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WO2013111840A1 - Liquide d'application pour formation de couche anti-diffusion, procédé de fabrication de substrat semi-conducteur avec couche de diffusion de dopant mettant en œuvre ce liquide d'application, et procédé de fabrication de batterie solaire - Google Patents

Liquide d'application pour formation de couche anti-diffusion, procédé de fabrication de substrat semi-conducteur avec couche de diffusion de dopant mettant en œuvre ce liquide d'application, et procédé de fabrication de batterie solaire Download PDF

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Publication number
WO2013111840A1
WO2013111840A1 PCT/JP2013/051529 JP2013051529W WO2013111840A1 WO 2013111840 A1 WO2013111840 A1 WO 2013111840A1 JP 2013051529 W JP2013051529 W JP 2013051529W WO 2013111840 A1 WO2013111840 A1 WO 2013111840A1
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Prior art keywords
diffusion
layer
forming
semiconductor substrate
coating solution
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English (en)
Japanese (ja)
Inventor
勝間　勝彦
佐藤　弘章
加藤　邦泰
由佳 堤
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Mitsubishi Chemical Corp
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Nippon Synthetic Chemical Industry Co Ltd
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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
    • H01L21/228—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 liquid phase, e.g. alloy diffusion processes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • 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
    • 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 coating solution for forming an anti-diffusion layer that is applied to the surface of a semiconductor substrate to prevent dopant diffusion, a method for producing a semiconductor substrate with a dopant diffusion layer using the same, and a method for producing a solar cell. .
  • a pn junction solar cell has a structure in which a p-type semiconductor and an n-type semiconductor are joined. Then, photoelectrons are generated by the light striking the joint surface (internal photoelectric effect), and the photoelectrons move in a certain direction due to the rectifying action of the semiconductor. ) Can be obtained.
  • a dopant such as phosphorus or boron is diffused on one surface of the semiconductor substrate, and a p-type or n-type semiconductor is used depending on the type of the dopant.
  • a method for forming a layer is widely used.
  • a diffusion prevention layer is formed on the semiconductor substrate surface in advance, and after the diffusion of the dopant A technique of removing the diffusion preventing layer has been studied.
  • the diffusion prevention layer can be formed by printing an organic solvent-based solution containing metal oxide fine particles such as titanium oxide and aluminum oxide by screen printing or the like, or by spin coating or the like. (See Patent Documents 1 and 2).
  • the organic solvent-based anti-diffusion layer forming solution as described above has insufficient dispersibility of the metal oxide fine particles, so that the anti-diffusion layer formed thereby has poor uniformity of anti-diffusion performance.
  • the coating by spin coating is difficult to form a coating having a uniform thickness when performed over a wide range, the solution for forming a diffusion preventing layer having poor uniformity of the diffusion preventing performance as described above is applied to this coating method. It is unsuitable.
  • the present invention has been made in view of such circumstances, a coating liquid for forming an anti-diffusion layer having high uniformity of anti-diffusion performance and excellent coating film formation by screen printing, etc., and a dopant using the same
  • the object is to provide a method for producing a semiconductor substrate with a diffusion layer and a method for producing a solar cell.
  • the present invention provides a coating solution for forming a diffusion prevention layer for preventing diffusion of a dopant by coating on the surface of a semiconductor substrate, comprising the following components (A) and (B):
  • the coating liquid for forming the diffusion preventing layer is a first gist.
  • A Polyvinyl alcohol resin.
  • B Metal oxide fine particles.
  • the present invention also includes a step of coating the part of the surface of the semiconductor substrate with the coating liquid for forming the diffusion prevention layer according to the first aspect to form a diffusion prevention layer, and the surface of the semiconductor substrate with the diffusion prevention layer.
  • the manufacturing method of the semiconductor substrate with a dopant diffusion layer provided is a second gist.
  • the diffusion-preventing layer-forming coating solution according to the first aspect is applied so as to cover the application surface, and diffusion is performed.
  • a step of forming a prevention layer, a heat treatment, a step of diffusing the dopant in the applied dopant diffusion solution into the surface layer portion of the semiconductor substrate to form a dopant diffusion layer, and formation of the dopant diffusion layer A method for producing a semiconductor substrate with a dopant diffusion layer, comprising a step of removing a diffusion preventing layer from the semiconductor substrate thus formed, is a third gist.
  • this invention is a manufacturing method of the solar cell provided with the semiconductor substrate with a dopant diffusion layer, Comprising: The manufacturing method of the solar cell which forms the said semiconductor substrate with a dopant diffusion layer by the manufacturing method of the said 2nd or 3rd summary. This is the fourth gist.
  • the present inventors have conducted intensive research to solve the above problems.
  • the present inventors recalled a coating solution containing a polyvinyl alcohol resin (A component) together with metal oxide fine particles (B component) as a solution for forming a diffusion prevention layer.
  • a component polyvinyl alcohol resin
  • B component metal oxide fine particles
  • the presence of the polyvinyl alcohol resin in the coating liquid has led to excellent dispersibility of the metal oxide fine particles, and thus the uniformity of the anti-diffusion performance is increased, and the intended purpose can be achieved.
  • the present invention has been reached.
  • the diffusion-preventing layer forming coating solution of the present invention contains a polyvinyl alcohol resin (component A) and metal oxide fine particles (component B). Therefore, the uniformity of the anti-diffusion performance is high, and the coating film formability by screen printing or the like is excellent. Further, the diffusion preventing layer made of the coating solution can be easily removed by washing with hydrofluoric acid (HF).
  • HF hydrofluoric acid
  • a step of forming a diffusion prevention layer by applying a coating solution for forming a diffusion prevention layer on a part of the surface of the semiconductor substrate, and a diffusion of a dopant on the surface of the semiconductor substrate with the diffusion prevention layer, the diffusion prevention layer A method for producing a semiconductor substrate with a dopant diffusion layer, comprising: a step of forming a surface layer portion of a semiconductor substrate in which no dopant is formed as a dopant diffusion layer; and a step of removing the diffusion prevention layer from the semiconductor substrate on which the dopant diffusion layer is formed.
