represented by the chemical formula (4), ch3(CH3〇)3SiC3H6OCC=CH2(4) 0 by chemical formula ( 5) 3-methoxypropenyloxypropyltriethoxydecane, ch3(C2H50)3SiC3H60CC=CH2 (5) 6 3-Acryloxypropyltrimethoxy fluorene represented by the chemical formula (6) CH3〇)3SiC3H6OCCH=CH2 (6) 6 N-phenyl-3-aminopropyltrimethoxysilane represented by the chemical formula (7)·(CH30)3SiC3H6NH-^^ (7) 0 In this case, control Hydrolysis reaction, from the viewpoint of forming a microporous structure, m is preferably vinyltriethoxydecane, vinyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxy矽 、, 3 _ -17 - 201245215 hydrated glyceryl propyl trimethoxy decane, 3-glycidoxy propyl trioxy decane. Composition for transparent conductive film relative to transparent conductive film The solid content (conductive oxide particles, binder, etc.) in the material is preferably from 98 to 65 parts by mass, more preferably from 95 to 65 parts by mass, based on 1 part by mass, more preferably from 95 to part by mass. The reason is that the upper limit is exceeded. When the adhesion is lowered, the conductivity is lowered when the crucible is not reached. Further, the conductive component is contained in an amount of 90 to 70 parts by mass based on 100 parts by mass of the solid component. The content of the binder is relative to the transparent conductive film. The solid content (isoelectric oxide particles, binder, etc.) in the composition: 100 parts by mass, preferably 5 to 50 parts by mass, more preferably 1 to 30 parts by mass. With the formula (1): The content of the organotrialkoxyquinone and/or the hydrolyzate thereof represented by WSi(OR2) 3 is preferably from 10 to 95 parts by mass based on 100 parts by mass of the binder. If the upper limit is exceeded, the transparent conductive film is present. When the adhesiveness of the adhesiveness is lowered, it is difficult to obtain an effect of sufficiently increasing the shot when the lower limit is not reached. The adhesive is contained in the formula (1) in an amount of 55 to 100 parts by mass based on 100 parts by mass of the binder. Organic trialkoxy alkane, water and organic solvent, and acid and alkali as catalyst When the binder component is formed as a material, the content of the trialkoxy decane and/or its hydrolyzate in the binder may be adjusted to the above-mentioned range. The preferred content of the component is relative to the binder. : 1 part by mass, 55 to 90 parts by mass, more preferably 65 to 85 parts by mass. The coupling agent content in the case of containing a coupling agent can be alkane-containing and anti-mute with respect to the transparent conductive film group B> The solid content (conductive oxide particles, binder, coupling agent, etc.) in the mass of -18-201245215: 100 parts by mass, preferably 〇. 2 to 10 parts by mass, more preferably 0. 3 to 7 parts by mass. The composition for a transparent conductive film preferably contains a dispersion medium to make the film formation good. The dispersion medium is exemplified by water; alcohols such as methanol, ethanol, isopropanol and butanol; ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone; toluene, xylene, hexane and cyclohexane Hydrocarbons such as alkane; amides such as N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide; arylene or the like; or diols such as ethylene glycol; A glycol ether such as a cellosolve. In order to obtain good film formability, the content of the dispersion medium is preferably from 65 to 99 parts by mass based on 1 part by mass of the composition for the transparent conductive film. Further, depending on the component to be used, a low-resistance agent or a water-soluble cellulolytic derivative or the like is preferably added. The low-resistance agent is preferably one or more selected from the group consisting of inorganic acid salts and organic acid salts of cobalt, iron, indium, nickel, lead, tin, titanium and zinc. For example, a mixture of nickel acetate and ferric chloride, a mixture of zinc naphthenate, tin octoate and cerium chloride, a mixture of indium nitrate and lead acetate, a mixture of titanium acetylate and cobalt octoate, and the like. The content of the low-resistance agent is preferably 0.1% by mass based on the conductive oxide powder. 2 to 15 parts by mass. The water-soluble cellulose derivative is a non-ionizing surfactant, and the ability to disperse the conductive oxide powder is extremely high, even if added in a small amount, compared with other surfactants, and is further derived by adding water-soluble cellulose. The material can also improve the transparency of the formed transparent conductive film. The water-soluble cellulose derivative is exemplified by hydroxypropylcellulose 'hydroxypropylmethylcellulose. The amount of the water-soluble cellulose derivative added is preferably from 0 to 100 parts by mass, preferably from 0. 2 to 5 parts by mass. The composition for a transparent conductive film can be mixed with a desired component by a general method, a paint shaker, a ball mill, a sand mill, a center honing machine (Centrimill), a triaxial roll, or the like to form conductive oxide particles and sesquiterpene oxide. Particles are dispersed and manufactured. Of course, it can also be manufactured by a general stirring operation. [Transparent Conductive Film for Ultra-Linear Thin Film Solar Cell] The transparent conductive film (hereinafter referred to as a transparent conductive film) used in a thin film solar cell of the present invention is characterized in that it contains conductive oxide particles and a hardened adhesive, and is hardened. The binder comprises a hydrolyzate of an organotrialkoxydecane represented by the formula (1): R1 Si (OR2) 3 (wherein R1 and R2 are as defined above). The hydrolyzate of the transparent conductive film conductive oxide particles and the organotrialkoxysilane is as described above, and the hardened binder is one in which the above-mentioned binder is cured. In other words, the transparent conductive film is cured by curing the composition for a transparent conductive film used in a thin film solar cell. The method for producing a transparent conductive film of the present invention is a method for producing a transparent conductive film of a thin film solar cell comprising a substrate, a transparent electrode layer, a photoelectric conversion layer and a transparent conductive film, which is characterized by a wet coating method. The composition for a transparent conductive film described above is applied onto a photoelectric conversion layer formed on a transparent electrode layer of a substrate to form a transparent conductive coating film, and then fired at 130 to 400 ° C to form a substrate having a transparent conductive coating film. Form thickness: 〇. 〇3~0. 