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WO2017057238A1 - COMPOSITION DE DIFFUSION D'IMPURETÉS DE TYPE p, PROCÉDÉ DE FABRICATION D'ÉLÉMENT SEMI-CONDUCTEUR L'UTILISANT, ET PROCÉDÉ DE FABRICATION DE CELLULE SOLAIRE - Google Patents

COMPOSITION DE DIFFUSION D'IMPURETÉS DE TYPE p, PROCÉDÉ DE FABRICATION D'ÉLÉMENT SEMI-CONDUCTEUR L'UTILISANT, ET PROCÉDÉ DE FABRICATION DE CELLULE SOLAIRE Download PDF

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WO2017057238A1
WO2017057238A1 PCT/JP2016/078193 JP2016078193W WO2017057238A1 WO 2017057238 A1 WO2017057238 A1 WO 2017057238A1 JP 2016078193 W JP2016078193 W JP 2016078193W WO 2017057238 A1 WO2017057238 A1 WO 2017057238A1
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type impurity
impurity diffusion
group
carbon atoms
diffusion composition
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Japanese (ja)
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北田剛
稲葉智雄
池上由洋
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Toray Industries Inc
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Toray Industries Inc
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Priority to CN201680055017.4A priority Critical patent/CN108028188B/zh
Priority to JP2016560609A priority patent/JP6772836B2/ja
Priority to KR1020187006711A priority patent/KR20180063056A/ko
Publication of WO2017057238A1 publication Critical patent/WO2017057238A1/fr
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a p-type impurity diffusion composition for diffusing impurities in a semiconductor substrate, a method for manufacturing a semiconductor element using the same, and a method for manufacturing a solar cell.
  • a p-type impurity diffusion component as boron tribromide (BBr 3), the sulforylurea chloride (POCl 3) used as the n-type impurity diffusion component
  • BBr 3 boron tribromide
  • POCl 3 the sulforylurea chloride
  • Patent Document 1 a first impurity diffusing agent layer is formed on the surface of a semiconductor substrate, after baking, a second impurity diffusing agent layer is formed, and the semiconductor substrate is heated at a temperature higher than the baking temperature, A method of simultaneously diffusing a first impurity component and a second impurity component in a semiconductor substrate is disclosed.
  • n-type impurity for example, phosphorus element
  • the present invention has been made based on the above-described circumstances, and an object thereof is to provide a p-type impurity diffusion composition having excellent diffusibility to a semiconductor substrate and sufficient barrier properties against n-type impurities. To do.
  • the p-type impurity diffusion composition of the present invention has the following configuration. That is, a p-type impurity diffusion composition containing (A) polysiloxane and (B) a p-type impurity diffusion component having a Si—O—B bond.
  • a p-type impurity diffusion composition having excellent diffusibility of p-type impurities into a semiconductor substrate and excellent barrier properties against n-type impurities.
  • the p-type impurity diffusion composition of the present invention contains (A) polysiloxane and (B) a p-type impurity diffusion component having a Si—OB bond.
  • the p-type impurity diffusion composition of the present invention is used as a p-type impurity diffusion source for forming a p-type impurity region in a semiconductor substrate.
  • an n-type impurity diffusion source is separately provided on the same semiconductor substrate, and the p-type impurity and the n-type impurity are simultaneously diffused in the semiconductor substrate (hereinafter simply referred to as “simultaneous diffusion”).
  • “simultaneously” means “in one step”), it is possible to prevent n-type impurities from being mixed into the p-type impurity region. This is because the p-type impurity diffusion composition of the present invention contains polysiloxane, which is considered as follows.
  • n-type impurities are mixed into the p-type impurity region.
  • n-type impurities released into the air from the n-type impurity diffusion source are mixed into the p-type impurity diffusion source, and this is caused by solid phase diffusion. It is considered that the diffusion is to the p-type impurity region directly under the diffusion source. Since the polysiloxane contained in the p-type impurity diffusion composition of the present invention has a high barrier property against n-type impurities, it is considered that the n-type impurities can be prevented from being mixed into the p-type impurity diffusion source.
  • the p-type impurity diffusion composition of the present invention can be suitably used even when simultaneous diffusion is performed, but of course, the present invention is not limited to such a case, and is generally applied when diffusing p-type impurities. Is possible.
  • the p-type impurity diffusion composition of the present invention can form a uniform film and contain a uniform diffusion by containing polysiloxane.
  • the terminal group of the polysiloxane is any one of hydrogen, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. It is.
  • the number of carbons represents the total number of carbons including a group further substituted with the group.
  • a butyl group substituted with a methoxy group has 5 carbon atoms.
  • (A) polysiloxane is represented by the following general formula (1).
  • R 1 represents an aryl group having 6 to 15 carbon atoms, and a plurality of R 1 may be the same or different.
  • R 2 is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
  • the plurality of R 2 may be the same or different.
  • R 3 and R 4 represent any one of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms.
  • R 3 and R 4 may be the same or different.
  • the hydroxyl group in R 2 to R 4 , the alkoxy group having 1 to 6 carbon atoms, and the acyloxy group having 1 to 6 carbon atoms are the hydroxyl group in another R 2 to R 4 , the alkoxy group having 1 to 6 carbon atoms, the carbon number A crosslinked structure condensed with any one of 1 to 6 acyloxy groups may be formed.