  • the coating solution for forming a diffusion preventing layer of the present invention containing a polyvinyl alcohol resin (component A) and fine metal oxide particles (component B) is used as the coating solution for forming the diffusion preventing layer, the portion other than the desired portion
  • the dopant diffusion layer can be effectively formed on the semiconductor substrate while preventing the diffusion of the dopant into the semiconductor substrate.
  • a diffusion prevention layer forming coating solution so as to cover the coating surface, forming a diffusion prevention layer, and heat treatment.
  • a process for producing a semiconductor substrate with a dopant diffusion layer comprising: a polyvinyl alcohol-based resin (component A) and metal oxide fine particles (component B) as the diffusion-preventing layer forming coating solution.
  • Using a diffusion barrier layer forming coating solution effectively forms a dopant diffusion layer on a semiconductor substrate while preventing diffusion of the dopant to other than the desired location. It can be.
  • the solar cell can be efficiently manufactured.
  • the coating solution for forming the diffusion preventing layer of the present invention contains a polyvinyl alcohol resin (hereinafter abbreviated as “PVA resin”) (A component) and metal oxide fine particles (B component). Moreover, as the solvent, water is mainly used and alcohol is used together as needed. Thus, since the coating liquid for forming the diffusion preventing layer of the present invention is water-based, it is different from conventional organic solvent-based coating solutions. Hereinafter, each of these materials will be described.
  • PVA resin polyvinyl alcohol resin
  • B component metal oxide fine particles
  • the PVA resin used in the coating solution for forming the diffusion prevention layer of the present invention has a saponification degree (measured in accordance with JIS K 6726) of usually 60 to 100 mol%, preferably 70 to 99.9. Those having a mol%, more preferably 80 to 99.9 mol%, particularly preferably 90 to 99.9 mol%, still more preferably 97 to 99.8 mol% are used. That is, if the degree of saponification is too low, the solubility of the PVA-based resin in water decreases, and it may be difficult to obtain a uniform coating solution.
  • the average polymerization degree (measured in accordance with JIS K 6726) of the PVA resin is usually 100 to 8000, preferably 100 to 4000, more preferably 200 to 2000, and still more preferably 250. Those of ⁇ 1500 are used. That is, if the average degree of polymerization is too small, the coating solution becomes low in viscosity, so that the coating film becomes a thin film, and the dispersibility of the metal oxide fine particles is insufficient, so that sufficient diffusion preventing performance can be obtained. This is because, on the contrary, when the average degree of polymerization is too large, the coatability tends to be lowered.
  • the PVA resin used for the coating solution for forming the diffusion preventing layer may be unmodified polyvinyl alcohol or various known modified polyvinyl alcohols. These may be used alone or in combination of two or more.
  • R 1 to R 3 and R 4 to R 6 in the general formula are all hydrogen.
  • R 1 to R 3 and R 4 to R 6 may be organic groups as long as they do not significantly impair the resin characteristics.
  • the organic group include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
  • the said organic group may have functional groups, such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, and a sulfonic acid group, as needed.
  • X in the 1,2-diol structural unit represented by the general formula (1) is most preferably a single bond in terms of thermal stability and stability under high temperature and acidic conditions. preferable. However, a binding chain may be used as long as the effect of the present invention is not impaired.
  • linking chain examples include hydrocarbons such as alkylene, alkenylene, alkynylene, phenylene and naphthylene (these hydrocarbons may be substituted with halogen such as fluorine, chlorine and bromine), -O-, — (CH 2 O) m —, — (OCH 2 ) m —, — (CH 2 O) m CH 2 —, —CO—, —COCO—, —CO (CH 2 ) m CO—, —CO (C 6 H 4 ) CO—, —S—, —CS—, —SO—, —SO 2 —, —NR—, —CONR—, —NRCO—, —CSNR—, —NRCS—, —NRNR—, —HPO 4 -, - Si (OR) 2 -, - OSi (OR) 2 -, - OSi (OR) 2 O -, - Ti (OR) 2 -, - OT
  • an alkylene group having 6 or less carbon atoms, particularly a methylene group, or —CH 2 OCH 2 — is preferable from the viewpoint of stability during production or use.
  • the production method of the PVA resin used in the coating solution for forming the diffusion preventing layer of the present invention is not particularly limited.
  • a co-polymer of a vinyl ester monomer and a compound represented by the following general formula (2) A method of saponifying a polymer, (ii) a method of saponifying and decarboxylating a copolymer of a vinyl ester monomer and a compound represented by the following general formula (3), and (iii) a vinyl ester monomer
  • a method of saponifying and deketalizing a copolymer with a compound represented by the following general formula (4) is preferably used.
  • R 1 to R 6 and X are all the same as those in the general formula (1).
  • R 7 and R 8 are each independently a hydrogen atom or R 9 —CO— (wherein R 9 is an alkyl group having 1 to 4 carbon atoms).
  • R 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the compound represented by the general formula (2) is 3, from the viewpoint of excellent copolymerization reactivity and industrial handleability.
  • 4-diasiloxy-1-butene is preferably used, and 3,4-diacetoxy-1-butene is particularly preferably used.
  • each of the copolymerized copolymer with 3,4-diacetoxy-1-butene is used.
  • 3,4-diacetoxy-1-butene is a by-product generated during saponification of the copolymer, and is a by-product generated during the saponification from a structural unit derived from vinyl acetate that is frequently used as a vinyl ester monomer. Is the same as Therefore, it is not necessary to provide a special apparatus or process for the post-treatment or solvent recovery system, and it is an industrially significant advantage that conventional equipment can be used.