5μπι transparent conductive film. First, the transparent conductive film composition -20-201245215 is applied onto a photoelectric conversion layer of a thin film solar cell having a substrate, a transparent electrode layer, a photoelectric conversion layer, and a transparent conductive film by a wet coating method. . The coating here is such that the thickness after firing is 0. 03~0. 5 μηι, preferably 0. 05~0. 2 μηη thickness. Next, the coating film is dried at a temperature of 20 to 120 ° C for 1 to 30 minutes, preferably 2 to 10 minutes at 25 to 60 ° C. The transparent conductive coating film is thus formed. The substrate may be any one of a light-transmitting substrate made of glass, ceramic or a polymer material, or two or more kinds of light-transmitting laminates selected from the group consisting of glass, ceramics, a cylinder molecular material, and sand. . The polymer substrate is exemplified by a substrate formed of an organic polymer such as polyimide or PET (polyethylene terephthalate). Further, the wet coating method is preferably a spray coating method, a coater coating method, a spin coating method, a knife coating method, a slit coating method, an inkjet coating method, a screen printing method, or the like. Any of lithographic printing methods or gravure printing methods, but is not limited thereto, and all methods can be utilized. The spray coating method is a method in which a composition for a transparent conductive film is sprayed on a substrate by using a compressed air, or a dispersion is applied to a substrate by pressurization into a mist, and a dip coating method is used. For example, a method in which a composition for a transparent conductive film is placed in a syringe and a dispersion is ejected from a fine nozzle at the tip end of the syringe by pressing the plunger of the syringe to be applied to the substrate. In the spin coating method, a composition for a transparent conductive film is dropped onto a rotating substrate, and the composition of the dropped transparent conductive film is extended to the periphery of the substrate by centrifugal force, and the substrate is applied by a doctor blade method. It is set to be movable in the horizontal direction with a specific gap at the front end of the blade, and the composition for the transparent conductive film is supplied from the blade to the substrate on the upstream side, and the substrate is moved toward the downstream side water - 21,452,521 The method. The slit coating method is a method in which a composition for a transparent conductive film is discharged from a narrow slit and applied to a substrate, and the inkjet coating method is a method of coating a transparent conductive film composition with a commercially available inkjet. The method of inkjet printing on a substrate in the inkjet of a printer. The screen printing method uses a yarn as a pattern indicating material, and a method of transferring a transparent conductive film composition onto a substrate through a plate image made thereon. The lithographic printing method is a composition for a transparent conductive film attached to a plate, which is not directly attached to a substrate, but is temporarily transferred from a plate to a rubber sheet, and is transferred from the rubber sheet to the substrate by using a transparent conductive material. A printing method for water repellency of a composition for a film. The die coating method is a method in which a composition for a transparent conductive film supplied into a nozzle is extruded from a slit which is dispensed by a manifold onto a film to coat a surface of the substrate in progress. The die coating method includes a slit coating method, a slant plate coating method, and a curtain coating method. Finally, the substrate having the transparent conductive coating film is kept in the atmosphere or in an inert gas atmosphere such as nitrogen or argon, at a temperature of 130 to 400 ° C, preferably 150 to 350 ° C, for 5 to 60 minutes. It is preferably calcined in 15 to 40 minutes. Here, the thickness of the transparent conductive film after firing is made 0. 03-0. The reason for coating the composition for a transparent conductive film in the range of 5 μm is that the thickness after firing is less than 0. 03μηι or more than 0. When 5 μη is used, the effect of increasing the reflection cannot be sufficiently obtained. The reason why the baking temperature of the substrate having the coating film is in the range of 130 to 400 ° C is that when the temperature is less than 130 ° C, the surface resistance 値 becomes too high in the transparent conductive film in the composite film. . Further, when it exceeds 400 ° C, the production advantage of the low temperature process cannot be produced, that is, the manufacturing cost is increased and the productivity is lowered. The reason is that, in particular, amorphous germanium, microcrystalline germanium, or a hybrid solar cell using the same, such as -22-201245215, is relatively weak in heat resistance, and the conversion efficiency by the firing step is lowered. The reason why the baking time of the substrate having the coating film is in the range of 5 to 60 minutes is that when the firing time is less than the lower limit, the surface resistance of the transparent conductive film in the composite film becomes too high. bad. When the firing time exceeds the upper limit, the manufacturing cost is increased as necessary, the productivity is lowered, and the conversion efficiency of the solar cell element is lowered. According to the above, the transparent conductive film of the present invention can be formed. According to this, in the production method of the present invention, by using the wet coating method, since a vacuum process such as a vacuum deposition method or a sputtering method can be eliminated as much as possible, the transparent conductive film can be manufactured more inexpensively. Further, since the transparent conductive film of the present invention contains a hydrolyzate of an organic trialkoxy decane, it is considered that a microporous structure represented by a sesquiterpene oxide structure is formed, and the refractive index of the transparent conductive film is lowered. When the refractive index difference between the photoelectric conversion layer and the transparent conductive film is larger than in the past, the reflected light from the transparent conductive film toward the photoelectric conversion layer is increased, and the photoelectric conversion efficiency is improved by the light blocking effect. Further, since the hydrolyzate (such as sesquioxanes) of the organotrialkoxydecane has a structure having a hydrocarbon group, it imparts stress relaxation property to the transparent conductive film. For example, the conversion efficiency after the accelerated durability test using the thermal cycle test of the repeated thermal cycle of -40 to 90 ° C is less than that of the past, and it becomes a long-term stable thin film solar cell. [Thin film solar cell] The thin film solar cell of the present invention The battery includes the