WO2014126117A1 - バリア層形成用組成物、バリア層付き半導体基板、太陽電池用基板の製造方法及び太陽電池素子の製造方法 - Google Patents
バリア層形成用組成物、バリア層付き半導体基板、太陽電池用基板の製造方法及び太陽電池素子の製造方法 Download PDFInfo
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- WO2014126117A1 WO2014126117A1 PCT/JP2014/053227 JP2014053227W WO2014126117A1 WO 2014126117 A1 WO2014126117 A1 WO 2014126117A1 JP 2014053227 W JP2014053227 W JP 2014053227W WO 2014126117 A1 WO2014126117 A1 WO 2014126117A1
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- barrier layer
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
- H01L21/2251—Diffusion into or out of group IV semiconductors
- H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
- H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
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- 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
- Y02E10/547—Monocrystalline silicon PV cells
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- 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
Definitions
- the present invention relates to a barrier layer forming composition, a semiconductor substrate with a barrier layer, a method for manufacturing a solar cell substrate, and a method for manufacturing a solar cell element.
- a p-type silicon substrate having a texture structure formed on the light-receiving surface is prepared so as to promote the light confinement effect and increase the efficiency, and then in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen, 800
- An n-type diffusion layer is uniformly formed on the surface of the p-type silicon substrate by performing several tens of minutes of processing at a temperature between 0 ° C. and 900 ° C.
- an electrode paste such as silver (Ag) on the light receiving surface and an electrode paste such as aluminum (Al) on the back side
- a solar cell element was obtained by heat treatment (firing).
- a method of forming such a back electrode type solar cell will be described.
- a barrier layer is formed on the entire light receiving surface and back surface of the n-type silicon substrate.
- the barrier layer has a function of suppressing the diffusion of the dopant into the silicon substrate.
- a part of the barrier layer on the back surface of the silicon substrate is removed to form an opening.
- a p + -type diffusion layer is formed in a region corresponding to the opening.
- a barrier layer is formed again on the entire back surface of the silicon substrate.
- a part of the barrier layer in a region different from the region where the p + -type diffusion layer is formed is removed to form an opening, and an n-type dopant is diffused from the opening to the back surface of the silicon substrate.
- a + type diffusion layer is formed.
- a p + -type diffusion layer and an n + -type diffusion layer are formed on the back surface.
- a back electrode type solar cell is completed by forming a texture structure, an antireflection layer, a passivation layer, an electrode, and the like.
- barrier layer As the barrier layer, a method using an oxide film formed on the surface of a silicon substrate by a thermal oxidation method has been proposed (see, for example, JP-A-2002-329880). On the other hand, a method of forming a barrier layer using a masking paste containing a SiO 2 precursor has also been proposed (see, for example, JP 2011-119341 A).
- the method of generating an oxide film on the surface of a silicon substrate by the thermal oxidation method described in Japanese Patent Application Laid-Open No. 2002-329880 described above has a problem that the manufacturing cost is high because the throughput is long.
- the method using a masking paste containing a SiO 2 precursor described in Japanese Patent Application Laid-Open No. 2011-119341 assumes a low-viscosity paste of 0.1 mPa ⁇ s to 30 mPa ⁇ s. It was difficult to apply a thick mask layer. Therefore, in this method, there is a problem that the diffusion of the dopant cannot be sufficiently prevented.
- the present invention has been made in view of the above conventional problems, and a barrier layer forming composition capable of sufficiently preventing the diffusion of a donor element or an acceptor element into a semiconductor substrate, and a barrier layer using the same It is an object of the present invention to provide a method for manufacturing an attached semiconductor substrate, a solar cell substrate, and a solar cell element.
- At least one silicon-containing compound selected from the group consisting of at least one alkoxysilane represented by the following general formula 1, polysilazane, and a siloxane resin obtained by hydrolysis and condensation polymerization of the alkoxysilane, and an organic binder And a dispersion medium, and a viscosity at 25 ° C. of 1 Pa ⁇ s to 100 Pa ⁇ s.
- R 1 and R 2 each independently represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 4. When two or more R 1 or R 2 are contained, each R 1 or each R 2 may be the same or different.
- composition for forming a barrier layer according to ⁇ 1> wherein the content of the silicon-containing compound is 1% by mass to 18% by mass in terms of SiO 2 .
- composition for forming a barrier layer according to ⁇ 1> wherein the content of the silicon-containing compound is 5% by mass to 16% by mass in terms of SiO 2 .
- composition for forming a barrier layer according to ⁇ 1> wherein the content of the silicon-containing compound is 6% by mass to 13% by mass in terms of SiO 2 .
- composition for forming a barrier layer according to any one of ⁇ 1> to ⁇ 4>, wherein the organic binder includes at least one selected from the group consisting of a cellulose derivative, an acrylic resin, and an alkyd resin. .
- composition for forming a barrier layer according to any one of ⁇ 1> to ⁇ 5>, wherein the organic binder includes ethyl cellulose.
- ⁇ 7> The dispersion medium according to any one of ⁇ 1> to ⁇ 6>, wherein the dispersion medium includes at least one selected from the group consisting of water, alcohol solvents, ether solvents, glycol monoether solvents, and terpene solvents.
- a barrier layer forming composition is a composition.
- ⁇ 8> For forming a barrier layer according to any one of ⁇ 1> to ⁇ 6>, wherein the dispersion medium includes at least one selected from the group consisting of terpineol, butyl carbitol, and butyl carbitol acetate. Composition.
- ⁇ 9> The barrier layer-forming composition according to any one of ⁇ 1> to ⁇ 8>, wherein the viscosity at 25 ° C. is 10 Pa ⁇ s to 80 Pa ⁇ s.
- a barrier layer which is a dried body of the composition for forming a barrier layer according to any one of ⁇ 1> to ⁇ 9>, which is provided on the conductive substrate;
- a semiconductor substrate with a barrier layer which is provided on the conductive substrate.