  • X is any one of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms.
  • Y represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 1 to 6 carbon atoms.
  • the polysiloxane represented by the general formula (1) may be a block copolymer or a random copolymer.
  • n 25 or more, that is, the unit containing an aryl group having 6 to 15 carbon atoms in the polysiloxane is contained in an amount of 25 mol% or more in terms of Si atoms, the crosslinking density between the polysiloxane skeletons does not become too high, Even with a thick film, cracks are further suppressed. Thereby, since cracks are less likely to occur in the firing and thermal diffusion steps, barrier properties against other impurities can be improved during simultaneous diffusion, and stability of impurity diffusion can be improved.
  • n is 95 or less, that is, the unit containing an aryl group having 6 to 15 carbon atoms in the polysiloxane is 95 mol% or less in terms of Si atom, it is possible to eliminate the peeling residue after diffusion.
  • Residues are considered to be carbides that remain after organic substances are not completely decomposed and volatilized, which not only hinders diffusibility but also increases contact resistance with electrodes that are formed later, and reduces the efficiency of solar cells. It becomes.
  • the number of units containing an aryl group having 6 to 15 carbon atoms exceeds 95 mol%, it is considered that the composition film becomes too dense before the organic components are completely decomposed and volatilized, and a residue is likely to be generated.
  • the structural unit of the polysiloxane represented by the general formula (1) has a structure obtained by polycondensing a tetrafunctional or trifunctional organosilane, a hydroxyl group in R 2 to R 4 , a carbon number of 1 to 6
  • the alkoxy group having 1 to 6 carbon atoms forms a cross-linked structure with any one of the hydroxyl group, the alkoxy group having 1 to 6 carbon atoms, and the acyloxy group having 1 to 6 carbon atoms in another R 2 to R 4 . Also good.
  • the p-type impurity diffusion composition of the present invention is such that R 2 and R 4 are a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an acyloxy group having 1 to 6 carbon atoms. It is preferable that R 3 represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms. That is, it is preferable that all the polysiloxane constituent units have a structure obtained by polycondensation of a trifunctional organosilane.
  • the aryl group having 6 to 15 carbon atoms in R 1 and R 2 in the general formula (1) may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition.
  • Specific examples of the aryl group having 6 to 15 carbon atoms include phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-hydroxyphenyl group, p-styryl group, p-methoxyphenyl group, and naphthyl.
  • a phenyl group, a p-tolyl group, and an m-tolyl group are particularly preferable.
  • R 2 ⁇ alkyl group having 1 to 6 carbon atoms for R 4 in the general formula (1), an alkoxy group having 1 to 6 carbon atoms, any alkenyl group an acyloxy group and having 2 to 10 carbon atoms having 1 to 6 carbon atoms Either an unsubstituted product or a substituted product may be used and can be selected according to the characteristics of the composition.
  • alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, trifluoromethyl group, 3, Examples include 3,3-trifluoropropyl group, 3-methoxy-n-propyl group, glycidyl group, 3-glycidoxypropyl group, 3-aminopropyl group, 3-mercaptopropyl group, and 3-isocyanatopropyl group.
  • a methyl group having 4 or less carbon atoms an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group are preferable.
  • alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and t-butoxy group.
  • acyloxy group having 1 to 6 carbon atoms include an acetoxy group, a propionyloxy group, an acryloyloxy group, and a benzoyloxy group.
  • alkenyl group having 2 to 10 carbon atoms include vinyl group, 1-propenyl group, 1-butenyl group, 2-methyl-1-propenyl group, 1,3-butanedienyl group, and 3-methoxy-1-propenyl. Group, 3-acryloxypropyl group, and 3-methacryloxypropyl group. From the viewpoint of residue, vinyl group having 1 to 4 carbon atoms, 1-propenyl group, 1-butenyl group, 2-methyl-1-propenyl group The group, 1,3-butanedienyl group and 3-methoxy-1-propenyl group are particularly preferred.
  • organosilane used as the raw material of the unit having R 1 and R 2 of the general formula (1) include phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, p-tolyltri Examples include methoxysilane, p-styryltrimethoxysilane, p-methoxyphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, and 2-naphthyltriethoxysilane. Of these, phenyltrimethoxysilane, p-tolyltrimethoxysilane, and p-methoxyphenyltrimethoxysilane are particularly preferable.
  • organosilane used as the raw material of the unit having R 3 and R 4 in the general formula (1) include tetrafunctional organosilanes such as tetramethoxysilane, tetraethoxysilane, and tetraacetoxysilane, methyltrimethoxysilane, Methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltri Ethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, glycidyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxy
  • the polysiloxane represented by the general formula (1) can be obtained by hydrolyzing an organosilane and then subjecting the hydrolyzate to a condensation polymerization reaction in the presence of a solvent or without a solvent.
  • Various conditions for the hydrolysis reaction such as acid concentration, reaction temperature, reaction time, etc. can be appropriately set in consideration of the reaction scale, reaction vessel size, shape, etc. It is preferable to add the acid catalyst and water over 1 to 180 minutes and then react at room temperature to 110 ° C. for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed.