above transparent conductive film used for a thin film solar cell. Fig. 1 shows an example of a cross section of a thin film solar cell -23-201245215 of the present invention. Figure 1 shows the case of an ultra-straight thin film solar cell. The ultra-straight thin film battery is provided with the substrate 10, the transparent electrode layer 3, the photoelectric conversion layer 2, the transparent conductive film 1, and the conductive reflective film 4 in this order, and sunlight is incident from the substrate 10 side. The incident sunlight is often reflected at the conductive reflective film 4, and returns to the photoelectric conversion layer 2 to improve the conversion efficiency. Here, the interface between the transparent conductive film 1 and the photoelectric conversion layer 2 also causes solar light to be reflected. The transparent conductive film 1 using the composition for a transparent conductive film of the present invention can increase the transparent conductive film 1 due to the low refractive index. The reflected light at the interface of the photoelectric conversion layer 2 improves the power generation efficiency of the thin film solar cell. The step of producing the ultrastraight type thin film battery as described above is such that the transparent electrode layer 3 is formed on the substrate 10, and the transparent conductive film 1 of the present invention is formed on the transparent electrode layer 3 where the photoelectric conversion layer 2 is formed. At this time, the transparent conductive film 1 can be produced by the method for producing a transparent conductive film of the present invention. The thin film solar cell of the present invention is not limited to a type of a substrate, a transparent electrode, a photoelectric conversion layer, etc., for example, any of a light-transmitting substrate made of glass, ceramic or a polymer material may be used as the substrate, or Two or more light-transmitting laminates selected from the group consisting of glaze, ceramic, polymer material, and bismuth. For example, a laminate of glass and SiO 2 may be used as the substrate. The transparent electrode layer may be formed of a Sn02 film or the like, and the photoelectric conversion layer may be formed, for example, as P-type a-Si: Η (amorphous hydrogen hydride, i-type a-Si (amorphous germanium), and n-type pc-Si (micro [Examples] The present invention will be described in detail below by way of examples, but the present invention is not limited to -24 to 201245215. The composition shown in Tables 1 to 3 (numbers represent mass parts) In a manner, a total of 60g is fed into a 100cm3 glass bottle, using a diameter of 0. A transparent conductive film composition of Examples 1 to 20 and Comparative Example 1 was prepared by dispersing a zirconia ball of 3 mm: 100 g in a paint shaker for 6 hours. Further, in the ratio column of Tables 1 to 3, the conductive oxide particles are not referred to as "conductive", and the coupling agent is omitted as "even". Here, the binders 1 to 5 containing (R1 Si (OR2) 3) and the Si 02 binders 1 to 7 used as a binder were produced as follows. [Bounding agent 1 containing (R4i (OR2) 3)] Using a 500 cm3 glass four-necked flask, 140 g of methyltrimethoxydecane and 140 g of methanol were added, and the mixture was added once with stirring to make 1. 7 g of 60% solution of nitric acid dissolved in 120 g of pure water, followed by reaction at 50 ° C for 3 hours to obtain a hydrolysis reaction liquid. Further, using a tube pump, in 120 minutes, by O. An alkali solution of lg is added to a mixture of 30 g of pure water and 7 g of ethanol to be poured into a hydrolysis reaction liquid to produce. [Bound agent containing (Rii (OR2) 3) 2] A 500-cm glass 4-neck flask was used, and 140 g of methyltriethoxy sand pot and 140 g of methanol were added, and the mixture was added once with stirring to make 1. 5 g of formic acid was dissolved in a solution of 120 g of pure water, followed by a reaction at 50 ° C for 3 hours to obtain a hydrolyzed reaction liquid. Then, using a tube pump, an alkali solution in which 〇· 〇 5 g of aqueous ammonia was added to a mixed liquid of 30 g of pure water and 70 g of ethanol was put into the hydrolysis reaction liquid for 90 minutes. -25- 201245215 [Bounding agent containing (R Si (OR2) 3) 3] A 4-necked flask made of glass of 20 〇 cm 3 was added. 5g methyltrimethoxydecane, 2. 3 g of phenyltrimethoxydecane and 80 g of ethanol were added at a time to make 0. A solution of 03 g of formic acid dissolved in 8 g of pure water was then reacted at 2 ° C for 1 hour to obtain a hydrolyzate A. A 5-neck flask made of glass of 500 cm3 was added to make 0. A solution of 25 g of potassium hydroxide dissolved in 1 g of pure water was kept at 20 ° C with stirring, and a hydrolyzate A was added dropwise thereto over 2 hours using a tube pump, and the mixture was further stirred for 2 hours. Manufacturing. [BSi (OR2) 3)-containing binder 4] A 500-neck flask made of 500 cm3 was used, and 120 g of methyltriethoxydecane, 25 g of phenyltriethoxydecane, and 140 g of ethanol were added, and the mixture was stirred. The tube pump is added dropwise in 90 minutes to make 0. A solution of 0.05 g of nitric acid dissolved in 30 g of pure water was added and reacted at 30 ° C for 4 hours to produce. [Beta (VSi(OR2) 3 )-containing binder 5] A 500-cm 3 glass four-necked flask was used, and 140 g of methyltrimethoxydecane, 1 g of 3-aminopropyltrimethoxydecane, and 140 g of methanol were added. Add it once while stirring. 7 g of a solution of 60% nitric acid dissolved in 120 g of pure water was then reacted at 50 ° C for 3 hours to obtain a hydrolysis reaction liquid. Next, use a tube pump in 120 minutes by using O. An aqueous solution of lg of ammonia is added to a hydrolysis reaction solution by adding an alkali solution of a mixture of 3 gram of pure water and 70 g of ethanol. -26- 201245215 [Si〇2 binder 1] A four-necked flask made of 500 cm3 glass was used, and 14 g of decane and 140 g of ethanol were added, and the mixture was added once with stirring to make 1. 7 g of a solution dissolved in 120 g of pure water was subsequently reacted at 50 °C. [SiO 2 Binding Agent 2] A 500-cm glass 4-necked flask was used, and 85 g of tetraoxane and 1 g of ethanol were added, and a tube pump was used at room temperature with stirring, and it took a minute to put it into the crucible. 9 g of 60% nitric acid was dissolved in 110 g of solution. Subsequently, using a tube pump, it takes 1 to 15 minutes to mix 45 g of the third-second butadiene alumina and 60 g of ethanol to the resulting mixed solution. After stirring at room temperature for about 30 minutes, it should be made for 3 hours. [Si02 bond 3] A 500-cm glass 4-neck flask was used, and 115 g of decane and 175 g of ethanol were added, and the mixture was added once with stirring. 