- ⁇ 12> The method for producing a solar cell substrate according to ⁇ 11>, wherein the method for applying the barrier layer forming composition to the semiconductor substrate is a screen printing method.
- a method for producing a solar cell element comprising a step of forming an electrode on a diffusion layer of a solar cell substrate obtained by the production method according to ⁇ 11> or ⁇ 12>.
- a composition for forming a barrier layer that can sufficiently prevent the diffusion of a donor element or an acceptor element into a semiconductor substrate, a semiconductor substrate with a barrier layer using the composition, a method for producing a substrate for a solar cell, And the manufacturing method of a solar cell element can be provided.
- composition for forming a barrier layer of the present invention will be described, and then a semiconductor substrate with a barrier layer using the composition for forming a barrier layer, a method for manufacturing a solar cell substrate, and a method for manufacturing a solar cell element will be described.
- the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used if the intended action of the process is achieved. included.
- “ ⁇ ” indicates a range including the numerical values described before and after the values as the minimum value and the maximum value, respectively.
- the amount of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
- the term “layer” includes a configuration formed in a part in addition to a configuration formed in the entire surface when observed as a plan view.
- the donor element or the acceptor element may be referred to as a dopant.
- the barrier layer in the present invention includes not only the case where it is formed on the entire surface when the semiconductor substrate is observed as a plan view but also the case where it is formed on a part thereof.
- the composition for forming a barrier layer of the present invention is at least one selected from the group consisting of at least one alkoxysilane represented by the following general formula 1, polysilazane, and a siloxane resin obtained by hydrolysis and condensation polymerization of the alkoxysilane.
- the barrier layer forming composition of the present invention has a viscosity at 25 ° C. of 1 Pa ⁇ s to 100 Pa ⁇ s.
- R 1 and R 2 each independently represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 4. When two or more R 1 or R 2 are contained, each R 1 or each R 2 may be the same or different.
- the following is selected from the group consisting of at least one alkoxysilane represented by the general formula (R 1 ) 4-n Si (OR 2 ) n , polysilazane, and a siloxane resin obtained by hydrolysis and condensation polymerization of the alkoxysilane.
- At least one silicon-containing compound is also referred to as a “specific silicon-containing compound”.
- a siloxane compound refers to a compound having a Si—O—Si bond.
- the barrier layer forming composition of the present invention inhibits the diffusion of a donor element or acceptor element as a dopant into a semiconductor substrate. Therefore, by forming a barrier layer using the barrier layer forming composition of the present invention in a region where the donor element or the acceptor element is not desired to be diffused in the semiconductor substrate, the donor element and the acceptor element are diffused in the region. It can be sufficiently prevented. Therefore, it is possible to selectively form a doping region in the semiconductor substrate. The reason for this can be considered as follows.
- a specific silicon-containing compound is included in the composition for forming a barrier layer together with an organic binder and a dispersion medium that can be adjusted to a specific viscosity, and this barrier layer-forming composition is applied to a semiconductor substrate by a screen printing method and heat-treated.
- the formed barrier layer has a high barrier performance. This is because a thick barrier layer can be easily formed by the screen printing method.
- a barrier layer forming composition having a viscosity adjusted to 1 Pa ⁇ s to 100 Pa ⁇ s, a barrier layer in which cracks are hardly generated can be formed. This barrier layer can effectively prevent high barrier performance, that is, dopant diffusion.
- the specific silicon-containing compound is at least one selected from the group consisting of at least one alkoxysilane represented by the following general formula 1, polysilazane, and a siloxane resin obtained by hydrolysis and condensation polymerization of the alkoxysilane.
- R 1 and R 2 are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 6 carbon atoms, and n is any integer of 1 to 4. When two or more R 1 or R 2 are contained, each R 1 or each R 2 may be the same or different.
- R 1 and R 2 are each independently an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, phenyl group, alkyl halide Examples include groups.
- the alkoxysilane it is preferable to use at least one selected from the group consisting of tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane, from tetraethoxysilane and tetramethoxysilane. It is more preferable to use at least one selected from the group consisting of Since tetraethoxysilane and tetramethoxysilane are rich in reactivity, a dense layer can be easily formed and a barrier layer with high barrier performance can be formed.
- examples of the siloxane resin obtained by hydrolyzing and polymerizing alkoxysilane include compounds represented by the following general formulas 2 and 3.
- n independently represents an integer of 2 to 100, n is preferably 2 to 20, and n is more preferably 3 to 8.
- Examples of such commercially available products include methyl silicate oligomer “MKC silicate” manufactured by Mitsubishi Chemical Corporation, silicate manufactured by Tama Chemical Industry Co., Ltd. (silicate 40, silicate 45, M silicate 51, etc.), and silicate manufactured by Colcoat Co., Ltd. (methyl silicate 51).
- polysilazane may be used as the specific silicon-containing compound.
- highly reactive polysilazane a dense layer can be easily formed and a barrier layer with high barrier performance can be formed.
- Either inorganic or organic polysilazane may be used, and examples of the inorganic polysilazane include linear compounds having a structural unit represented by the following general formula 4.
- n an integer.
- the weight average molecular weight of the inorganic polysilazane is preferably 690 to 2,000. In particular, it has 3 to 10 SiH 3 groups in one molecule, and the element ratios by chemical analysis are Si: 59 to 61, N: 31 to 34, and H: 6.5 to 7.5. Examples thereof include perhydropolysilazane and perhydropolysilazane having an average molecular weight in terms of polystyrene within the range of 3,000 to 20,000. In addition, the weight average molecular weight of inorganic polysilazane is converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- Examples of commercial products of polysilazane include “NN110” from AZ Electronic Materials, “Aquamica” from Clariant Japan, “Hard Barrier XR” from Leeds Factory, and the like.
- Catalysts include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, boric acid, phosphoric acid, hydrofluoric acid, and formic acid, acetic acid, propionic acid, butyric acid, oleic acid, linoleic acid, salicylic acid, benzoic acid, phthalic acid, oxalic acid And organic acids such as lactic acid and succinic acid.