  • Acid catalysts include hydrochloric acid, hydrobromic acid, hydroiodic acid and other halogenated inorganic acids, sulfuric acid, nitric acid, phosphoric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, boric acid, tetrafluoroboric acid, Other inorganic acids such as chromic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, sulfonic acid such as trifluoromethanesulfonic acid, acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, Examples thereof include carboxylic acids such as tartaric acid, pyruvic acid, citric acid, succinic acid, fumaric acid and malic acid.
  • the acid catalyst that can be used for preparing the polysiloxane preferably contains no atoms other than silicon, hydrogen, carbon, oxygen, and nitrogen as much as possible from the viewpoint of doping properties. It is preferable to use an acid-based acid catalyst. Of these, formic acid is preferred.
  • the content of the acid catalyst is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total organosilane used in the hydrolysis reaction.
  • the reaction solution is preferably heated as it is at 50 ° C. or more and below the boiling point of the solvent for 1 to 100 hours to carry out the condensation polymerization reaction. Moreover, in order to raise the polymerization degree of polysiloxane, you may reheat.
  • the solvent used in the organosilane hydrolysis reaction and the hydrolyzate condensation reaction is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, and the like of the resin composition.
  • two or more solvents may be combined, or the reaction may be performed without solvent.
  • the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, 1-methoxy-2-propanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2- Alcohols such as butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol, terpineol and texanol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol t-butyl ether , Propylene glycol n-butyl ether ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol
  • a solvent When a solvent is generated by a hydrolysis reaction, it can be hydrolyzed without solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the reaction. Further, after hydrolysis according to the purpose, an appropriate amount of the produced alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.
  • the amount of the solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the total organosilane. By making the quantity of a solvent into the said range, it can control easily so that a hydrolysis reaction may progress sufficiently and necessary.
  • the water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of Si atoms.
  • the polysiloxane represented by the general formula (1) is preferably an organosilane represented by R 1 R 2 Si (OR 8 ) 2 and an organosilane represented by R 3 R 4 Si (OR 9 ) 2.
  • R 8 and R 9 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 1 to 6 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, and n-hexyl group.
  • acyl group having 1 to 6 carbon atoms include acetyl group, propionyl group, benzoyl group and the like.
  • the molar ratio of each unit of the polysiloxane represented by the general formula (1) can be adjusted by the type and amount of the organosilane used in the hydrolysis / condensation reaction.
  • the content of the polysiloxane represented by the general formula (1) in the diffusion composition of the present invention is such that all the polysiloxanes from the viewpoint of improving the barrier property against other impurities during simultaneous diffusion and the diffusion stability of p-type impurities.
  • the siloxane component preferably contains 60% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
  • the weight average molecular weight (Mw) of the polysiloxane used in the present invention is preferably 1000 or more and more preferably 2000 or more in terms of polystyrene as measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the upper limit value of Mw is preferably less than 50000, and more preferably less than 20000.
  • the weight average molecular weight of the polysiloxane is a value determined by the method described later.
  • the polysiloxane preferably has a 20% thermal decomposition temperature of 550 ° C. or higher.
  • the 20% thermal decomposition temperature is a temperature at which the weight of polysiloxane is reduced by 20% due to thermal decomposition.
  • the thermal decomposition temperature can be measured using a thermogravimetric measuring device (TGA) or the like.
  • the p-type impurity diffusion component having Si—O—B bond is uniformly mixed with polysiloxane and in the semiconductor substrate during thermal diffusion. It is a component for diffusing boron.
  • boron atoms can be immobilized on the impurity diffusion source up to the diffusion temperature, so that stable diffusion can be achieved.
  • XPS X-ray photoelectron spectroscopy
  • IR infrared spectroscopy
  • B-NMR nuclear magnetic resonance
  • Si-NMR Si-NMR
  • the p-type impurity diffusion component having a Si—O—B bond is not particularly limited, but it is preferable to use a reaction product of an organosilane and a boron compound.
  • the (B) p-type impurity diffusion component having a Si—OB bond includes a partial structure represented by the following general formula (2).
  • R 5 and R 6 are a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms.
  • Each of R 5 and R 6 may be the same as or different from each other.
  • the alkoxy group having 1 to 6 carbon atoms and the acyloxy group having 1 to 6 carbon atoms in R 5 and R 6 in the general formula (2) may be either unsubstituted or substituted, depending on the characteristics of the composition. You can choose.
  • alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, trifluoromethyl group, 3, Examples include 3,3-trifluoropropyl group, 3-methoxy-n-propyl group, glycidyl group, 3-glycidoxypropyl group, 3-aminopropyl group, 3-mercaptopropyl group, and 3-isocyanatopropyl group.
  • a methyl group having 4 or less carbon atoms an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group are preferable.
  • alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and t-butoxy group.
  • acyloxy group having 1 to 6 carbon atoms include an acetoxy group, a propionyloxy group, an acryloyloxy group, and a benzoyloxy group.
  • alkenyl group having 2 to 10 carbon atoms include vinyl group, 1-propenyl group, 1-butenyl group, 2-methyl-1-propenyl group, 1,3-butanedienyl group, and 3-methoxy-1-propenyl. Group, 3-acryloxypropyl group, and 3-methacryloxypropyl group. From the viewpoint of residue, vinyl group having 1 to 4 carbon atoms, 1-propenyl group, 1-butenyl group, 2-methyl-1-propenyl group The group, 1,3-butanedienyl group and 3-methoxy-1-propenyl group are particularly preferred.