4 g of the solution dissolved in 1 1 〇g of pure water 'then reacted at 45 ° C for 3 hours [SiO 2 binder 4] Using a 500-neck flask made of 500 cm 3 glass, adding 130 g of tetraethoxy 6 0 % nitric acid hourly The ethoxylated oxime is charged between 10 and 15 pure water, and the pre-formed solution is poured into 50 ° C anti-tetraethoxy 3 5 % hydrochloric acid to produce tetraethoxy-27-201245215 decane and 145 g of ethanol. Add it once while stirring. 25 g of a solution of 30% aqueous ammonia dissolved in 124 g of pure water was subsequently produced by reacting at 45 ° C for 3 hours to prepare [SiO 2 binder 5] using a 500 cm 3 glass four-necked flask, and adding 145 g of tetraethoxysilane and 140 g of ethanol. Add it while stirring. 15 g of a 60% solution of nitric acid dissolved in 115 g of pure water was subsequently produced by reacting at 50 ° C for 3 hours. [Si02 bond 6] A 500-cm glass four-necked flask was used, and 140 g of tetraethoxysilane, 5 g of 3-glycidoxypropyltriethoxydecane, and 140 g of ethanol were added, and the mixture was added once with stirring. . 7 g of a 60% nitric acid solution was dissolved in 120 g of pure water, followed by a reaction at 50 ° C for 3 hours. [Si02 bond 7] A 500-cm glass four-necked flask was used, and 145 g of tetraethoxy decane, 2 g of vinyl triethoxy decane, and 140 g of ethanol were added, and the mixture was added once with stirring to make 0. 015 g of a 60% nitric acid solution was dissolved in 115 g of pure water, followed by a reaction at 50 ° C for 3 hours. [Coupling Agent] The decane coupling agent used vinyl triethoxy decane. Titanium coupling agent -28- 201245215 A titanium coupling agent having a dialkyl pyrophosphate group represented by the chemical formula (8) is used. 0 C-0-Ti-H2C——Ο Ο 0 ΌΡΟ P-|〇C8H17) 2 2 (8) [Mixed solvent] Mixed solvent 1 uses isopropanol, ethanol and N,N-dimethylformamide The mixed solution (mass ratio 4:2:1), and the mixed solvent 2 is a mixture of ethanol and butanol (mass ratio 98:2). [Non-polymeric binder] Non-polymeric binder 1 is a mixture of 2-n-butoxyethanol and 3-isopropyl-2,4-pentanedione, non-polymeric binder 2 A mixture of 2,2-dimethyl-3,5-hexanedione and isopropyl acetate (mass ratio 1:1), non-polymeric binder 3 using 2-isobutoxyethanol and 2 a mixture of hexyloxyethanol and n-propyl acetate (mass ratio 4: 1: 1). [Examples 1 to 20] Example 1 was prepared by mixing ITO powder having an average particle diameter of 25 nm as conductive oxide particles in ethanol as a dispersion medium in the mixing ratio of Table 1 and in composition with respect to the transparent conductive film. The solid content in the material is a ratio of 25 mass % / 〇 as a binder (r| si ( 〇R 2 ) 3 ) containing binder -29 - 201245215 Example 2 is mixed as IP A as a dispersion medium The ITO powder having an average particle diameter of 25 nm of the conductive oxide particles is mixed at a ratio of 30% by mass to the solid content in the composition for a transparent conductive film to be a combination of the binder (WSi(OR2) 3 ). The agent 1 and the SiO 2 bonding agent 1 are mixed at a ratio of 90 to 10%. In Example 3, a cerium powder having an average particle diameter of 40 nm as a conductive oxide particle was mixed with ethanol as a dispersion medium, and mixed at a ratio of 10% by mass to the solid content in the composition for a transparent conductive film. The binder (WSi (OR2) 3)-containing binder 2 and the SiO 2 binder 2 are mixed at a ratio of 85 to 15 as a binder. Example 4 is a mixture of TZO powder having an average particle diameter of 30 nm as the conductive oxide particles in IP A as a dispersion medium, and a ratio of 30% by mass to the solid content in the composition for a transparent conductive film. The mixing is carried out as a binder (WSi (OR2) 3)-containing binder 2 and SiO 2 binder 1 in a ratio of 70 to 30. In Example 5, an I TO powder having an average particle diameter of 30 nm as a conductive oxide particle was mixed with ethanol as a dispersion medium, and the solid content in the composition for a transparent film was 15% by mass. The ratio mixing is carried out by mixing the binder (WSi (OR2) 3 )-containing binder 3 and the SiO 2 binder 5 in a ratio of 8 5 to 15 . In the mixed solvent 1 as the dispersion medium, the ITO powder having an average particle diameter of 35 nm as the conductive oxide particles is mixed, and the ratio of the solid content in the composition for the transparent conductive film is 20% by mass. Mixing the binder containing the (R1 S i ( 0 R2 ) 3 ) as the binder and the Si〇 2 binder 7 containing the -30-201245215 decane coupling agent at a ratio of 80 to 20 〇 7 is an ITO powder having an average particle diameter of 40 nm as a conductive oxide particle in an ethanol as a dispersion medium, and is mixed as a binder in a ratio of 20% by mass to the solid content in the composition for a transparent conductive film. The binder (WSi(OR2) 3 )-containing binder 1 and the SiO 2 binder 4 are mixed at a ratio of 70 to 30. In the example 8, the ITO powder having an average particle diameter of 25 nm as the conductive oxide particles is mixed with ethanol as a dispersion medium, and the mixture is mixed at a ratio of 30% by mass to the solid content in the composition for a transparent conductive film. The binder (R1 Si (OR2) 3 )-containing binder 4 and the non-polymer binder 1 are mixed at a ratio of 90 to 10, and further become a solid component after being formed with respect to the coating film. The titanium coupling agent having a dialkyl pyrophosphate group represented by the chemical formula (8) is mixed at a ratio of the mass of the composition of the oxide particles and the binder component to 5% by mass. In the mixed solvent 2 as a dispersion medium, the cerium powder having an average particle diameter of 50 nm as the conductive oxide particles was mixed and mixed at a ratio of 30% by mass to the solid content in the composition for a transparent conductive film. The binder 5 containing the (I^SiC OR2) 3 ) and the SiO 2 binder 2 containing a decane coupling agent as a binder are mixed at a ratio of 70 to 30. Example 1 A ruthenium powder having an average particle diameter of 30 nm as a conductive oxide particle is mixed with a lanthanum as a conductive medium in a dispersion medium, and is 15 mass% with respect to the solid content in the composition for a transparent conductive film. Ratio -31 - 201245215 A binder containing 5 (R^SiC OR2) 3) containing a decane coupling agent as a binder and a Si〇2 binder 丨 are mixed at a ratio of 60 to 40. In the mixed solvent 2 as the dispersion medium, the ITO powder having an average particle diameter of 40 nm as the conductive oxide particles was mixed and mixed at a ratio of 30% by mass to the solid content in the composition for the transparent conductive film. The binder 1 containing the (R1 Si (OR2) 3 ) as the binder and the non-polymer binder 3 are mixed at a ratio of 80 to 20. Example 1 2 is an ITO powder having an average particle diameter of 35 nm as a