  • 3,4-diacetoxy-1-butene can be synthesized, for example, by an epoxy butene derivative described in WO 00/24702, USP 5,623,086, USP 6,072,079, 1,4-diacetoxy-1-butene, which is an intermediate product in the diol production process, can be produced by isomerization using a metal catalyst such as palladium chloride. At the reagent level, Across products can be obtained from the market.
  • the PVA resin obtained by the method (ii) or (iii) is insufficiently decarboxylated or deacetalized, a carbonate ring or an acetal ring remains in the side chain.
  • the PVA resin obtained by the method (i) is preferably used in the present invention.
  • vinyl ester monomers used in the methods (i) to (iii) include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, and vinyl caprate. Vinyl laurate, vinyl stearate, vinyl benzoate, vinyl versatate, etc., and vinyl acetate is preferably used economically.
  • copolymer component examples include ⁇ -olefins such as ethylene and propylene; hydroxy group-containing ⁇ such as 3-buten-1-ol, 4-penten-1-ol, and 5-hexene-1,2-diol.
  • -Derivatives such as olefins and acylated products and esterified products thereof; unsaturated acids such as itaconic acid, maleic acid and acrylic acid, or salts or mono- or dialkyl esters thereof; nitriles such as acrylonitrile, methacrylamide, diacetone acrylamide, etc.
  • AMPS acrylamido-2-methylpropane sulfonic acid
  • the content of 1,2-diol structural units contained in the PVA resin in the coating solution for forming the diffusion preventing layer of the present invention is preferably 0.5 to 30 mol%, more preferably 1 to 20 It is in the range of mol%, more preferably 3 to 15 mol%. That is, if the content is too low, the effect of using a PVA resin into which a 1,2-diol structural unit is introduced tends to be too low. On the other hand, if the content is too high, the drying property is lowered and the productivity is lowered. Because there is a tendency to.
  • the content of the 1,2-diol structural unit in the PVA resin was determined by 1 H-NMR spectrum (solvent: DMSO-d6, internal standard substance: tetramethylsilane) of a completely saponified PVA resin. Specifically, from the peak area derived from the hydroxyl proton, methine proton, and methylene proton in the 1,2-diol unit, methylene proton in the main chain, hydroxyl proton linked to the main chain, etc. What is necessary is just to calculate.
  • the content of the PVA resin in the coating solution for forming the diffusion preventing layer of the present invention is usually 1 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight. That is, if the content of the PVA-based resin is too small, the viscosity of the coating liquid tends to be low, and the coating film tends to be difficult to be formed stably. Conversely, if the content is too large, the viscosity of the coating liquid increases. For this reason, the coating workability is likely to be lowered, and further, when screen printing is performed, the screen mesh tends to be clogged.
  • metal oxide fine particles In the coating liquid for forming the diffusion preventing layer of the present invention, metal oxide fine particles are blended together with the PVA resin.
  • the metal oxide species of the fine particles is at least one selected from Group 4 metal oxides, Group 5 metal oxides, and Group 13 metal oxides of the Periodic Table. Specifically, periodic table group 4 metal oxides such as titanium oxide and zirconium oxide, periodic table group 5 metal oxides such as vanadium oxide, niobium oxide, and tantalum oxide, and periodic periods such as aluminum oxide and gallium oxide. Table 13 Group 13 metal oxides. These may be used alone or in combination of two or more.
  • metal oxides of Group 4 and Group 13 of the periodic table are preferable, and aluminum oxide and titanium oxide are particularly preferable.
  • metal oxide fine particles that are amphoteric oxides are preferred, and fine particles made of aluminum oxide are more preferred.
  • the metal oxide fine particles have an average primary particle size of usually 1 to 500 nm, preferably 3 to 200 nm, particularly preferably 3 to 50 nm, and particularly preferably 3 to 20 nm.
  • the average primary particle size is a value calculated from the BET specific surface area of the metal oxide fine particles.
  • a plurality of metal oxide fine particles having different average primary particle sizes can be used.
  • the average primary particle size is relatively small (for example, the average primary particle size is 1 to 50 nm, preferably 1 to 20 nm), and the average primary particle size is relatively large (for example, the average primary particle size is more than 50 to 500 nm, preferably Are used at the same time, it is possible to reduce the gaps between the metal oxide fine particles in the coating film after coating the coating solution, thereby improving the uniformity of the coated surface.
  • the content of the metal oxide fine particles in the coating solution for forming the diffusion preventing layer of the present invention is usually 0 in terms of the total amount of metal oxide fine particles, even when a plurality of fine particles having different average primary particle sizes are contained. 0.1 to 40% by weight, preferably 0.5 to 35% by weight, more preferably 0.8 to 30% by weight, still more preferably 5 to 30% by weight, and particularly preferably 10 to 30% by weight. is there.
  • the content of the metal oxide fine particles with respect to 100 parts by weight of the PVA resin is usually 0.05 to 200 parts by weight, preferably 10 to 180 parts by weight, more preferably 30 to 150 parts by weight, particularly preferably. Is in the range of 50 to 120 parts by weight.
  • the content of the metal oxide fine particles is too small, the desired anti-diffusion performance cannot be obtained. Conversely, if the content of the metal oxide fine particles is too large, the coating property and the like are hindered. This is because it comes to come.
  • water is used as the solvent.
  • water used for the said coating liquid for diffusion prevention layer formation what has few impurities, such as an alkali metal and a heavy metal, and a foreign material is preferable, Usually, total organic carbon (henceforth TOC) may be 50 ppb or less, Preferably, it is 10 ppb or less, and the electrical resistivity is usually 16 M ⁇ ⁇ cm or more, preferably 17 M ⁇ ⁇ cm or more, more preferably 18 M ⁇ ⁇ cm or more. Ultrapure water is most preferable, but ion-exchanged water or distilled water can also be used.