- bases such as ammonia and an amine, as a catalyst.
- the content of the specific silicon-containing compound in the composition for forming a barrier layer is preferably 1% by mass to 18% by mass, more preferably 5% by mass to 16% by mass in terms of SiO 2 . More preferably, it is 6 mass% to 13 mass%. Within the above range, a sufficient barrier layer control effect tends to be obtained.
- the barrier layer forming composition of the present invention contains a dispersion medium.
- the dispersion medium is a medium in which the specific silicon-containing compound or the organic binder is dispersed or dissolved in the composition.
- the solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, Ketone solvents such as propyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diethyl ether, methyl ethyl ether, methyl-n-propyl ether, diisopropyl ether , Tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethylene glycol dimethyl ether, ethylene glyco
- the dispersion medium is preferably at least one selected from the group consisting of water, alcohol solvents, ether solvents, glycol monoether solvents and terpene solvents, water, alcohol, Cellosolve, terpineol (such as ⁇ -terpineol), diethylene glycol mono-n-butyl ether, or acetic acid diethylene glycol mono-n-butyl ether is more preferable, and at least one selected from the group consisting of terpineol, butyl carbitol, and butyl carbitol acetate is further included. preferable.
- the content of the dispersion medium in the composition for forming a barrier layer is determined in consideration of applicability and dopant concentration.
- the content is preferably 5% by mass to 99% by mass, and more preferably 20% by mass to 95% by mass. More preferably, it is 40 mass% or more and 90 mass% or less.
- the barrier layer forming composition of the present invention contains an organic binder.
- an organic binder By containing an organic binder, the viscosity can be adjusted, and sagging of printed lines during screen printing can be suppressed.
- organic binder examples include polyvinyl alcohol, polyacrylamide resin, polyvinylamide resin, polyvinylpyrrolidone resin, polyethylene oxide resin, polysulfone resin, acrylamide alkylsulfone resin, cellulose ether, carboxymethylcellulose, hydroxyethylcellulose, ethylcellulose and other cellulose derivatives, gelatin , Gelatin derivative, starch, starch derivative, sodium alginate compound, xanthan, guar gum, guar gum derivative, scleroglucan, scleroglucan derivative, tragacanth, tragacanth derivative, dextrin, dextrin derivative, (meth) acrylic acid resin, alkyl (meth) Contains amino groups such as acrylate resin and dimethylaminoethyl (meth) acrylate resin Meth) acrylic acid ester resins, butadiene resins, styrene resins, butyral resins, and may select these copolymers as appropriate.
- the organic binder preferably contains at least one selected from the group consisting of an acrylic acid resin, an alkyd resin, and a cellulose derivative from the viewpoints of degradability and prevention of dripping when screen printed. More preferably, it contains a cellulose derivative.
- the cellulose derivative include ethyl cellulose, nitrocellulose, acetyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, and hydroxyethyl cellulose.
- ethyl cellulose is preferably used. These are used singly or in combination of two or more.
- the molecular weight of the organic binder is not particularly limited, and it is desirable to adjust appropriately in view of the desired viscosity as the composition.
- the organic binder content in the barrier layer forming composition is preferably 0.5% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, and more preferably 3% by mass. More preferably, it is 20 mass% or less.
- a dispersion medium in which an organic binder is dissolved may be used as the dispersion medium and the organic binder.
- composition for barrier layer formation may use isobornyl cyclohexanol exemplified as a solvent together with the organic binder or as a material replacing the organic binder.
- Isobornylcyclohexanol is commercially available as “Telsolve MTPH” (Nippon Terpene Chemical Co., Ltd., trade name).
- Isobornylcyclohexanol has a high boiling point of 308 ° C to 318 ° C, and when it is removed from the barrier layer, it does not need to be degreased by firing like an organic binder, but must be vaporized by heating. Can do.
- the content of isobornylcyclohexanol is 0.5% by mass to 85% by mass in the total mass of the composition for forming a barrier layer. It is preferably 1% by mass to 80% by mass, more preferably 2% by mass to 80% by mass.
- the barrier layer-forming composition includes a thickener, a wetting agent, a surfactant, an inorganic powder, a thixotrope as other components as necessary. You may contain various additives, such as an agent.
- the surfactant examples include nonionic surfactants, cationic surfactants, and anionic surfactants.
- nonionic surfactants or cationic surfactants are preferred because impurities such as heavy metals are not brought into the semiconductor device.
- silicon-containing surfactants, fluorine-containing surfactants, and organic surfactants are exemplified as nonionic surfactants, and organic surfactants are preferred because they are baked quickly during heating such as diffusion.
- organic surfactants include ethylene oxide-propylene oxide block copolymers, acetylene glycol compounds, and the like, and acetylene glycol compounds are more preferred because they reduce the variation in resistance of semiconductor devices.
- Examples of the inorganic powder include silicon oxide, silicon nitride, silicon carbide powder and the like.
- the barrier layer forming composition may contain a thixotropic agent.
- thixotropy can be easily controlled, and a composition for forming a barrier layer for screen printing having a viscosity suitable for screen printing can be constituted.
- thixotropy is controlled, it is possible to suppress bleeding and sagging of the printing pattern of the composition for forming a barrier layer during printing.
- thixotropic agents polyether compounds, fatty acid amides, organic fillers, inorganic fillers, hydrogenated castor oil, urea urethane amide, bio gum, guar gum, locust bean gum, carrageenan, pectin, agar, ⁇ -glucan, tamarind seed gum, psyllium seed gum , Polyvinyl pyrrolidone, silicone-based thickening gelling agent and oil-based gelling agent (trade name: Gelol (Shin Nihon Rika Co., Ltd.), “Gelall” is a registered trademark).
- the organic binder described above may also serve as a thixotropic agent. Examples of such a material include ethyl cellulose.
- the composition for forming a barrier layer of the present invention does not contaminate the semiconductor substrate, that is, from the viewpoint of suppressing the recombination of carriers in the semiconductor substrate, the content of metal such as iron, tungsten, gold, nickel, chromium, manganese, etc.