conductive oxide particle in a mixed solvent 2 as a dispersion medium, and is 25% by mass based on the solid content in the composition for a transparent conductive film. The ratio mixing is carried out as a binder (R1 Si (OR2) 3 )-containing binder 2 and a decane-containing coupling agent SiO 2 binder 6 in a ratio of 65 to 35. Example 13 is used as a dispersion medium. An ITO powder having an average particle diameter of 3 Onm as the conductive oxide particles is mixed with ethanol, and is mixed as a binder in a ratio of 25% by mass to the solid content in the composition for a transparent conductive film (WSi (OR2) 3) The binder 2 and the SiO 2 binder 3 are mixed at a ratio of 90 to 10, and further composed of a conductive oxide particle and a binder component which are solid components after being formed with the coating film. The amount is 0. A ratio of 7 mass% was mixed with a decane coupling agent (KBE-1003 manufactured by Shin-Etsu Silicone Co., Ltd.). [Example 1] 4 is an IZO powder having an average particle diameter of 25 nm as a conductive oxide particle mixed in IPA as a dispersion medium, and the solid content in the composition for a conductive film relative to 32-201245215 is 25 The ratio of % by mass will be used as a binder for the binder (Rii ( 〇r2 ) 3 )! The Si〇2 binder 2 and the non-polymer binder 2 are mixed at a ratio of 65 to 30 to 5. In the example 15, the ITO powder having an average particle diameter of 25 nm as the conductive oxide particles is mixed with butanol as a dispersion medium, and mixed at a ratio of 10% by mass to the solid content in the composition for a transparent conductive film. The binder (WSi(OR2) 3 )-containing binder 3 and the SiO 2 binder 4 are mixed at a ratio of 60 to 40 as a binder. Example 16 is a mixture of IZO powder having an average particle diameter of 25 nm as the conductive oxide particles in IPA as a dispersion medium, and mixing at a ratio of 25% by mass to the solid content in the composition for a transparent conductive film. The binder (WSi(OR2)3)-containing binder 4, the SiO 2 binder 7 and the non-polymer binder 1 are mixed at a ratio of 70 to 20 to 10%. Example 1 7 In the mixed solvent 1 as a dispersion medium, an IZO powder having an average particle diameter of 25 nm as the conductive oxide particles is mixed, and mixed as a binder in a ratio of 30% by mass to the solid content in the composition for a transparent conductive film. The (R1 Si(OR2)3)-containing binder 5 and the SiO 2 binder 3 containing a decane coupling agent are mixed at a ratio of 90 to 10. Example 1 8 is a mixture of a TZO powder having an average particle diameter of 30 nm as a conductive oxide particle in a mixed solvent 1 as a dispersion medium, and a ratio of 15% by mass to the solid content in the composition for a transparent conductive film. -33- 201245215 The mixing is carried out as a binder (Ιΐϋ(OR2)3)-containing binder 3, SiO 2 binder 5 and non-polymer binder 3 in a ratio of 85 to 12 to 3. Example 1 is a mixture of ITO powder having an average particle diameter of 50 nm as the conductive oxide particles in a mixed solvent 1 as a dispersion medium, and a ratio of 15% by mass to the solid content in the composition for a transparent conductive film. The mixing agent 1 and the Si 2 bonding agent 2 containing the binder (WSU OR2 ) 3 ) were mixed at a ratio of 75 to 25. In Example 20, a cerium powder having an average particle diameter of 40 nm as the conductive oxide particles was mixed in the PA as a dispersion medium, and mixed at a ratio of 30% by mass to the solid content in the composition for a transparent conductive film. (R1 Si (OR2) 3 )-containing binder 5, SiO 2 bonding agent 1 and decane coupling agent-containing Si 〇 2 binder 7 as a binder containing decane coupling agent at a ratio of 5 5 to 30 to 15 The ratio is mixed. [Comparative Example 1] In Comparative Example 1, ITO powder having an average particle diameter of 25 nm as conductive oxide particles was mixed in IPA as a dispersion medium, and the solid content in the composition for a transparent conductive film was 30 mass. The ratio of % is mixed with SiO 2 binder 1 as a binder. [Evaluation of Composition for Transparent Conductive Film] For the composition for a transparent conductive film shown in Examples 1 to 20 and Comparative Example 1, a glass substrate having a known optical constant was wet-coated -34-201245215 The cloth method (spin coating method, nozzle coating method, spray coating method, lithography method) forms a transparent electrode film and then fires at 160 to 220 ° C for 20 to 60 minutes to form a thickness 〇. 〇 5~0. 2 μηη transparent conductive film. For the film, a spectroscopic ellipsometer is used (Japan J.  A.  Woollam (manufactured by olla-2000) was measured, and the data was analyzed for the transparent conductive film portion to obtain an optical constant. From the optical constant of the analysis, 値 63 3 nm is used as the refractive index. These results are shown in Tables 1~3. As shown in FIG. 1 , a glass substrate of 3102 layers (not shown) having a thickness of 5 Onm is prepared as a substrate 10 on a main surface, and a surface having a textured surface and doped F (fluorine) is formed on the SiO 2 layer. A surface electrode layer (Sn02 film) 3 having a thickness of 800 nm was used as the transparent electrode layer 3. The transparent electrode layer 3 is patterned into a matrix shape by a laser processing method, and the electrical interconnections are connected to each other to form a wiring. Next, a photoelectric conversion layer 2 is formed on the transparent electrode layer 3 by a plasma CVD method. In this embodiment, the photoelectric conversion layer 2 is laminated from the side of the substrate 1 by p-type a-Si: Η (amorphous hydrogenated ruthenium), i-type a-Si (amorphous ruthenium), and n-type. Obtained by a film formed of pC-Si (microcrystalline niobium carbide) The above-described photoelectric conversion layer 2 is patterned by a laser processing method. This was used as a solar cell element which was subjected to film formation, and was used for evaluation of a composition for a transparent conductive film shown in the examples. For the solar cell elements which have been formed into films for the transparent conductive film compositions shown in Examples 1 to 20 and Comparative Example 1, the thickness after firing was set to 0. 07~0. 15μπι by the wet coating method (spin coating method, die coating method, spray coating method, lithography method, screen printing method) after coating at a low temperature of 25~60 ° C After drying for 5 minutes, a transparent -35 - 201245215 conductive film 1 was formed. Tables 1 to 3 show the coating method. Next, the following method is used to make the thickness after firing to be 0. 