  • the water content in the coating solution for forming the diffusion preventing layer of the present invention is usually 10 to 80% by weight, preferably 15 to 75% by weight, more preferably 20 to 70% by weight, and particularly preferably 20 to 50% by weight. % Range. That is, if the water content is too small, the viscosity of the coating solution becomes too high, the coating workability tends to be lowered, and further, when screen printing is performed, the screen mesh tends to be clogged. This is because, if the amount is too large, the viscosity becomes too low to form a coating film stably.
  • the diffusion-preventing layer forming coating liquid of the present invention contains a PVA-based resin, metal oxide fine particles, and water as a solvent.
  • PVA-based resin a polyvinyl alcohol
  • metal oxide fine particles metal oxide fine particles
  • water a solvent
  • other materials such as known general alcohols, surfactants, inorganic fine particles and the like can be further blended.
  • the storage stability and flow stability of the coating solution and the leveling property of the coating film can be improved.
  • the alcohols include monohydric alcohols such as methanol (65 ° C.), ethanol (78 ° C.), and isopropanol (82 ° C.); ethylene glycol (197 ° C.), diethylene glycol (244 ° C.), triethylene Dihydric alcohols such as glycol (287 ° C.), tetraethylene glycol (314 ° C.), propylene glycol (188 ° C.); glycerin (290 ° C.), trimethylolpropane (292 ° C.), sorbitol (296 ° C.), mannitol (290) ⁇ 295 ° C.), pentaerythritol (276 ° C.), trihydric or higher polyhydric alcohols such as polyglycerin; and ethylene glycol monomethyl ether (124 ).
  • alcohols having a boiling point higher than that of water that is, alcohols having a boiling point of 100 to 350 ° C.
  • the boiling point is 150 to 350 ° C.
  • the boiling point is 190 to 300 ° C. This is because when the boiling point is too high, there is a tendency to require drying at a high temperature for a long time when alcohols are used.
  • the blending amount is usually 5 to 70 parts by weight, preferably 10 to 60 parts by weight, more preferably based on the total amount of the coating solution. Is in the range of 30 to 50 parts by weight.
  • the blending amount of the alcohol with respect to 100 parts by weight of water is usually 5 to 200 parts by weight, preferably 20 to 170 parts by weight, more preferably 80 to 150 parts by weight. That is, if the content of such alcohols is too small, the fluidity improving effect and the leveling effect cannot be obtained sufficiently. On the other hand, if the content is too large, the solubility of the PVA resin is lowered and a uniform coating solution is obtained. This is because it tends to be difficult to be made.
  • surfactants used in the coating solution can be broadly classified into nonionic surfactants, cationic surfactants, and anionic surfactants, and any of them can be used. Of these, nonionic surfactants are preferred because they are less likely to bring metal components into the semiconductor.
  • nonionic surfactant examples include hydrocarbon surfactants such as ethylene oxide-propylene oxide block copolymers and acetylene glycol derivatives, silicon surfactants, and fluorine surfactants.
  • hydrocarbon surfactants particularly acetylene glycol derivatives, are preferably used in the coating solution for forming the diffusion preventing layer because they are excellent in suppressing foaming and defoaming.
  • acetylene glycol derivative those represented by the following general formula (5) are preferably used.
  • R 12 and R 15 in the general formula (5) each independently represents an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, more preferably 3 to 5 carbon atoms. It is an alkyl group.
  • R 13 and R 14 each independently represents an alkyl group having 1 to 3 carbon atoms, and a methyl group is particularly preferred.
  • R 12 and R 15 , and R 13 and R 14 may be the same or different, but those having the same structure are preferably used.
  • n and m are integers from 0 to 30, respectively.
  • m + n is preferably 1 to 10, more preferably m + n is 1 to 5, and still more preferably m + n is 1 to 3.
  • acetylene glycol derivative examples include 2,5,8,11-tetramethyl-6-dodecin-5,8-diol ethylene oxide adduct, 5,8-dimethyl-6-dodecin-5, 8-diol ethylene oxide adduct, 2,4,7,9-tetramethyl-5-decyne-4,7diol ethylene oxide adduct, 4,7-dimethyl-5-decyne-4,7-diol Ethylene oxide adduct, 2,3,6,7-tetramethyl-4-octyne-3,6diol ethylene oxide adduct, 3,6-dimethyl-4-octyne-3,6-diol ethylene oxide adduct 2,5-dimethyl-3-hexyne-2,5-diol ethylene oxide adduct and the like.
  • acetylene glycol derivatives examples include the Surfinol series manufactured by Nissin Chemical Industry.
  • the amount is usually 0.01 to 10% by weight, preferably 0.1 to 8%, based on the total amount of the coating solution. % By weight, more preferably in the range of 0.3 to 5% by weight. That is, if the amount of such a surfactant is too small, the anti-foaming / defoaming effect tends to be low, and conversely if too large, it tends to be difficult to obtain a uniform solution by separating from the liquid. Because.
  • various inorganic fine particles other than the metal oxide fine particles can be blended for the purpose of improving screen printing characteristics and the like.
  • silicas such as colloidal silica, amorphous silica, and fumed silica are preferable, and colloidal silica is more preferably used.
  • the blending amount of such inorganic fine particles is usually 0.5 to 20% by weight, preferably 1 to 10% by weight in the coating solution.
  • the diffusion-preventing layer-forming coating solution of the present invention contains a PVA-based resin, metal oxide fine particles, and water as a solvent. Other materials such as an activator and inorganic fine particles are further blended.
  • a preparation method of the said coating liquid after making PVA resin into aqueous solution, for example, the method of mix
  • the coating property resulting from the uniformity of the solution Printing stability can be obtained.
  • conventional organic solvent-based anti-diffusion layer-forming solutions have insufficient dispersibility of metal oxide fine particles, and thus there is a problem that it is difficult to form a uniform-thickness coating film particularly by spin coating.