- the content is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less.
- the viscosity at 25 ° C. of the barrier layer forming composition is 1 Pa ⁇ s to 100 Pa ⁇ s.
- the viscosity is a measured value obtained by rotating an EMD-type rotational viscometer at 25 ° C. for 1 minute at predetermined times (min ⁇ 1 , 1/60 sec ⁇ 1 ), and a predetermined conversion factor. It is defined as a value multiplied by. The conversion factor varies depending on the rotational speed and the type of cone used.
- the viscosity of the composition for forming a barrier layer maintained at 25 ⁇ 1 ° C. is measured using an EMD type rotational viscometer equipped with a cone rotor having a cone angle of 3 ° and a cone radius of 14 mm.
- Barrier layer forming composition of the present invention at 25 ° C., at EHD type rotational viscometer, viscosity measured at a rotation speed of 0.5 min -1 ⁇ 5min -1 is 1Pa ⁇ s ⁇ 100Pa ⁇ s, 5Pa More preferably, it is s to 80 Pa ⁇ s, still more preferably 10 Pa ⁇ s to 80 Pa ⁇ s, and particularly preferably 10 Pa ⁇ s to 60 Pa ⁇ s.
- the barrier layer-forming composition has a viscosity of 1 Pa ⁇ s or more, dripping hardly occurs when applied to a semiconductor substrate, and when it is 100 Pa ⁇ s or less, a fine coating pattern can be formed.
- the composition for forming a barrier layer of the present invention is a mixture of a specific silicon-containing compound, an organic binder, a dispersion medium, and components added as necessary using a blender, mortar, rotor, rotation / revolution mixer, and the like. You can get it. Moreover, when mixing, you may add a heat
- the heating temperature at this time can be, for example, 30 ° C. to 100 ° C.
- the semiconductor substrate with a barrier layer of the present invention includes a semiconductor substrate and a barrier layer that is a dried body of the composition for forming a barrier layer provided on the semiconductor substrate.
- the impurity diffusion layer can be selectively formed in a region other than the region where the barrier layer is provided.
- the amount of the barrier layer forming composition applied to the semiconductor substrate is not particularly limited, and is preferably 0.01 g / m 2 to 100 g / m 2, and preferably 0.1 g / m 2 to 20 g / m 2 . It is preferable.
- the thickness of the barrier layer formed by applying the composition for forming a barrier layer is not particularly limited, and is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 30 ⁇ m.
- the barrier layer is a dried body of the barrier layer forming composition, and is formed by removing at least a part of the dispersion medium contained in the barrier layer forming composition.
- a method for removing the dispersion medium for example, a method of performing heat treatment at a temperature of about 80 ° C. to 500 ° C. for about 1 to 10 minutes when using a hot plate, and about 10 to 30 minutes when using a dryer or the like. Can be mentioned.
- the heat treatment conditions are adjusted according to the type and content of the dispersion medium of the barrier layer forming composition, and are not particularly limited to the above conditions in the present invention.
- the content rate (residual rate) of the dispersion medium in the barrier layer is not particularly limited.
- the content of the dispersion medium in the barrier layer is preferably 30% by mass or less, more preferably 0.01% by mass to 15% by mass, and further preferably 0.1% by mass to 5% by mass. preferable.
- the content of the dispersion medium in the barrier layer can be calculated from the content of the nonvolatile component in the barrier layer forming composition and the amount of the barrier layer forming composition applied to the semiconductor substrate.
- the barrier layer forming composition is formed on a semiconductor substrate to form a patterned barrier layer, and the barrier layer on the semiconductor substrate is formed. And a step of diffusing a donor element or an acceptor element in a portion where the diffusion layer is not formed to partially form a diffusion layer in the semiconductor substrate.
- the manufacturing method of the solar cell element of this invention includes the process of forming an electrode on the diffusion layer of the board
- FIG. 1 is a schematic cross-sectional view conceptually showing an example of a manufacturing process of a solar cell substrate and a solar cell element of the present invention.
- FIG. 1 demonstrates the board
- the composition for barrier layer formation of this invention is applicable to the board
- other types other than the back electrode type include a selective emitter type and a double-sided light receiving type.
- a diffusion layer having a dopant concentration higher than that of other regions is formed immediately below the electrode on the light receiving surface side.
- the barrier layer forming composition of the present invention can be used to form the high concentration diffusion layer region.
- finger bars and bus bars are formed on both surfaces as electrodes, an n + type diffusion layer is formed on one surface of the semiconductor substrate, and a p + type diffusion layer is formed on the other surface.
- the barrier layer forming composition of the present invention can be used.
- an alkaline solution is applied to a silicon substrate which is an n-type semiconductor substrate 10 to remove a damaged layer, and a texture structure is obtained by etching.
- the damaged layer on the surface of the silicon substrate generated when slicing from the ingot is removed with a 20% by mass aqueous sodium hydroxide solution.
- the silicon substrate is etched with an aqueous solution containing a 1 mass% sodium hydroxide aqueous solution and 10 mass% isopropyl alcohol to form a texture structure on the n-type semiconductor substrate 10 (the description of the texture structure is omitted in the figure).
- the solar cell element by forming a texture structure on the light receiving surface side of the n-type semiconductor substrate 10, a light confinement effect is promoted and high efficiency is achieved.
- the barrier layer forming composition of the present invention is applied to the light receiving surface of the n-type semiconductor substrate 10 and the back surface opposite to the light receiving surface to form the barrier layer 11.
- the application method is not limited, and examples thereof include a printing method, a spin coating method, a brush coating method, a spray method, a doctor blade method, a roll coating method, and an ink jet method, and it is preferable to use a screen printing method.
- the composition for forming a barrier layer there is no particular limitation as application amount of the composition for forming a barrier layer, it is possible to 0.01 g / m 2 or more 100 g / m 2 or less and preferably, 0.1 g / m 2 or more 20 g / m 2 or less Is more preferable.