05~2. In the method of Ομηι, the prepared conductive reflective film composition is applied onto the transparent conductive film 1 by a wet coating method, and then dried at a low temperature of 25 to 60 ° C for 5 minutes to form a conductive reflective film. . Then, a composite film was formed on the solar cell by firing at 160 to 220 ° C for 20 to 60 minutes. Tables 1 to 3 show the film thickness after firing of the transparent conductive film 1. Here, the film thickness was measured by a cross-sectional observation using a scanning electron microscope (SEM, device name: S-4300, SU-8000) manufactured by Hi-Tech Co., Ltd. Further, a method of preparing a composition for a conductive reflective film is as follows. First, silver nitrate was dissolved in deionized water to prepare a metal ion aqueous solution. Further, sodium citrate was dissolved in deionized water to prepare a sodium citrate aqueous solution having a concentration of 26% by weight. The ferrous ferrous sulfate was directly added to the aqueous sodium citrate solution and dissolved in a nitrogen gas stream maintained at 35 ° C to prepare a reducing agent containing citrate ions and ferrous ions in a molar ratio of 3:2. Aqueous solution. Next, the nitrogen gas flow is maintained at 35 ° C, the stirrer of the magnetic stirrer is placed in the reducing agent aqueous solution, and the stirrer is rotated at a rotation speed of 10 rpm to stir the aqueous solution of the reducing agent. The aqueous solution of the above metal salt was added dropwise to the aqueous solution of the reducing agent to synthesize it. Here, the concentration of each solution is adjusted so that the amount of the metal salt aqueous solution added to the reducing agent aqueous solution is 1/10 or less of the amount of the reducing agent aqueous solution, and the reaction temperature is also caused when the room temperature metal salt aqueous solution is added dropwise. Keep at 40 ° C. Further, the mixing ratio of the aqueous solution of the reducing agent to the aqueous metal salt solution is adjusted so that the equivalent of the ferrous ion added as the reducing agent is three times the equivalent of the metal ion -36-201245215. After the dropwise addition of the aqueous solution of the metal salt to the aqueous solution of the reducing agent, the mixture was stirred for 15 minutes to generate metal particles in the mixed liquid to obtain a metal particle dispersion in which the metal particles were dispersed. The pH of the metal particle dispersion is 5. 5. The stoichiometric amount of metal particles in the dispersion is 5 g/liter. The resulting dispersion was allowed to stand at room temperature to precipitate metal particles in the molten metal, and the agglomerates of the precipitated metal particles were separated by decantation. The deionized water was added to the separated metal condensate to form a dispersion, and desalination treatment was carried out by ultrafiltration, and then washed with methanol to make the metal (silver) content 50% by mass. Subsequently, using a centrifugal separator, the centrifugal force of the centrifugal separator was adjusted, and by separating large silver particles having a particle diameter exceeding l 〇〇 nm, it was adjusted to have a primary particle diameter of 71% by a number average of 1 〇 5 5 nm. Silver nanoparticles in the range. That is, the ratio of the silver nanoparticles in the range of 10 to 5 Onm of the primary particle diameter of 100% of all the silver nanoparticles is adjusted to be 7 1 %. The obtained silver nanoparticles are chemically modified with a protective agent having an organic backbone having a carbon skeleton of carbon number 3. Then, 10 parts by mass of the obtained metal nanoparticles were added to 90 parts by mass of a mixed solution containing water, ethanol and methanol, and dispersed by mixing. Then, 4% by mass of polyvinylpyrrolidone and 1% by mass of citric acid anhydride were added to the dispersion so that the ratio of the metal nanoparticles was 95% by mass to obtain a composition for a reactive reflective film. So that the thickness after firing becomes a flaw.  〇 5 ~ 2 .  Ο μηι's method of applying the composition for a conductive reflective film to the transparent conductive film 1 by a wet coating method, and then firing at 160 to 22 (TC for 20 to 60 minutes under heat treatment conditions) Conductive back surface reflective film is formed on the transparent conductive film 1 - 37 - 201245215 Next, when evaluating the power generation efficiency as a solar cell, the solar cell element which has been formed into a conductive reflective film by a die coater is used. In the above, the composition for the reinforcing film is applied as a reinforcing film on the conductive reflective film so that the thickness of the composition for the reinforcing film after firing is 35 5 nm, and the coating film for self-reinforcing film is removed by vacuum drying. After the solvent, the solar cell was held in a hot air drying oven at 180 ° C for 20 minutes to thermally cure the film for a reinforcing film to obtain a reinforcing film for a conductive reflective film. The method for preparing a composition for a reinforcing film is as follows. 8% by mass of ITO particles having an average particle diameter of 25 nm as conductive oxide fine particles, and 2% by mass of a titanium coupling agent having a dialkyl pyrophosphate group as a coupling agent, 90% by mass As the dispersion medium of ethanol and butanol mixed solution (mass ratio 98: 2) and stirred at room temperature at a rotational speed of 800rpm 1 hour then the mixture was placed in a glass bottle lOOcc of 60g, a diameter of the square. 100 g of 3 mm oxidized cone beads were dispersed in a paint shaker for 6 hours to prepare a dispersion of ITO particles. Here, the titanium coupling agent having a dialkyl pyrophosphate group is represented by the above formula (8). Then, 4% by mass of the dispersion of the ITO particles and 86% by mass of the ethanol in the dispersion medium are mixed, and then the SiO 2 bonding agent 1 is mixed at 10% by mass to obtain a base liquid for the composition for a reinforcing film, and then the base liquid 95 is mixed. The mass % and the fumed cerium oxide dispersion as an additive were 5% by mass, and the mixture was dispersed and mixed at room temperature for 10 minutes in an ultrasonic vibrator to form a coating liquid for a composition for a reinforcing film. The solar cell element formed to the reinforcing film for a conductive reflective film is subjected to a laser processing method, and the photoelectric conversion layer 2 and the transparent film formed thereon are -38-201245215 conductive film 1, conductive reflective film 4, and The conductive film is patterned with a reinforcing film. The evaluation method of the solar cell element is a method of performing wire bonding on a substrate subjected to patterning by a laser processing method, and confirming the output characteristic and the short-circuit current (Jsc) when the IV characteristic curve is used. The photoelectric conversion layer obtained