  • the solvent easily volatilizes, when continuous printing is performed by screen printing or the like, there has been a problem that printing tends to become unstable.
  • these can be solved by the above method.
  • Examples of a method for obtaining a semiconductor substrate with a dopant diffusion layer by forming a dopant diffusion layer on the surface of the semiconductor substrate using the coating solution for forming the diffusion prevention layer include the following methods (I) and (II): can give.
  • a semiconductor substrate with a dopant diffusion layer is manufactured by a step of making a surface layer portion of a semiconductor substrate on which no layer is formed a dopant diffusion layer and a step of removing the diffusion prevention layer from the semiconductor substrate on which the dopant diffusion layer is formed.
  • FIG. 1 specifically shows the manufacturing process shown in (I), which is performed in the order of (i) to (iv).
  • (i) shows a state in which a diffusion prevention layer forming coating solution is applied to one surface of a semiconductor substrate 1 to form a diffusion prevention layer 3
  • (ii) shows the atmosphere of a dopant gas
  • a dopant gas For example, a state in which a dopant gas is brought into contact with the surface of the semiconductor substrate 1 with the diffusion prevention layer 3 filled with phosphorus oxychloride (POCl 3 ) gas or boron tribromide (BBr 3 ) gas
  • POCl 3 phosphorus oxychloride
  • BBr 3 boron tribromide
  • FIG. 2 specifically shows the manufacturing process shown in (II), which is performed in the order of (i) to (iv) shown in the figure.
  • (i) shows a state in which a dopant diffusion solution is applied to one surface of the semiconductor substrate 1 to form dopant solution application layers 2a and 2b
  • (ii) shows the application of the dopant solution.
  • the diffusion preventing layer forming coating solution is applied so as to cover the layers 2a and 2b, and the diffusion preventing layer 3 is formed.
  • (Iii) is a heat treatment, and the dopant solution coating layer 2a, The dopant in 2b is diffused in the surface layer portion of the semiconductor substrate 1 to form the dopant diffusion layers 11a and 11b.
  • the diffusion preventing layer 3 prevents the dopant in the dopant diffusion layers 11a and 11b from being used only for forming the dopant diffusion layers 11a and 11b.
  • Iv shows a state in which the diffusion preventing layer 3 is removed from the semiconductor substrate 1 on which the dopant diffusion layers 11a and 11b are formed.
  • the heat treatment in the production process shown in (II) above means the following drying process, firing process, and diffusion process.
  • volatile components such as water are removed from the coating layer.
  • the conditions may be set as appropriate, but are usually 1 to 60 minutes, particularly 5 to 30 minutes under a temperature condition of 20 to 300 ° C., particularly 100 to 200 ° C.
  • the drying method is not particularly limited, and the drying is performed by a known method such as hot air drying, infrared heat drying, or vacuum drying.
  • the volatile components in the coating layer are removed using an electric furnace or the like.
  • the conditions of such a process need to be adjusted as appropriate depending on the composition of the solution and the thickness of the coating layer, but are usually 300 to 1000 ° C., particularly 400 to 800 ° C., 1 to 120 minutes, particularly 5 to 60 minutes Will be implemented in the time.
  • the dopant is further diffused in the semiconductor substrate in the diffusion step, and a diffusion layer is formed.
  • an electric furnace or the like is used in the same manner as in the firing step, and is performed under a temperature condition of 800 to 1400 ° C., in a state of single wafers or a plurality of stacked sheets.
  • Examples of the semiconductor substrate 1 used in the manufacturing method shown in the above (I) and (II) include those made of single crystal or polycrystalline p-type silicon, those made of single crystal or polycrystalline n-type silicon, gallium A material made of doped p-type or n-type silicon is used.
  • the semiconductor substrate 1 may be manufactured by any one of the Czochralski (CZ) method and the float zone (FZ) method.
  • CZ Czochralski
  • FZ float zone
  • various coating methods such as spin coating, spraying, offset printing, and screen printing can be used as the coating method of the coating solution for forming the diffusion preventing layer of the present invention.
  • screen printing is preferable because it is easy to form a uniform coating film in a wide range, and since the coating solution is water-based, there is an advantage that printing is not easily destabilized even if continuous printing is performed. .
  • the dopant may be diffused by a method of applying a dopant diffusion solution in addition to a method of diffusing the dopant by gas contact.
  • a dopant diffusion solution for example, an aqueous solution of phosphoric acid or boric acid is used for this solution.
  • water-soluble compounds such as phosphoric acids and boric acids are used for the dopant diffusion solution used in the method shown in (II) above.
  • the dopant diffusing solution may be blended with materials such as PVA resins, alcohols, surfactants, inorganic fine particles, and the like from the viewpoints of coating properties, forming properties of the dopant solution coating layer, and the like.
  • various coating methods such as a spin coat method, offset printing, and screen printing, are normally applied.
  • an immersion treatment in hydrofluoric acid (HF) is performed.
  • hydrofluoric acid is usually used as an aqueous solution of 3 to 50% by weight, and for the purpose of improving the treatment efficiency, the immersion treatment is heated or irradiated with ultrasonic waves. This is also a preferred embodiment.
  • the dopant glass (phosphorus glass, boron glass, etc.) formed on the surface of the dopant diffusion layer is also removed by the immersion treatment in hydrofluoric acid.
  • the immersion treatment in a basic liquid may be performed.
  • the basic liquid include a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution.
  • the concentration of the basic liquid is usually 0.1 to 10% by weight in terms of workability, and preferably 0.02 to 5% by weight, particularly preferably in terms of preventing excessive etching of the substrate surface. 0.2 to 1% by weight.
  • the working temperature is preferably 50 ° C. or less, more preferably room temperature, specifically 20 to 30 ° C. in terms of preventing excessive etching of the substrate surface.