  • the aryl group having 6 to 15 carbon atoms may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition.
  • Specific examples of the aryl group having 6 to 15 carbon atoms include phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-hydroxyphenyl group, p-styryl group, p-methoxyphenyl group, and naphthyl.
  • a phenyl group, a p-tolyl group, and an m-tolyl group are particularly preferable.
  • the compound containing the partial structure represented by the general formula (2) is preferably obtained by polycondensation reaction of organosilane and boron compound in the presence of a solvent or without solvent.
  • organosilane used as a raw material of the unit having R 5 and R 6 of the compound including the partial structure represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, Tetrapropyloxysilane, tetrabutoxysilane and the like can be mentioned.
  • Trifunctional organosilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin- Butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, glycidyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, trifluoromethyltri Methoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane,
  • Bifunctional organosilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxy.
  • Examples thereof include silane, dibutyldiethoxysilane, dibutyldipropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, and phenylmethyldimethoxysilane.
  • methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and diphenyldimethoxysilane are preferably used.
  • These organosilanes may be used alone or in combination of two or more.
  • the p-type impurity diffusion composition of the present invention has R 5 as an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms. It is preferable that R 6 represents any one of a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and an acyloxy group having 1 to 6 carbon atoms. That is, the organosilane is preferably a trifunctional organosilane.
  • the p-type impurity diffusion composition of the present invention is represented by R 5 .
  • the component (B) Improves the reflow effect of polysiloxane.
  • the reflow effect of polysiloxane refers to the effect that when an organic substance such as a binder is decomposed during firing and voids are generated in the film, the polysiloxane flows and fills the voids to form a dense film.
  • the molar ratio of the aryl group having 6 to 15 carbon atoms in R 5 is 95% or less, more preferably 80% or less, it is possible to eliminate the peeling residue after diffusion.
  • Residues are considered to be carbides that remain after organic substances are not completely decomposed and volatilized, which not only hinders diffusibility but also increases contact resistance with electrodes that are formed later, and reduces the efficiency of solar cells. It becomes.
  • the ratio of aryl groups having 6 to 15 carbon atoms exceeds 95%, more preferably 80%, the composition film becomes too dense before the organic components are completely decomposed and volatilized, and residues are likely to be generated. Conceivable.
  • the molar ratio of the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 15 carbon atoms in R 5 in the general formula (2) can be adjusted by the type and amount of the organosilane used in the polycondensation reaction. .
  • Boron acid, diboron trioxide, trimethyl borate, boric acid may be used as a raw material for the p-type impurity diffusion component having a Si—O—B bond, including the partial structure represented by the general formula (2).
  • Examples include triethyl, tripropyl borate, tributyl borate and the like that generate boric acid by hydrolysis. Of these, boric acid is preferably used.
  • the p-type impurity diffusion component having a Si—O—B bond including the partial structure represented by the general formula (2) is preferably represented by the following general formula (3).
  • R 5 and R 6 in the general formula (3) are as described above.
  • l represents an integer of 2 or more, and is preferably 2 to 10.
  • boron atoms can be more fixed in the impurity diffusion composition film up to the diffusion temperature, so that stable diffusion is possible.
  • the terminal group in the case where the p-type impurity diffusion component having a Si—O—B bond represented by the general formula (3) has a terminal group is not particularly limited, but is a hydrogen atom, a hydroxyl group, a carbon number of 1 to 6 A group selected from the group consisting of an alkyl group, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms is preferable.
  • the structural units in parentheses in the general formula (3) are each a head-to-tail bond. Even if it couple
  • the p-type impurity diffusion component having a Si—OB bond may include a partial structure represented by the following general formula (4).
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the plurality of R 7 may be the same or different.
  • k represents an integer of 1 or more, and preferably 2 to 10.
  • the structural units in parentheses in the general formula (4) are each connected by a head-to-tail bond (head-to-tail bond). head-to-head connection).
  • alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, trifluoromethyl group, 3, Examples include 3,3-trifluoropropyl group, 3-methoxy-n-propyl group, glycidyl group, 3-glycidoxypropyl group, 3-aminopropyl group, 3-mercaptopropyl group, and 3-isocyanatopropyl group.
  • reaction temperature and reaction time can be appropriately set in consideration of reaction scale, reaction vessel size, shape, etc.
  • reaction time After mixing the boron compound, the reaction is preferably performed at room temperature to 110 ° C. for 1 to 180 minutes.
  • the compound containing the partial structure represented by the general formula (2) is preferably taken out in a liquid state, and after completion of the reaction, a solvent is further added to obtain an appropriate concentration as a composition. It is also preferable to adjust.
  • the solvent used in the polycondensation reaction between the organosilane and the boron compound is not particularly limited, and can be appropriately selected in consideration of the stability, paintability, volatility, etc. of the resin composition. In addition, two or more solvents may be combined, or the reaction may be performed without solvent.
  • the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, 1-methoxy-2-propanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2- Alcohols such as butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol, terpineol and texanol; glycols such as ethylene glycol and propylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol t-butyl ether, propylene glycol n-butyl ether ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Di
  • Tate like Aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane, ethyl benzoate, naphthalene, 1,2,3,4-tetrahydronaphthalene; ⁇ -butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylimidazolidinone, dimethyl sulfoxide, propylene carbonate; And so on.
  • Aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane, ethyl benzoate, naphthalene, 1,2,3,4-tetrahydronaphthalene; ⁇ -butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylimidazolidinone, dimethyl sulfoxide, propylene carbonate; And so on.
  • a range is preferable. By setting the mass ratio within the above range, excellent doping performance can be obtained.
  • the mass ratio is more preferably in the range of 95: 5 to 40:60, and most preferably in the range of 90:10 to 50:50.
  • the SiO 2 equivalent mass of the Si component is a value obtained by converting the content of the Si component in the composition into the mass of SiO 2 . This mass ratio can be calculated by inorganic analysis such as ICP emission analysis or fluorescent X-ray analysis.
  • the p-type impurity diffusion composition of the present invention preferably contains a solvent.
  • a solvent can be used without a restriction
  • the content of the solvent having a boiling point of 100 ° C. or higher is preferably 20% by weight or more based on the total amount of the solvent.
  • Solvents having a boiling point of 100 ° C. or higher include diethylene glycol methyl ethyl ether (boiling point 176 ° C.), ethylene glycol monoethyl ether acetate (boiling point 156.4 ° C.), ethylene glycol monomethyl ether acetate (boiling point 145 ° C.), methyl lactate (boiling point 145 ° C.
  • the solvent having a boiling point of less than 100 ° C. include alcohols such as methanol, ethanol, propanol, isopropanol, and t-butanol; ethers such as diethyl ether and diisopropyl ether; ketones such as methyl ethyl ketone; isopropyl acetate, ethyl Examples thereof include acetates such as acetate, propyl acetate, n-propyl acetate, and 3-methyl-3-methoxybutyl acetate; aliphatic hydrocarbons such as hexane and cyclohexane.
  • the p-type impurity diffusion composition of the present invention may contain a surfactant. By containing the surfactant, coating unevenness is improved and a uniform coating film is obtained.
  • a fluorine-based surfactant or a silicone-based surfactant is preferably used.
  • fluorosurfactant examples include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl. Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2 , 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (Perf Oloocty
  • silicone surfactants examples include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (above, manufactured by Toray Dow Corning Co., Ltd.), BYK067A, BYK310, BYK322, BYK331, BYK333, BYK355 (above, Big Chemie Japan) Etc.).
  • the content of the surfactant is preferably 0.0001 to 1% by weight in the p-type impurity diffusion composition.
  • the p-type impurity diffusion composition of the present invention preferably contains a thickener for viscosity adjustment. Thereby, it can apply
  • organic thickener cellulose, cellulose derivative, starch, starch derivative, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene Resin, polyester resin, synthetic rubber, natural rubber, polyacrylic acid, various acrylic resins, polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, silicone oil, sodium alginate, xanthan gum polysaccharide, gellan gum polysaccharide, guar gum Polysaccharides, carrageenan polysaccharides, locust bean gum polysaccharides, carboxyvinyl polymers, hydrogenated castor oil
  • bentonite montmorillonite, magnesia montmorillonite, tetsu montmorillonite, tectum magnesia montmorillonite, beidellite, aluminite, sapphire, aluminian saponite, laponite, aluminum silicate, aluminum silicate
  • examples thereof include magnesium, organic hectorite, fine particle silicon oxide, colloidal alumina, and calcium carbonate. You may use these in combination of multiple types.
  • a cellulosic thickener 1110, 1120, 1130, 1140, 1150, 1160, 1170, 1180, 1190, 2200, 2260, 2280, 2450 (above, manufactured by Daicel Finechem Co., Ltd.) There is.
  • polysaccharide thickeners examples include Viscarin PC209, Viscarin PC389, SeaKemXP8012, (manufactured by FM Chemicals), CAM-H, GJ-182, SV-300, LS-20, LS-30, XGT, XGK. -D, G-100, LG-10 (all of which are Mitsubishi Corporation).
  • acrylic thickeners # 2434T, KC-7000, KC-1700P (above, manufactured by Kyoeisha Chemical Co., Ltd.), AC-10LHPK, AC-10SHP, 845H, PW-120 (above, Toagosei Co., Ltd.) Etc.).
  • Examples of hydrogenated castor oil thickeners include Disparon 308, AMLONNT-206 (above, manufactured by Enomoto Kasei Co., Ltd.), T-20SF, T-75F (above, made by Ito Oil Co., Ltd.), and the like.
  • Examples of the oxidized polyethylene-based thickener include D-10A, D-120, D-120-10, D-1100, DS-525, DS-313 (above, manufactured by Ito Oil Co., Ltd.), Disparon 4200-20, Same PF-911, Same PF-930, Same 4401-25X, Same NS-30, Same NS-5010, Same NS-5025, Same NS-5810, Same NS-5210, Same NS-5310 Co., Ltd.), Flownon SA-300, SA-300H (above, manufactured by Kyoeisha Chemical Co., Ltd.), PEO-1, PEO-3 (above, manufactured by Sumitomo Seika Co., Ltd.), and the like.
  • T-250F, T-550F, T-850F, T-1700, T-1800, T-2000 above, manufactured by Ito Oil Co., Ltd.