by the same manufacturing method was evaluated for the relative output of the ultra-straight solar cell element in which all of the transparent conductive film 'conductive reflective film and the reinforcing film were formed by sputtering. Tables 1 to 3 show the results. Here, as shown in FIG. 1 , the ultra-straight solar cell element formed by sputtering is first prepared as a substrate 10 in which a Si 2 layer (not shown) having a thickness of 50 nm is formed on a main surface. A surface electrode layer (Sn02 film) 3 having a concave-convex texture and having a F (fluorine) thickness of 800 nm was formed on the SiO 2 layer. The transparent electrode layer 3 is patterned into a matrix by laser processing, and wirings for electrically connecting the same are formed. Next, a photoelectric conversion layer 2 is formed on the transparent electrode layer 3 by a plasma CVD method. In this embodiment, the photoelectric conversion layer 2 is laminated from the substrate 1 side by P-type a-Si: Η (amorphous hydrogenated ruthenium), i-type a-Si (amorphous ruthenium), and n-type. Obtained by a film composed of μο-S i (microcrystalline niobium carbide). After the above-described photoelectric conversion layer 2 is patterned by a laser processing method, a transparent conductive film (ZnO layer) 1 having a thickness of 80 nm and a thickness of 200 nm are sequentially formed on the photoelectric conversion layer 2 by using a magnetron-connected sputtering apparatus. The conductive reflective film (silver electrode layer) 4 is used. -39- 201245215 [I嗽] Implementing I]7 ITO 〇s ^•(R'Si(OR2)3) ο i y5 1 I Et-OH S3 1 1 〇 Coating 〇δ ON s Π Example 6 ITO • Ry 1 ' 1 " •^(R'SiCOR^) Μ Si02 bond 7 1 I 93. 9 Sand touch 潍 j mm cloth 〇 〇 \ vC v〇 s Carrying ITO S3 containing (R'SKOR2)]) Si02 bond 5 1 1 V) Et-OH §s 1 1 lithography 0. 13 1. 70 2 s nmm TZO ο Contains (R 丨 Si(OR2)3) Ο SiOz^^ll 沄 1 1 s IPA 72. 3 1 1 Na coating 0. 15 5g ro s Implement egg ΑΤΟ 〇 g i- Contains (R'SKOR2)]) | 1 1 o Et-OH 1 1 1 雠 Coating 〇 1. 72 inch s nmm ITO (N ο i- containing (R 丨 Si(OR2)3) § s w o 1 1 IPA 1 72. 3 ! 1 1 wrap coating 〇〇 \ v〇in s lion J1 ITO V) (N JO 1- containing (R'Si(OR2)3) 8 1 1 1 1 Et-OH 1 1 1 mm fabric Co Sm 3ητη ff flat domain fiber (10)) s mt7* § most g苎11 s? house li 11 SI «μ ΓΤΠ 昼 ff 1 P li 11 N葙Jnrll η ΓΛ m 5TM w li 杓1 [Π} i tfirrli P ^ m li ^ a 1 灵m Jml) P 霊® 1 § 疏m P eBb § 暴 4®5 ±π ® m; 泰 泰 葙 葙 cm coating method thief film thickness ((4) refractive index relative to ^3⁄43⁄43⁄4% Phase Sim Current Density (%) Conductive Oxidizer Viscous 1 Even Miscellaneous J 1 1 -40- 201245215 [Table 2]

CT Example 8 Example 9 Example 1 〇W Example 11 Π Example 12 U Example U cr Example 14 Vapor particles mm ITO ΑΤΟ ΑΤΟ 1TO 1TO 1ΤΟ 1ZO Average particle size (nm > 25 50 30 40 35 30 25 ratio (quality (4) vs. cobalt mixture + Ϊ5) 70 70 85 70 75 75 75 Adhesive mmi contains (R'SitOR^ bond 4 ^(R'SKOR^j) binder 5 (I^ The combination of SiiO^W's binder S ^(R'SitOR1),) contains a binder of I(SitO^W's binding agent 2 (RiSitOR1^ Binding Agent 2^(R'SitOR1)), 1 lion Ratio of (mi%> Relative Na mixture 90 70 60 80 65 90 65 Remuneration 2 Non-polymeric binder SiO! Bonded JS2 SiOz binder 1 Non-polymerized bonding boat SiO, binder (S SiO: binder) 3 SiO: ratio of binder 2 (JTSV·) relative to binder 10 30 40 20 35 10 30 Na 3 - - - - one - non-polymeric binder 2 ratio of fii class 3 (ϊϊβν·> relative to Adhesive - - - - - - 5 Adhesive ratio (ϊϊββ/·) For fishing (along + adhesive ΉΚ) 30 30 1S 30 25 25 25 Fractional turn Et-OH Condensation solvent 2 iU solvent 1 Mix混合 混合 mixed 惭 2 EI-OH ΙΡΛ proportion 継%) relative to the pulse 86 8 1 69.4 81 90 88 89 «a mixture mm titanium coupling agent 剞矽 剞矽 © 合 _ 矽 偶 coupling agent 矽 ϊΐ ϊΐ 比例 ratio (苡 相对 relative to (捣 + binder he 0.5 4.6 4 - 1.1 0.7 - fine dressing Method Rotating Reverse Cloth Rotary Coating Screen Printing «Box Coating tmm wm Swirling Sweeping Ruler 0.13 0.1 0.15 0.07 0.07 ΰ.ι 0.07 μ Discount "1.64 1.66 1.70 1.67 1.68 1.66 1.65 Relative Hair Efficiency ( 1⁄4) 120 118 116 119 119 118 120 Phase-to-phase short-circuit m-stream density (called 104 104 103 105 104 104 10S -41 - 201245215 [Table 3] Example IS Decoration Example 16 Ώ π Π Example 18 W Example 19简体 2 〇mm το IZO IZO TZO ΙΤΟ ITO ITO average average diameter (nm> 25 25 25 30 50 40 25 a compound particle ratio (0β%> relative to (W+«合90 75 70 85 85 70 70 (R'SKOR1))) The combination of RSMORW 剤4 contains (RSitOR,) combination of knots (R*Si (OR: W bond 3 contains (RiSitOI^W combination of mi (RiSKORW's combination of ms - Ke® 丨 ratio < Π ϋ ϋ Λ) Relative to the adhesive 60 70 90 85 75 55 - Lion 2 Si. 】Combination (10) combined with fl!|7 SiO] binder 3 SiO: combined with SiOxiK mixture 2 SiO, binder 1 SiOz binder 1 station mixture M2 ratio _%> relative ffl 40 20 10 12 25 30 100 3 - Non-polymeric conformity ffll - Non- ί« combined adhesive 3 - SiOiiK combined with 7 - «The ratio of Ϊ3 to W 剤 - 10 - 3 - 15 - The ratio of 玷 剖 ΪΠ ΪΠ ΪΠ &卯+Binder+Yang 10 25 30 15 15 30 30 Ding drunk 1PA ΪΒ合雠 Mixed solvent 1 S solvent 1 IPA 1PA Fraction ratio ma%) Relative to composition 90.5 88 86 69.4 92.3 88 72.3 Face _ 矽倒矽娜合馆_ _ 矽院 coupling _ _ mixture ratio _%> Relative to ("+ adhesive move - 0.3 5.9 - - 3.8 - m loading method (four) 平 lithography lithography Mouth digging cloth 65 spray reverse cloth rotation cloth to the order of JTO ("n〇0.1 0.15 0.1 0.07 0.08 0.11 0.1 refraction string 1.71 1.64 1.64 1.69 1.72 1.63 1.90 相对 Relative efficiency (%> 116 121 122 117 116 121 99 Relative short circuit m flow density <%) 104 105 106 104 103 105 100 -42- 201245215 It can be understood from Tables 1 to 3 that Examples 1 to 20 The refracting power generation efficiency is as high as 8 to 122, and the relative short-circuit current density is 102 to 106. In particular, compared with the binder: 1 part by mass, 55 parts of the organic tri-potassium oxylate and/or its hydrolysis The embodiment has an extremely high power generation efficiency of 1 13 to 122% and a relative short-circuit current of 103 to 106%, which is comparable to that of the first embodiment. Moreover, the relative power generation efficiency of the sand chamber coupling agent examples 16, 17, 20' is 121 to 122° /., in contrast to this, it does not contain, as a binder, an organotrialkoxide represented by the formula (1): ...Si (wherein, R1 and R2 are specific hydrocarbon groups) and/or Comparative Example 1 of the hydrolyzate has a high refractive index and a relative short-circuit current density of slightly 100% relative to the power generation effect. Further, a binder containing 1 〇〇 mass of the binder (R1 Si (OR2) 3) Although the refractive index is the lowest, the workability at the time of patterning by the laser processing of the reinforcing film for a conductive reflective film is inferior, and it is considered that the relative short-circuit current density is lowered. As described above, the composition for a transparent conductive film of the present invention can be applied onto a photoelectric conversion layer by a wet method and fired, and by using a compound containing the formula (1): R1 Si (OR2) 3 (formula) In the organic trialkoxy decane represented by the hydrocarbon group of R1 and R2 and/or its hydrolyzate, a transparent conductive film having a low refractive index can be obtained. Therefore, it can be seen that a transparent conductive iridium having improved power generation efficiency of a thin film solar cell can be obtained. [FIG. 1 shows a low profile rate of the thin film solar cell of the present invention, which is also as high as ~90 mass 2 to 20, and density. The implementation is also inconsistent. OR2) 3 base decane ratio, phase example 1, and subsequent electro-efficiency coating to bond to a specific compound is simply an example -43- 201245215 Figure [Major component symbol description] 1 : Conductive transparent film 2: photoelectric conversion Layer 3: Transparent Electrode Layer 4: Conductive Reflective Film 10: Substrate-44-