  • the immersion time in the basic liquid is preferably 5 minutes or less, more preferably 1 minute or less in terms of preventing excessive etching of the substrate surface.
  • the solar cell provided with the semiconductor substrate with the dopant diffusion layer
  • the semiconductor substrate with the dopant diffusion layer is formed by the method as shown in the above (I) and (II)
  • the solar cell is efficiently produced. Can be manufactured.
  • the semiconductor substrate with a dopant diffused layer manufactured by the method as shown to said (I) and (II) has a favorable pn junction structure, generation
  • the semiconductor device include a solar cell, a diode, and a transistor.
  • ultrapure water means water having a TOC of 1.0 ppb or less and an electrical resistivity of 18.2 M ⁇ ⁇ cm.
  • unmodified PVA (a) (saponification degree 78 mol%, average polymerization degree 1400) and modified PVA (a) (saponification degree 98.9 mol%, average polymerization degree 350).
  • modified PVA (a) having a modification degree of 8 mol%.
  • the modified PVA (a) was produced as follows.
  • the methanol solution was further diluted with methanol, adjusted to a concentration of 40%, charged into a kneader, and a 2% methanol solution of sodium hydroxide was added to the vinyl acetate structural unit in the copolymer while maintaining the solution temperature at 40 ° C.
  • saponification was carried out by adding 8 mmol with respect to 1 mol of the total amount of 3,4-diacetoxy-1-butene structural units. As saponification progressed, when saponified substances were precipitated and became particulate, they were separated by filtration, washed well with methanol and dried in a hot air dryer to obtain the desired modified PVA (a).
  • the degree of saponification of the obtained modified PVA (a) was 98.9 mol% when analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and 3,4-diacetoxy-1-butene.
  • the average degree of polymerization was 350 when analyzed according to JIS K 6726.
  • the content of the 1,2-diol structural unit represented by the general formula (1) is 1 H-NMR (300 MHz proton NMR, DMSO-d6 solution, internal standard substance: tetramethylsilane, 50 ° C.). It was 8 mol% when it computed from the integrated value measured in this way.
  • Example 1 ⁇ Preparation of coating solution ( ⁇ ) for forming diffusion preventing layer> 22 parts of modified PVA (a) was added to 36.5 parts of ultrapure water, and dissolved while stirring under heating to prepare a solution ( ⁇ 1). Further, 40 parts of glycerin, ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol as a surfactant (Shinfin Chemical 420, Surfynol 420) 5 parts were added to prepare a solution ( ⁇ 2).
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ , whereas the surface resistance of the surface on which the coating solution for forming the diffusion preventing layer was applied. was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • Example 2 Same as Example 1, except that 31.5 parts of ultrapure water was used in the coating solution ( ⁇ ) for forming the diffusion preventing layer used in Example 1, ethylene glycol was used instead of glycerin, and 6.0 parts of aluminum oxide fine particles were used. Thus, a water-based anti-diffusion layer forming coating solution was prepared. Then, “application to semiconductor substrate”, “diffusion”, and “measurement of surface resistance value” were performed in the same manner as in Example 1 except that this coating solution for forming the diffusion prevention layer was used.
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ , whereas the surface resistance of the surface on which the coating solution for forming the diffusion preventing layer was applied. was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • Example 3 In the coating liquid ( ⁇ ) for forming the diffusion preventing layer used in Example 1, the above-mentioned unmodified PVA (a) (saponification degree 78 mol%, average polymerization degree 1400) was used instead of the modified PVA (a). Then, a coating solution for forming a diffusion preventing layer was prepared. Then, “application to semiconductor substrate”, “diffusion”, and “measurement of surface resistance value” were performed in the same manner as in Example 1 except that this coating solution for forming the diffusion prevention layer was used.
  • the above-mentioned unmodified PVA (a) (saponification degree 78 mol%, average polymerization degree 1400) was used instead of the modified PVA (a). Then, a coating solution for forming a diffusion preventing layer was prepared. Then, “application to semiconductor substrate”, “diffusion”, and “measurement of surface resistance value” were performed in the same manner as in Example 1 except that this coating solution for forming the diffusion prevention layer was used.
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ , whereas the surface resistance of the surface on which the coating solution for forming the diffusion preventing layer was applied.
  • the surface resistance was 1000 ⁇ / ⁇ . Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • Example 4 In the coating liquid ( ⁇ ) for forming the diffusion preventing layer used in Example 1, the above-mentioned unmodified PVA (a) (saponification degree 78 mol%, average polymerization degree 1400) was used instead of the modified PVA (a).
  • a water-based anti-diffusion layer forming coating solution was prepared in the same manner except that 31.5 parts of ultrapure water was used, ethylene glycol was used instead of glycerin, and 6.0 parts of aluminum oxide fine particles were used. Then, “application to semiconductor substrate”, “diffusion”, and “measurement of surface resistance value” were performed in the same manner as in Example 1 except that this coating solution for forming the diffusion prevention layer was used.
  • Example 5 Using the coating liquid for forming the diffusion prevention layer used in Example 2, “application to a semiconductor substrate” and “diffusion” were performed in the same manner as in Example 1. Thereafter, the obtained semiconductor substrate was immersed in a 46 wt% hydrofluoric acid (HF) aqueous solution for 3 minutes, washed with ultrapure water, and sufficiently dried. Subsequently, as a post-treatment, the semiconductor substrate was immersed in an aqueous NaOH solution (3 wt% (produced with ultrapure water)) for 30 seconds. In this way, after removing the PSG (phosphorus glass) layer and the diffusion prevention layer, washing with ultrapure water and drying at 150 ° C. (10 minutes) were performed (see FIGS. 1 (ii) to (iv)).
  • HF hydrofluoric acid
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the diffusion-preventing layer forming coating solution was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • the aluminum oxide residue after washing was thin and could be washed cleanly.