  • Disparon 6500, 6300, 6650 6700, 3900EF above, manufactured by Enomoto Kasei Co., Ltd.
  • Bentonite-based thickeners include Bengel, Wenger HV, HVP, F, FW, Bright 11, A, W-100, W-100U, W-300U, SH, Multiben, and Sven. , Sven C, E, W, P, WX, Organite, Organite D (above, manufactured by Hojun Co., Ltd.).
  • Fine particle silicon oxide thickeners include AEROSILR972, R974, NY50, RY200S, RY200, RX50, NAX50, RX200, RX300, VPNKC130, R805, R104, R711, OX50. 50, 90G, 130, 200, 300, 380 (above, manufactured by Nippon Aerosil Co., Ltd.), WACKER HDK S13, V15, N20, N20P, T30, T40, H15 , H18, H20, H30 (above, manufactured by Asahi Kasei Co., Ltd.).
  • the thickener preferably has a 90% thermal decomposition temperature of 400 ° C. or less from the viewpoint of dense film formation and residue reduction.
  • polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, and various acrylic ester resins are preferable, and among them, polyethylene oxide, polypropylene oxide, or acrylic ester resins are more preferable. From the viewpoint of storage stability, an acrylic ester resin is particularly preferable.
  • the 90% thermal decomposition temperature is a temperature at which the weight of the thickener is reduced by 90% by thermal decomposition.
  • the thermal decomposition temperature can be measured using a thermogravimetric measuring device (TGA) or the like.
  • acrylic ester resins include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyhydroxyethyl
  • acrylic ester component may be 60 mol% or more as a polymerization ratio, and other copolymerizable components such as polyacrylic acid and polystyrene may be copolymerized.
  • Acrylic acid ester resins, polyethylene oxide, and polypropylene oxide are all preferably those having a weight average molecular weight of 100,000 or more because of their high thickening effect.
  • the content of these thickeners is preferably 3% by weight or more and 20% by weight or less in the p-type impurity diffusion composition. By being in this range, a sufficient viscosity adjusting effect can be obtained, and at the same time a dense film can be formed.
  • the viscosity of the p-type impurity diffusion composition of the present invention is not limited and can be appropriately changed according to the printing method and the film thickness.
  • the solid content concentration of the p-type impurity diffusion composition of the present invention is not particularly limited, but it is preferably 1% by weight or more and 90% by weight or less. If it is lower than this concentration range, the coating film thickness becomes too thin and it is difficult to obtain a desired doping property, and if it is higher than this concentration range, the storage stability is lowered.
  • a first aspect of the method for manufacturing a semiconductor device of the present invention includes a step of applying a p-type impurity diffusion composition of the present invention to a semiconductor substrate to form a p-type impurity diffusion composition film, and the p-type impurity diffusion composition. And a step of diffusing p-type impurities from the material film to form a p-type impurity diffusion layer.
  • the second aspect of the method for manufacturing a semiconductor element of the present invention is a method of applying an n-type impurity diffusion composition to a semiconductor substrate to form an n-type impurity diffusion composition film, applying a p-type impurity diffusion composition to form a p-type impurity diffusion composition film; heating the semiconductor substrate; and simultaneously forming an n-type impurity diffusion layer and a p-type impurity diffusion layer; The manufacturing method of the semiconductor element containing this.
  • a third aspect of the method for producing a semiconductor element of the present invention includes a step of applying a p-type impurity diffusion composition of the present invention to one surface of a semiconductor substrate to form a p-type impurity diffusion composition film, An n-type impurity diffusion composition is applied to the other surface of the semiconductor substrate to form an n-type impurity diffusion composition film, and the semiconductor substrate is heated to thereby form a p-type impurity diffusion layer and an n-type Forming an impurity diffusion layer at the same time.
  • FIG. 1 shows a method for forming an impurity diffusion layer by applying a p-type impurity diffusion composition of the present invention to a semiconductor substrate and diffusing the p-type impurity into the semiconductor substrate therefrom.
  • a p-type impurity diffusion composition film 2 is formed on a semiconductor substrate 1.
  • the semiconductor substrate 1 for example, a crystalline silicon substrate in which an n-type single crystal silicon having an impurity concentration of 10 15 to 10 16 atoms / cm 3 , polycrystalline silicon, and other elements such as germanium and carbon are mixed. Is mentioned. It is also possible to use p-type crystalline silicon or a semiconductor other than silicon.
  • the semiconductor substrate 1 is preferably a substantially rectangular shape having a thickness of 50 to 300 ⁇ m and an outer shape of 100 to 250 mm on a side. In order to remove the slice damage and the natural oxide film, it is preferable to etch the surface with a hydrofluoric acid solution or an alkaline solution.
  • a protective film may be formed on the light receiving surface of the semiconductor substrate 1.
  • a known protective film such as silicon oxide or silicon nitride formed by a method such as a CVD (chemical vapor deposition) method or a spin-on-glass (SOG) method can be applied.
  • Examples of the p-type impurity diffusion composition coating method include spin coating, screen printing, ink jet printing, slit coating, spray coating, letterpress printing, and intaglio printing.
  • the p-type impurity diffusion composition film 2 is preferably dried in a range of 50 to 200 ° C. for 30 seconds to 30 minutes with a hot plate, oven or the like.