- coating thickness of the said composition for barrier layer formation It is preferable that they are 0.1 micrometer or more and 50 micrometers or less, and it is more preferable that they are 1 micrometer or more and 30 micrometers or less.
- a drying step for volatilizing the dispersion medium contained in the composition may be necessary after application.
- drying is performed at a temperature of about 80 ° C. to 300 ° C. for about 1 to 10 minutes when using a hot plate, and about 10 to 30 minutes when using a dryer or the like.
- the drying conditions are adjusted according to the content of the dispersion medium of the barrier layer forming composition, and are not particularly limited to the above conditions in the present invention.
- the barrier layer can be obtained as a dried product obtained by drying the barrier layer forming composition.
- a barrier layer is formed in a pattern on the back surface.
- the patterned barrier layer is obtained by applying the barrier layer forming composition 11 in a pattern shape.
- spin coating method, brush coating, spraying method, doctor blade method, roll coating method, etc. after the barrier layer forming composition 11 is applied to the entire surface, it is partially removed by etching or the like. A barrier layer is obtained.
- coating diffusion materials 12 and 13 for forming an n + type diffusion layer and a p + type diffusion layer are applied.
- an n + -type diffusion layer 14 and a p + -type diffusion layer 15 are formed on the n-type semiconductor substrate 10 by thermal diffusion.
- the heat treatment temperature for thermal diffusion is not particularly limited, but the heat treatment is preferably performed at a temperature of 750 ° C. to 1050 ° C. for 1 minute to 300 minutes.
- a method of forming the n + -type diffusion layer 14 and the p + -type diffusion layer 15 in a lump is shown, but they may be diffused individually.
- the coating diffusion material 13 for forming the p + -type diffusion layer 15 is applied and thermally diffused to remove the heat-treated product (baked product) 13 ′ of the coating diffusion material, and then the n + -type diffusion layer 14.
- the diffusion material for application 12 for forming the film may be applied and thermally diffused, and the heat-treated product (baked product) 12 ′ of the diffusion material for application may be removed.
- the present invention can be similarly applied to a method using POCl 3 gas or BBr 3 gas.
- a region where the p + -type diffusion layer 15 is to be formed is used as an opening, and the barrier layer 11 is formed using a barrier layer forming composition other than the region used as the opening.
- the barrier layer 11 is removed.
- a region in which the n + -type diffusion layer 14 is to be formed is an opening, and the barrier layer 11 is formed using the barrier layer forming composition other than the region to be the opening.
- an n + type diffusion layer 14 is formed in the n type semiconductor substrate 10 corresponding to the opening.
- the barrier layer 11 and the heat-treated products (fired products) 12 ′ and 13 ′ of the diffusion material for coating are removed to obtain a solar cell substrate.
- the removal method include a method of immersing in an aqueous solution containing an acid, and a heat-treated product of a coating diffusion material for forming the barrier layer 11, the n + -type diffusion layer 14 and the p + -type diffusion layer 15. (Baking product) It is preferable to determine by the composition of 12 'and 13'.
- the method includes a step of etching the glass layers [heat treated products (baked products) 12 ′ and 13 ′] and the barrier layer 11 formed on the semiconductor substrate by a thermal diffusion treatment with an aqueous solution containing hydrofluoric acid. preferable.
- an antireflection layer 16 is provided on the light receiving surface and a passivation layer 17 is provided on the back surface.
- the antireflection layer 16 and the passivation layer 17 may have the same composition or different compositions.
- Examples of the antireflection layer 16 include a silicon nitride layer, and examples of the passivation layer 17 include a silicon oxide layer.
- the thickness of the antireflection layer and the passivation layer is not particularly limited, and is preferably 10 nm to 300 nm, more preferably 30 nm to 150 nm.
- portions where electrodes are formed are opened in the passivation layer 17 on the n + -type diffusion layer 14 and the p + -type diffusion layer 15 (on the back surface side).
- an opening can be formed by applying an etching solution (for example, a solution containing hydrofluoric acid, ammonium fluoride, or phosphoric acid) to a portion where the opening is desired by an inkjet method or the like, and performing heat treatment. .
- an n electrode 18 and a p electrode 19 are formed on the n + -type diffusion layer 14 and the p + -type diffusion layer 15 (on the back surface side), respectively.
- the material and forming method of the n electrode 18 and the p electrode 19 are not particularly limited.
- the n-electrode 18 and the p-electrode 19 may be formed by applying an electrode forming paste containing aluminum, silver, or copper and drying the paste.
- the n-electrode 18 and the p-electrode 19 are heat-treated (fired) to complete the solar cell element.
- the step of opening shown in FIG. 1 (7) can be omitted.
- an electrode forming paste containing glass frit is applied on the passivation layer 17 and heat-treated (fired) in the range of 600 ° C. to 900 ° C. for several seconds to several minutes, the glass frit melts the passivation layer 17 on the back surface side, and paste
- the metal particles for example, silver particles
- the metal particles inside form a contact portion with the silicon substrate 10 and solidify. Thereby, the formed back surface electrodes 18 and 19 and the silicon substrate 10 are electrically connected. This is called fire-through.
- the solar cell includes at least one of the solar cell elements, and is configured by arranging a wiring material on the electrode of the solar cell element.
- a plurality of solar cell elements may be connected via a wiring material as necessary, and may be further sealed with a sealing material.
- the wiring material and the sealing material are not particularly limited, and can be appropriately selected from those usually used in the industry.
- Example 1> (Preparation of barrier layer forming composition 11) To 8.5 g of terpineol (Nippon Terpene Chemical Co., Ltd. “Terpineol-LW”) was added 1.5 g of ethyl cellulose (“Etocel STD200”, (Etocel) is a registered trademark) and dissolved at 150 ° C. for 1 hour. 15 A mass% ethylcellulose / terpineol solution was prepared. Ethyl silicate (Tama Chemical Co., Ltd.