  • Example 6 Using the coating solution for forming a diffusion preventing layer used in Example 4, “application to a semiconductor substrate” and “diffusion” were performed in the same manner as in Example 1. Thereafter, the obtained semiconductor substrate was immersed in a 46 wt% hydrofluoric acid (HF) aqueous solution for 3 minutes, washed with ultrapure water, and sufficiently dried. Subsequently, as a post-treatment, the semiconductor substrate was immersed in an aqueous NaOH solution (3 wt% (produced with ultrapure water)) for 30 seconds. In this way, after removing the PSG (phosphorus glass) layer and the diffusion prevention layer, washing with ultrapure water and drying at 150 ° C. (10 minutes) were performed (see FIGS. 1 (ii) to (iv)).
  • HF hydrofluoric acid
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the diffusion-preventing layer forming coating solution was 1000 ⁇ / ⁇ . Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • the aluminum oxide residue after washing was thin and could be washed cleanly.
  • Example 7 In Example 5, post-treatment with an aqueous NaOH solution was performed in place of an aqueous KOH solution (3 wt% (prepared with ultrapure water)). Otherwise, “application to semiconductor substrate”, “diffusion”, and “cleaning treatment” were performed in the same manner as in Example 5.
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the diffusion-preventing layer forming coating solution was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • the aluminum oxide residue after washing was thin and could be washed cleanly.
  • Example 8 In Example 6, post-treatment with an aqueous NaOH solution was performed in place of an aqueous KOH solution (3 wt% (prepared with ultrapure water)). Other than that, “application to semiconductor substrate”, “diffusion”, and “cleaning treatment” were performed in the same manner as in Example 6.
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the diffusion-preventing layer forming coating solution was 1000 ⁇ / ⁇ . Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • the aluminum oxide residue after washing was thin and could be washed cleanly.
  • Example 9 titanium oxide (manufactured by Nippon Aerosil Co., Ltd., AEROXIDE TiO 2 P-25, average primary particle size 30 nm) was used in place of aluminum oxide in the coating solution for forming the diffusion prevention layer. Other than that, “application to semiconductor substrate”, “diffusion”, and “cleaning treatment” were performed in the same manner as in Example 7.
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the diffusion-preventing layer forming coating solution was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • the titanium oxide residue after washing was thin and could be washed cleanly.
  • Example 10 18 parts of modified PVA (a) was added to 29.5 parts of ultrapure water and dissolved while stirring under heating to prepare a solution ( ⁇ 1). In addition, 0.5 part of ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Shinfin Chemical Co., Surfynol 420) is added to 40 parts of ethylene glycol. The solution ( ⁇ 2) was prepared by addition.
  • the obtained semiconductor substrate was immersed in a 46 wt% hydrofluoric acid (HF) aqueous solution for 3 minutes, washed with ultrapure water, and sufficiently dried. Subsequently, as a post-treatment, the semiconductor substrate was immersed in a KOH aqueous solution (3 wt% (produced with ultrapure water)) for 30 seconds. In this way, after removing the PSG (phosphorus glass) layer and the diffusion prevention layer, washing with ultrapure water and drying at 150 ° C. (10 minutes) were performed (see FIGS. 1 (ii) to (iv)).
  • HF hydrofluoric acid
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the coating solution for forming the diffusion preventing layer was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate. In addition, the aluminum oxide residue after washing was thin and could be washed cleanly.
  • Example 11 In the coating solution ( ⁇ ) for forming the diffusion preventing layer used in Example 10, the amount of ultrapure water was 28.5 parts, the amount of ethylene glycol was 35 parts, and Tymicron TM-300 as aluminum oxide fine particles. And 12.0 parts of Tymicron TM-DA (manufactured by Daimei Chemical Industries, BET specific surface area 13.5 m 2 / g, average primary particle size 100 nm). Other than that was carried out similarly to Example 10, and performed "application
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the coating solution for forming the diffusion preventing layer was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate. In addition, the aluminum oxide residue after washing was thin and could be washed cleanly.
  • Example 12 In the coating solution for forming an anti-diffusion layer used in Example 11, the amount of Tymicron TM-300 was 12.0 parts, and the amount of Tymicron TM-DA was 6.0 parts. Other than that was carried out similarly to Example 11, and performed "application
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the coating solution for forming the diffusion preventing layer was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate. In addition, the aluminum oxide residue after washing was thin and could be washed cleanly.
  • Example 13 Using the coating liquid for forming the diffusion preventing layer used in Example 10, screen printing was performed on one side of a semiconductor substrate (p-type single crystal silicon, with alkali etching texture, 156 mm square, 200 ⁇ m thickness) under the following printing conditions. Then, a diffusion preventing layer was formed. Otherwise, “diffusion” and “measurement of surface resistance” were performed in the same manner as in Example 1. (Printing conditions) Printing machine: “LS-34GX” manufactured by Neurong Seimitsu Kogyo Co., Ltd. Squeegee: NM squeegee (Hardness: 60) manufactured by Neurong Precision Industry Co., Ltd.
  • the surface resistance of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇
  • the surface resistance of the surface coated with the coating solution for forming the diffusion preventing layer was It was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • Example 14 After the diffusion preventing layer was formed under the same printing conditions as in Example 13 using the diffusion preventing layer forming coating solution used in Example 10, “diffusion” was performed in the same manner as in Example 1. Thereafter, the obtained semiconductor substrate was immersed in a 46 wt% hydrofluoric acid (HF) aqueous solution for 3 minutes, washed with ultrapure water, and sufficiently dried. Subsequently, as a post-treatment, the semiconductor substrate was immersed in a KOH aqueous solution (0.3 wt% (produced with ultrapure water)) for 30 seconds. In this way, after removing the PSG (phosphorus glass) layer and the diffusion prevention layer, washing with ultrapure water and drying at 150 ° C. (10 minutes) were performed (see FIGS. 1 (ii) to (iv)).