Claims (1)

201245215 VII. Patent application scope: I. A composition for a transparent conductive film used in a thin film solar cell, which is characterized in that it contains conductive oxide particles and a binder which is hardened by heating. The binder contains a formula (1). ) : WSi ( OR2 ) 3 (wherein R 1 is a one-valent hydrocarbon group having 1 to 12 carbon atoms, and R 2 is a linear or branched alkyl group having a carbon number of 1 to 4) and/or Its hydrolyzate. 2. The composition for a transparent conductive film for use in a thin film solar cell according to the first aspect of the invention, wherein the binder (100 parts by mass) is contained in an amount of 50 to 95 parts by mass based on the above formula (1): R1 Si ( OR2) 3 represents an organotrialkoxydecane and/or a hydrolyzate thereof. 3. The composition for a transparent conductive film for a thin film solar cell according to the second aspect of the invention, wherein the binder comprises an organic trialkoxy decane represented by the above formula (1), water, and an organic solvent. And a binder component formed as a material of a mixture of one or a combination of an acid and a base of a catalyst. 4. The composition for a transparent conductive film for a thin film solar cell according to the second aspect of the invention, wherein the binder further comprises any one of a polymer type adhesive or a non-polymer type adhesive which is hardened by heating. Or both. 5. The composition for a transparent conductive film for a thin film solar cell according to any one of claims 1 to 4, wherein the binder comprises a sesquioxide. 6. The composition for a transparent conductive film for a thin film solar cell according to any one of claims 1 to 4, further comprising a coupling agent-45-201245215 7 - a composition for a transparent conductive film, It is a composition for a transparent conductive film used for a thin film solar cell according to claim 6 of the patent application, and the coupling agent is a decane coupling agent. 8. A transparent conductive film for use in a thin film solar cell, characterized by comprising conductive oxide particles and a hardened binder, wherein the hardened binder comprises the formula (1) zRiSiCOR2)" wherein R1 is carbon a hydrocarbyl group of a monovalent hydroxy group, R 2 is a linear or branched alkyl group having a carbon number of 1 to 4, which is represented by a linear or branched alkyl group; A transparent conductive film of a battery, wherein the hardened binder comprises sesquiterpene oxide. 10. The transparent conductive film for use in a thin film solar cell according to claim 8 or 9, wherein the hardened adhesive further comprises a hardening adhesive of a polymeric binder or a non-polymeric binder. 1 1 A thin film solar cell comprising a transparent conductive film for use in a thin film solar cell as claimed in claim 8 or 9. 12. A method for producing a transparent conductive film for a thin film solar cell, which comprises a method for producing a transparent conductive film of a thin film solar cell comprising a substrate, a transparent electrode layer, a photoelectric conversion layer and a transparent conductive film, characterized in that In order to wet-coat, a conductive oxide particle and a binder hardened by heating are used, and the binder contains the formula (1): R4i (OR2) 3 (wherein R1 is a carbon number 1) a composition for a transparent conductive film of 1,4-12-valent hydrocarbon group, R2 is a linear or branched alkyl group having a carbon number of 1 to 4, and an organic dialkoxy decane and/or a hydrolyzate thereof, is coated on the base. Transparent conductive material -46 - 201245215 On the photoelectric conversion layer on the electrode layer, after forming a transparent conductive coating film, the substrate having a transparent conductive coating film is fired at 130 to 400 ° C to form a transparent layer having a thickness of 0.03 to 0.5 μm. Conductive film. 13. The method for producing a transparent conductive film for a thin film solar cell according to the invention of claim 12, wherein the composition for the transparent conductive film contains 5 to 95 parts by mass based on 100 parts by mass of the binder. An organotrialkoxydecane represented by the formula (1) and/or a hydrolyzate thereof. 14. The method for producing a transparent conductive film for a thin film solar cell according to claim 13, wherein the binder comprises an organic trialkoxy decane represented by the above formula (1), water and an organic solvent, and A binder component formed as a material of a mixture of either or both of an acid and a base of a catalyst. 15. The method for producing a transparent conductive film for a thin film solar cell according to claim 14, wherein the binder further comprises any one of a polymer type adhesive or a non-polymer type adhesive which is hardened by heating. The method for producing a transparent conductive film for a thin film solar cell according to any one of claims 1 to 3, wherein the binder of the composition for a transparent conductive film comprises the binder Half a tweezer. The method for producing a transparent conductive film for a thin film solar cell according to any one of claims 13 to 15, wherein the composition for a transparent conductive film further contains a coupling agent. 1 8 The method for producing a transparent conductive film for use in a thin film solar cell-47-201245215, wherein the coupling agent is a decane coupling agent 〇 19. as disclosed in claim 13 to 15 A method for producing a transparent conductive film for use in a thin film solar cell, wherein the wet coating method is a spray coating method, a cloth coating method, a spin coating method, a knife coating method, or a slit coating method. A cloth method, an inkjet coating method, a die coating method, a screen printing method, a lithography method, or a gravure printing method. -48-