- Silicate 40 SiO 2 equivalent: 40%
- SiO 2 SiO 2 equivalent: 40%
- 1.5 g silicon compound is 6% by mass in terms of SiO 2
- 15% ethyl cellulose / terpineol solution 4.3 g (ethyl cellulose: 6.45% by mass)
- 4.2 g of terpineol terpineol: 63.55% by mass
- This barrier layer forming composition 11 had a viscosity of 25 Pa ⁇ s at 25 ° C. and 5 min ⁇ 1 .
- the viscosity was measured using an EHD type viscometer (Tokyo Keiki Co., Ltd., cone angle: 3 °, cone radius: 14 mm), and the sampling amount of the barrier layer forming composition was 0.4 ml.
- the barrier layer-forming composition 11 was applied by screen printing (MT-320T, Micro Tech Co., Ltd.), and 150 ° C. After drying for 5 minutes on a hot plate, the substrate was dried for 1 minute on a hot plate at 500 ° C. This is a substrate with a barrier layer. Next, another silicon substrate was prepared, spin-coated with a phosphorus diffusion solution at 500 min ⁇ 1 (Mikasa Corporation, MS-A100), and dried at 200 ° C. This is a counter diffusion substrate.
- the substrate with the barrier layer and the counter diffusion substrate were opposed to each other at a distance of 1 mm, and heated at 850 ° C. for 30 minutes to diffuse phosphorus into the substrate with the barrier layer. Thereafter, the substrate with the barrier layer was immersed in a 10% by mass hydrochloric acid aqueous solution for 5 minutes, washed with water, and further immersed in a 2.5% by mass hydrofluoric acid aqueous solution for 5 minutes. This was washed with water and dried, and then evaluated as follows.
- the sheet resistance of the substrate to which the barrier layer-forming composition was applied was measured by a four-probe method using a Mitsubishi Chemical Corporation, Loresta-EP MCP-T360 type low resistivity meter.
- the sheet resistance of the portion where the barrier layer forming composition 11 was applied was 190 ⁇ / ⁇ .
- the sheet resistance of the uncoated part was 40 ⁇ / ⁇ .
- the n-type silicon substrate after slicing was immersed in a 2.5 mass% HF aqueous solution for 5 minutes, washed with water, and measured for sheet resistance after drying. As a result, it was 240 ⁇ / ⁇ . .
- Examples 2 to 6 Comparative Example 1> A barrier layer forming composition having the composition shown in Tables 1 and 2 was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. The materials shown in Tables 1 and 2 are as follows. In the table, “-” indicates that no addition was made. Methyl silicate: Tama Chemical Co., Ltd., product name “M silicate 51, SiO 2 equivalent: 51% by mass Polysilazane: AZ Electronic Materials, product name “NN110” (10 mass% polysilazane / xylene solution), SiO 2 equivalent: about 13.3 mass% Butyl carbitol acetate: Wako Pure Chemical Industries, Ltd. Silicon oxide: High Purity Chemical Laboratory, product name Silicon oxide (average particle size: 1 ⁇ m)
- the semiconductor substrate of the dopant As described above, by using the barrier layer forming composition containing the specific silicon-containing compound, the organic binder, and the dispersion medium and having a viscosity at 25 ° C. of 1 Pa ⁇ s to 100 Pa ⁇ s, the semiconductor substrate of the dopant It has been found that the diffusion to can be sufficiently prevented. It was also found that surface roughness of the semiconductor substrate can be suppressed.
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Abstract
Description