  • HF hydrofluoric acid
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ .
  • the surface resistance of the surface coated with the diffusion-preventing layer forming coating solution was 1000 ⁇ / ⁇ or more. Therefore, it can be seen that the diffusion preventing property by the diffusion preventing layer completely prevents the diffusion of phosphorus to the diffusion preventing layer forming surface of the semiconductor substrate.
  • the aluminum oxide residue after washing was thin and could be washed cleanly.
  • the surface resistance of the surface of the semiconductor substrate after the diffusion treatment on which the coating solution for forming the diffusion preventing layer was not applied was 60 ⁇ / ⁇ , but the surface resistance of the surface to which the coating solution for forming the diffusion preventing layer was applied. Varied between 60 and 1000 ⁇ / ⁇ . Therefore, it can be seen that this diffusion preventing layer could not sufficiently prevent the diffusion of phosphorus.
  • Example 15 ⁇ Preparation of boron diffusion liquid ( ⁇ )> 15 parts of modified PVA (a) was added to 42.5 parts of ultrapure water, and dissolved while heating and stirring to prepare a solution ( ⁇ 1). Also, 0.5 part of 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethylene oxide adduct (Shinfin Chemical Co., Surfinol 420) is added to 40 parts of glycerin. Thus, a solution ( ⁇ 2) was prepared. To this solution ( ⁇ 1), 2.0 parts of boric acid was added, and further the solution ( ⁇ 2) was added and stirred to prepare a boron diffusion solution ( ⁇ ).
  • a solution ( ⁇ 2) was prepared by adding 15 parts of SiO 2 aqueous solution (Fujimi Incorporated, Planerlite 4101, SiO 2 20%, water 80%). To this solution ( ⁇ 1), 2.0 parts of phosphoric acid was added, and further the solution ( ⁇ 2) was added and stirred to prepare a phosphorus diffusion solution ( ⁇ ).
  • Example 1 Thereafter, the coating solution ( ⁇ ) for formation of the diffusion preventing layer used in Example 1 is applied under the same conditions as in Example 1 so as to cover the coated surfaces of the boron diffusion solution ( ⁇ ) and the phosphorus diffusion solution ( ⁇ ).
  • the screen was printed on the entire surface of one side of the semiconductor substrate (see FIG. 2 (ii)).
  • the semiconductor substrate is taken out and immersed in a 46% hydrofluoric acid (HF) aqueous solution (prepared with ultrapure water) for 3 minutes to provide a PSG (phosphorus glass) layer, BSG (boron glass) layer, and diffusion prevention. After removing the layers, washing with ultrapure water and drying at 150 ° C. (10 minutes) were performed (see FIGS. 2 (iii) and (iv)).
  • HF hydrofluoric acid
  • the diffusion preventing layer forming coating liquid used in the examples contains fine particles of aluminum oxide or titanium oxide, and prevents the diffusion of the dopant by the shielding effect of the fine particles. It can be said that the same result can be obtained even if this is a metal oxide fine particle composed of vanadium oxide, niobium oxide, and tantalum oxide.
  • the coating solution for forming the diffusion preventing layer of the present invention is for preventing the diffusion of the dopant by coating it on the surface of the semiconductor substrate, has a high uniformity of the diffusion preventing performance, and can also form a coating film by screen printing or the like. Since it is excellent, it can be used widely and suitably in the field of manufacturing semiconductors and semiconductor devices.

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PCT/JP2013/051529 2012-01-26 2013-01-25 Liquide d'application pour formation de couche anti-diffusion, procédé de fabrication de substrat semi-conducteur avec couche de diffusion de dopant mettant en œuvre ce liquide d'application, et procédé de fabrication de batterie solaire Ceased WO2013111840A1 (fr)

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WO2007020833A1 (fr) * 2005-08-12 2007-02-22 Sharp Kabushiki Kaisha Pâte de masquage, son procédé de production, et procédé de fabrication d’une cellule solaire utilisant cette pâte de masquage
WO2010101054A1 (fr) * 2009-03-02 2010-09-10 シャープ株式会社 Procédé de production de dispositif à semi-conducteur
JP2011029553A (ja) * 2009-07-29 2011-02-10 Sharp Corp 半導体装置の製造方法
JP2011035252A (ja) * 2009-08-04 2011-02-17 Sharp Corp 半導体装置の製造方法
WO2011132744A1 (fr) * 2010-04-23 2011-10-27 シャープ株式会社 Procédé de fabrication de dispositif à semi-conducteur

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TW201331312A (zh) * 2012-01-10 2013-08-01 Hitachi Chemical Co Ltd 遮罩形成用組成物、太陽電池用基板的製造方法以及太陽電池元件的製造方法
TW201335070A (zh) * 2012-01-10 2013-09-01 Hitachi Chemical Co Ltd 阻擋層形成用組成物、阻擋層、太陽電池用基板的製造方法以及太陽電池元件的製造方法

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Publication number Priority date Publication date Assignee Title
WO2007020833A1 (fr) * 2005-08-12 2007-02-22 Sharp Kabushiki Kaisha Pâte de masquage, son procédé de production, et procédé de fabrication d’une cellule solaire utilisant cette pâte de masquage
WO2010101054A1 (fr) * 2009-03-02 2010-09-10 シャープ株式会社 Procédé de production de dispositif à semi-conducteur
JP2011029553A (ja) * 2009-07-29 2011-02-10 Sharp Corp 半導体装置の製造方法
JP2011035252A (ja) * 2009-08-04 2011-02-17 Sharp Corp 半導体装置の製造方法
WO2011132744A1 (fr) * 2010-04-23 2011-10-27 シャープ株式会社 Procédé de fabrication de dispositif à semi-conducteur

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