  • the thickness of the p-type impurity diffusion composition film 2 after drying is preferably 100 nm or more from the viewpoint of p-type impurity diffusibility, and preferably 3 ⁇ m or less from the viewpoint of residues after etching.
  • p-type impurities are diffused into the semiconductor substrate 1 to form a p-type impurity diffusion layer 3.
  • a diffusion method of the p-type impurity a known thermal diffusion method can be used.
  • methods such as electric heating, infrared heating, laser heating, and microwave heating can be used.
  • the time and temperature of thermal diffusion can be appropriately set so that desired diffusion characteristics such as impurity diffusion concentration and diffusion depth can be obtained.
  • a p-type diffusion layer having a surface impurity concentration of 10 19 to 10 21 atoms / cm 3 can be formed by thermal diffusion at 800 ° C. to 1200 ° C. for 1 to 120 minutes.
  • the diffusion atmosphere is not particularly limited, and may be performed in the air, or the oxygen amount in the atmosphere may be appropriately controlled using an inert gas such as nitrogen or argon. From the viewpoint of shortening the diffusion time, the oxygen concentration in the atmosphere is preferably 3% or less. Further, if necessary, baking may be performed in the range of 200 ° C. to 850 ° C. before diffusion.
  • the p-type impurity diffusion composition film 2 formed on the surface of the semiconductor substrate 1 is removed by a known etching method.
  • a material used for an etching For example, what contains water, an organic solvent, etc. as an other component contains at least 1 sort (s) among hydrogen fluoride, ammonium, phosphoric acid, a sulfuric acid, and nitric acid. preferable.
  • a p-type impurity diffusion layer can be formed in the semiconductor substrate.
  • FIG. 2 illustrates a step of applying an n-type impurity diffusion composition to a semiconductor substrate, diffusing the n-type impurity from the n-type impurity diffusion composition into the semiconductor substrate, and the semiconductor substrate using the n-type impurity diffusion composition as a mask. And a step of applying and diffusing a p-type impurity to form a method for forming an impurity diffusion layer.
  • FIG. 3 illustrates a solar cell manufacturing method using the impurity diffusion layer, taking a back junction solar cell manufacturing method as an example.
  • an n-type impurity diffusion composition film 4 is formed on a semiconductor substrate 1.
  • Examples of the method for forming the n-type impurity diffusion composition film 4 include a screen printing method, an ink jet printing method, a slit coating method, a spray coating method, a letterpress printing method, and an intaglio printing method. After forming the coating film by these methods, it is preferable to dry the n-type impurity diffusion composition film 4 in a range of 50 to 200 ° C. for 30 seconds to 30 minutes using a hot plate, oven, or the like.
  • the thickness of the n-type impurity diffusion composition film 4 after drying is preferably 200 nm or more, and preferably 5 ⁇ m or less from the viewpoint of crack resistance in consideration of the masking property for p-type impurities.
  • n-type impurities in the n-type impurity diffusion composition film 4 are diffused into the semiconductor substrate 1 to form an n-type impurity diffusion layer 5.
  • a known thermal diffusion method can be used. For example, methods such as electric heating, infrared heating, laser heating, and microwave heating can be used.
  • the time and temperature of thermal diffusion can be appropriately set so that desired diffusion characteristics such as impurity diffusion concentration and diffusion depth can be obtained.
  • an n-type diffusion layer having a surface impurity concentration of 10 19 to 10 21 atoms / cm 3 can be formed by heat diffusion at 800 ° C. to 1200 ° C. for 1 to 120 minutes.
  • the diffusion atmosphere is not particularly limited, and may be performed in the air, or the oxygen amount in the atmosphere may be appropriately controlled using an inert gas such as nitrogen or argon. From the viewpoint of shortening the diffusion time, the oxygen concentration in the atmosphere is preferably 3% or less. Further, if necessary, baking may be performed in the range of 200 ° C. to 850 ° C. before diffusion.
  • the n-type impurity diffusion composition film 4 can be peeled off by peeling with a known etching solution such as hydrofluoric acid.
  • the p-type impurity diffusion composition may be applied to the semiconductor substrate after the n-type impurity diffusion layer is formed and the p-type impurity may be diffused. As described below, the n-type impurity diffusion composition is used. Printing of the p-type impurity diffusion composition and diffusion of the p-type impurities can be performed without peeling off the physical film 4, which is preferable from the viewpoint of reducing the number of steps.
  • the n-type impurity diffusion composition film 4 is baked as necessary, and then the n-type impurity diffusion composition film 4 is used as a mask as shown in FIG. A type impurity diffusion composition is applied.
  • the p-type impurity diffusion composition 2 may be formed on the entire surface, or may be formed only on a portion where the n-type impurity diffusion composition film 4 is not present. Alternatively, the p-type impurity diffusion composition 2 may be applied so as to partially overlap the n-type impurity diffusion composition film 4.
  • Examples of the p-type impurity diffusion composition coating method include spin coating, screen printing, ink jet printing, slit coating, spray coating, letterpress printing, and intaglio printing.
  • the p-type impurity diffusion composition film 2 is preferably dried in a range of 50 to 200 ° C. for 30 seconds to 30 minutes with a hot plate, oven or the like.