まず、光閉じ込め効果を促して高効率化を図るよう、受光面にテクスチャー構造を形成したp型シリコン基板を準備し、続いてオキシ塩化リン(POCl3)、窒素及び酸素の混合ガス雰囲気において800℃~900℃で数十分の処理を行って、p型シリコン基板の表面に一様にn型拡散層を形成する。次いで、受光面に銀(Ag)等の電極ペースト、裏面側にアルミニウム(Al)等の電極ペーストを塗布した後、熱処理(焼成)することにより、太陽電池素子を得ていた。
また、特開2011-119341号公報に記載の、SiO2前駆体を含有するマスキングペーストを用いる方法では、0.1mPa・s~30mPa・sの低粘度のペーストを想定しており、スクリーン印刷法での塗布が難しく、厚いマスク層を形成することが困難であった。そのため、この方法の場合、十分にドーパントの拡散を防止できないという問題があった。
<1> 下記一般式1で表される少なくとも一種のアルコキシシラン、ポリシラザン、及び前記アルコキシシランを加水分解し縮合重合させたシロキサン樹脂からなる群より選択される少なくとも一種のケイ素含有化合物と、有機バインダと、分散媒と、を含有し、25℃における粘度が1Pa・s~100Pa・sである、バリア層形成用組成物。
前記導体基板上に付与された、前記<1>~<9>のいずれか一項に記載のバリア層形成用組成物の乾燥体であるバリア層と、
を有するバリア層付き半導体基板。
前記半導体基板上の前記バリア層が形成されていない部分に、ドナー元素又はアクセプター元素を拡散して、前記半導体基板内に部分的に拡散層を形成する工程と、を含む、太陽電池用基板の製造方法。
尚、本発明におけるバリア層は、半導体基板を平面図として観察したときに、全面に形成される場合のみならず、一部に形成される場合をも包含される。
本発明のバリア層形成用組成物は、下記一般式1で表される少なくとも一種のアルコキシシラン、ポリシラザン、及び前記アルコキシシランを加水分解し縮合重合させたシロキサン樹脂からなる群より選択される少なくとも一種のケイ素含有化合物と、有機バインダと、分散媒と、を含有する。そして、本発明のバリア層形成用組成物は、25℃における粘度が1Pa・s~100Pa・sである。
SinOn-1(OC2H5)2(n+1) 一般式3
本発明のバリア層形成用組成物は分散媒を含有する。分散媒とは、組成物中において特定ケイ素含有化合物又は有機バインダを分散又は溶解させる媒体である。
本発明のバリア層形成用組成物は、有機バインダを含有する。有機バインダを含有することで、粘度を調節することができ、また、スクリーン印刷時の印刷線のダレを抑制することができる。
バリア層形成用組成物は、特定ケイ素含有化合物と、有機バインダと、分散媒と、に加え、必要に応じて、その他の成分として、増粘剤、湿潤剤、界面活性剤、無機粉末、チキソ剤等の各種添加剤を含有してもよい。
前述の有機バインダがチキソ剤の役割を兼ねていてもよく、このような材料としてエチルセルロースを挙げることができる。
本明細書において粘度とは、EMD型回転粘度計を25℃で1分間、所定の回毎分(min―1、1/60sec-1)で回転させたときの測定値に、所定の換算係数を乗じた値と定義する。換算係数は、回転数及び用いたコーンの種類によってによって異なる。本明細書では、25±1℃に保たれたバリア層形成用組成物について、コーン角度3゜、コーン半径14mmのコーンロータを装着したEMD型回転粘度計を用いて粘度が測定される。
本発明のバリア層付き半導体基板は、半導体基板と、前記半導体基板上に付与された前記バリア層形成用組成物の乾燥体であるバリア層と、を有する。半導体基板上にバリア層が設けられていることで、バリア層が設けられた領域以外の領域に選択的に不純物拡散層を形成することができる。
本発明の太陽電池用基板の製造方法は、前記バリア層形成用組成物を半導体基板上に付与してパターン状のバリア層を形成する工程と、前記半導体基板上の前記バリア層が形成されていない部分に、ドナー元素又はアクセプター元素を拡散して、前記半導体基板内に部分的に拡散層を形成する工程と、を含む。
また、本発明の太陽電池素子の製造方法は、上記製造方法により得られる太陽電池用基板の拡散層上に、電極を形成する工程を含む。
裏面電極型以外のその他の形式としては、選択エミッタ型及び両面受光型を例示することができる。選択エミッタ型の太陽電池用基板では、受光面側の電極直下に他の領域よりもドーパント濃度の高い拡散層が形成されている。この高濃度の拡散層の領域を形成するのに、本発明のバリア層形成用組成物を用いることができる。また、両面受光型の太陽電池素子では、両面に電極としてフィンガーバー及びバスバーが形成され、半導体基板の一方の面にはn+型拡散層、他方の面にはp+型拡散層が形成されている。このn+型拡散層及びp+型拡散層を位置選択的に形成するために、本発明のバリア層形成用組成物を用いることができる。
詳細には、インゴットからスライスした際に発生するシリコン基板表面のダメージ層を20質量%水酸化ナトリウム水溶液で除去する。次いで、1質量%水酸化ナトリウム水溶液と10質量%イソプロピルアルコールとを含む水溶液によりシリコン基板をエッチングし、n型半導体基板10にテクスチャー構造を形成する(図中ではテクスチャー構造の記載を省略する)。太陽電池素子は、n型半導体基板10の受光面側にテクスチャー構造を形成することにより、光閉じ込め効果が促され、高効率化が図られる。
太陽電池は、前記太陽電池素子の少なくとも一種を含み、太陽電池素子の電極上に配線材料が配置されて構成される。太陽電池は更に必要に応じて、配線材料を介して複数の太陽電池素子が連結され、更に封止材で封止されていてもよい。
前記配線材料及び封止材としては特に制限されず、当業界で通常用いられているものから適宜選択することができる。
(バリア層形成用組成物11の調製)
テルピネオール(日本テルペン化学株式会社「ターピネオール-LW」)8.5gにエチルセルロース(ダウケミカル社「エトセルSTD200」、(エトセル)は登録商標)1.5gを加え、150℃にて1時間溶解し、15質量%エチルセルロース/テルピネオール溶液を調製した。
エチルシリケート(多摩化学工業株式会社「シリケート40」、SiO2換算量:40%)1.5g(ケイ素化合物はSiO2換算で6質量%)、15質量%エチルセルロース/テルピネオール溶液4.3g(エチルセルロース:6.45質量%)、及びテルピネオール4.2g(テルピネオール:63.55質量%)をプラスチック製容器に入れた。これを自転・公転ミキサ(株式会社シンキー「AR-100」)を用い、10分間、混合し、バリア層形成用組成物11を調製した。
リン酸二水素アンモニウム(和光純薬工業株式会社)の20質量%水溶液を調製し、上澄みの飽和リン酸二水素アンモニウム水溶液をリン拡散液として用いた。
テクスチャー処理したn型シリコン基板(以下、「n型シリコン基板」ともいう)表面上に、スクリーン印刷(MT-320T、マイクロ・テック株式会社)によってバリア層形成用組成物11を塗布し、150℃のホットプレート上で5分間乾燥後、500℃のホットプレートで1分間乾燥させた。これをバリア層付き基板とする。
次いで、別のシリコン基板を用意し、リン拡散液を500min-1でスピンコート(ミカサ株式会社、MS-A100)し、200℃にて乾燥した。これを対向拡散用基板とする。
バリア層形成用組成物を塗布した部分の基板のシート抵抗は、三菱化学株式会社、Loresta-EP MCP-T360型低抵抗率計を用いて四探針法により測定した。バリア層形成用組成物11を塗布した部分のシート抵抗は190Ω/□であった。塗布しない部分のシート抵抗は40Ω/□であった。
表1及び2に示す組成のバリア層形成用組成物を調製し、実施例1と同様にして評価した。結果を表1及び2に示す。尚、表1及び2中に示した材料は、以下の通りである。尚、表中「-」は添加していないことを示す。
メチルシリケート:多摩化学工業株式会社、製品名「Mシリケート51、SiO2換算量:51質量%
ポリシラザン:AZエレクトロニックマテリアルズ社、製品名「NN110」(10質量%ポリシラザン/キシレン溶液)、SiO2換算量:約13.3質量%
ブチルカルビトールアセテート:和光純薬工業株式会社
酸化ケイ素:株式会社高純度化学研究所、製品名酸化ケイ素(平均粒子径:1μm)
Claims (13)
- 下記一般式1で表される少なくとも一種のアルコキシシラン、ポリシラザン、及び前記アルコキシシランを加水分解し縮合重合させたシロキサン樹脂からなる群より選択される少なくとも一種のケイ素含有化合物と、有機バインダと、分散媒とを含有し、25℃における粘度が1Pa・s~100Pa・sである、バリア層形成用組成物。
(R1)4-nSi(OR2)n ・・・一般式1
〔一般式1中、R1及びR2は、各々独立に、炭素数1~6の脂肪族炭化水素基又は芳香族炭化水素基を表し、nは1~4のいずれかの整数を表す。R1又はR2が2以上含まれる場合、各R1又は各R2は同一であっても異なってもよい。〕 - 前記ケイ素含有化合物の含有率が、SiO2換算で1質量%~18質量%である、請求項1に記載のバリア層形成用組成物。
- 前記ケイ素含有化合物の含有率が、SiO2換算で5質量%~16質量%である、請求項1に記載のバリア層形成用組成物。
- 前記ケイ素含有化合物の含有率が、SiO2換算で6質量%~13質量%である、請求項1に記載のバリア層形成用組成物。
- 前記有機バインダが、セルロース誘導体、アクリル樹脂及びアルキド樹脂からなる群より選択される少なくとも一種を含む、請求項1~請求項4のいずれか一項に記載のバリア層形成用組成物。
- 前記有機バインダが、エチルセルロースを含む、請求項1~請求項5のいずれか一項に記載のバリア層形成用組成物。
- 前記分散媒が、水、アルコール溶剤、エーテル溶剤、グリコールモノエーテル溶剤及びテルペン溶剤からなる群より選択される少なくとも一種を含む、請求項1~請求項6のいずれか一項に記載のバリア層形成用組成物。
- 前記分散媒が、テルピネオール、ブチルカルビトール及びブチルカルビトールアセテートからなる群より選択される少なくとも一種を含む、請求項1~請求項6のいずれか一項に記載のバリア層形成用組成物。
- 25℃における粘度が、10Pa・s~80Pa・sである、請求項1~請求項8のいずれか一項に記載のバリア層形成用組成物。
- 半導体基板と、
前記導体基板上に付与された、請求項1~請求項9のいずれか一項に記載のバリア層形成用組成物の乾燥体であるバリア層と、
を有するバリア層付き半導体基板。 - 請求項1~請求項9のいずれか一項に記載のバリア層形成用組成物を半導体基板上に付与してパターン状のバリア層を形成する工程と、
前記半導体基板上の前記バリア層が形成されていない部分に、ドナー元素又はアクセプター元素を拡散して、前記半導体基板内に部分的に拡散層を形成する工程と、
を含む、太陽電池用基板の製造方法。 - 前記バリア層形成用組成物を前記半導体基板に付与する方法が、スクリーン印刷法である、請求項11に記載の太陽電池用基板の製造方法。
- 請求項11又は請求項12に記載の製造方法により得られる太陽電池用基板の拡散層の上に、電極を形成する工程を含む、太陽電池素子の製造方法。
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JP2015500268A JP6447493B2 (ja) | 2013-02-12 | 2014-02-12 | バリア層形成用組成物、バリア層付き半導体基板、太陽電池用基板の製造方法及び太陽電池素子の製造方法 |
KR1020157018527A KR20150117644A (ko) | 2013-02-12 | 2014-02-12 | 배리어층 형성용 조성물, 배리어층을 갖는 반도체 기판, 태양 전지용 기판의 제조 방법 및 태양 전지 소자의 제조 방법 |
CN201480006954.1A CN104969364A (zh) | 2013-02-12 | 2014-02-12 | 阻挡层形成用组合物、带有阻挡层的半导体基板、太阳能电池用基板的制造方法以及太阳能电池元件的制造方法 |
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Cited By (3)
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KR101921328B1 (ko) | 2016-07-23 | 2018-11-22 | (주)디엔에프 | 반사방지용 코팅 조성물 |
US10749047B2 (en) | 2016-09-29 | 2020-08-18 | Kyocera Corporation | Solar cell element and method for manufacturing solar cell element |
JP2021170641A (ja) * | 2020-04-16 | 2021-10-28 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | シリカ膜形成用組成物、該組成物を用いて製造されたシリカ膜、およびシリカ膜を含む電子素子 |
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CN105355721B (zh) * | 2015-12-09 | 2017-09-29 | 苏州徕士达新材料科技有限公司 | 一种太阳能电池扩散阻挡隔离层的合成制备方法 |
JP2020180274A (ja) * | 2019-04-23 | 2020-11-05 | 住友化学株式会社 | 混合組成物 |
CN117148481B (zh) * | 2023-11-01 | 2023-12-29 | 南通创亿达新材料股份有限公司 | 一种增亮型光学板制备方法 |
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WO2011145521A1 (ja) * | 2010-05-21 | 2011-11-24 | シャープ株式会社 | 半導体装置および半導体装置の製造方法 |
WO2012105163A1 (ja) * | 2011-01-31 | 2012-08-09 | 東京応化工業株式会社 | ケイ素含有膜形成組成物、不純物拡散層の形成方法および太陽電池 |
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Publication number | Priority date | Publication date | Assignee | Title |
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KR101921328B1 (ko) | 2016-07-23 | 2018-11-22 | (주)디엔에프 | 반사방지용 코팅 조성물 |
US10749047B2 (en) | 2016-09-29 | 2020-08-18 | Kyocera Corporation | Solar cell element and method for manufacturing solar cell element |
JP2021170641A (ja) * | 2020-04-16 | 2021-10-28 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | シリカ膜形成用組成物、該組成物を用いて製造されたシリカ膜、およびシリカ膜を含む電子素子 |
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JPWO2014126117A1 (ja) | 2017-02-02 |
TW201434884A (zh) | 2014-09-16 |
CN104969364A (zh) | 2015-10-07 |
KR20150117644A (ko) | 2015-10-20 |
JP6447493B2 (ja) | 2019-01-09 |
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