  • the thickness of the p-type impurity diffusion composition 2 after drying is preferably 100 nm or more from the viewpoint of diffusibility of the p-type impurities, and preferably 3 ⁇ m or less from the viewpoint of residues after etching.
  • the p-type impurity diffusion composition 2 is diffused into the semiconductor substrate 1 using the fired n-type impurity diffusion composition film 4 as a mask layer, and the p-type impurity diffusion layer 3 is formed.
  • a diffusion method of the p-type impurity a known thermal diffusion method can be used. For example, methods such as electric heating, infrared heating, laser heating, and microwave heating can be used.
  • the time and temperature of thermal diffusion can be appropriately set so that desired diffusion characteristics such as impurity diffusion concentration and diffusion depth can be obtained.
  • a p-type diffusion layer having a surface impurity concentration of 10 19 to 10 21 atoms / cm 3 can be formed by thermal diffusion at 800 ° C. to 1200 ° C. for 1 to 120 minutes.
  • the diffusion atmosphere is not particularly limited, and may be performed in the air, or the oxygen amount in the atmosphere may be appropriately controlled using an inert gas such as nitrogen or argon. From the viewpoint of shortening the diffusion time, the oxygen concentration in the atmosphere is preferably 3% or less. Further, if necessary, baking may be performed in the range of 200 ° C. to 850 ° C. before diffusion.
  • the n-type impurity diffusion composition film 4 and the p-type impurity diffusion composition film 2 formed on the surface of the semiconductor substrate 1 are removed by a known etching method.
  • a material used for an etching For example, what contains water, an organic solvent, etc. as an other component contains at least 1 sort (s) among hydrogen fluoride, ammonium, phosphoric acid, a sulfuric acid, and nitric acid. preferable.
  • n-type and p-type impurity diffusion layers can be formed in the semiconductor substrate. By setting it as such a process, a process can be simplified compared with the conventional method.
  • the application / diffusion of the p-type impurity diffusion composition is performed after the application / diffusion of the n-type impurity diffusion composition.
  • the n-type impurity is applied after the application / diffusion of the p-type impurity diffusion composition.
  • FIG. 3 the method for manufacturing the solar cell of the present invention will be described by taking a back junction solar cell as an example.
  • a protective film 6 is formed on the entire back surface of the semiconductor substrate 1 having the n-type impurity diffusion layer 5 and the p-type impurity diffusion layer 3 formed on the back surface.
  • the protective film 6 is patterned by an etching method or the like to form a protective film opening 6a.
  • the n-type contact electrode 8 and the p-type are formed by applying and baking an electrode paste on the region including the protective film opening 6a by a stripe coating method or a screen printing method. Contact electrode 7 is formed. Thereby, the back junction solar cell 9 is obtained.
  • FIG. 4 shows a step of forming a pattern using an n-type impurity diffusion composition, a step of applying a p-type impurity diffusion composition using the n-type impurity diffusion composition as a mask, the n-type impurity diffusion composition, and and a step of diffusing n-type and p-type impurities from the p-type impurity diffusion composition into the semiconductor substrate.
  • an n-type impurity diffusion composition film 4 is patterned on the semiconductor substrate 1.
  • the p-type impurity diffusion composition film 2 is formed using the n-type impurity diffusion composition film 4 as a mask. Form.
  • the n-type impurity diffusion component in the n-type impurity diffusion composition film 4 and the p-type impurity diffusion component in the p-type impurity diffusion composition film 2 are simultaneously applied to the semiconductor substrate.
  • N-type impurity diffusion layer 5 and p-type impurity diffusion layer 3 are formed. Examples of the impurity diffusion composition coating method, firing method, and diffusion method include the same methods as described above.
  • the n-type impurity diffusion composition film 4 and the p-type impurity diffusion composition film 2 formed on the surface of the semiconductor substrate 1 are removed by a known etching method.
  • a known etching method Through the above steps, n-type and p-type impurity diffusion layers can be formed in the semiconductor substrate. By setting it as such a process, compared with the conventional method, a process can be simplified further.
  • the p-type impurity diffusion composition is applied after the n-type impurity diffusion composition is applied.
  • the n-type impurity diffusion composition is applied after the p-type impurity diffusion composition is applied. It is also possible to do this. That is, in FIG. 4A, a p-type impurity diffusion composition is applied instead of the n-type impurity diffusion composition, and in FIG. 4B, n is applied instead of the p-type impurity diffusion composition. It is also possible to apply a type impurity diffusion composition.
  • a p-type impurity diffusion composition film 2 of the present invention is formed on a semiconductor substrate 1.
  • the p-type impurity diffusion composition film 2 is baked as necessary, as shown in FIG. 5B, the surface of the semiconductor substrate 1 opposite to the surface on which the p-type impurity diffusion composition film 2 is formed.
  • an n-type impurity diffusion composition film 4 is formed.
  • the impurity diffusion composition coating method, firing method, and diffusion method include the same methods as described above.
  • the p-type impurity diffusion composition film 2 and the n-type impurity diffusion composition film 4 formed on the surface of the semiconductor substrate 1 are removed by a known etching method.
  • n-type and p-type impurity diffusion layers can be formed in the semiconductor substrate.
  • n-type impurity diffusion composition is applied after application of the p-type impurity diffusion composition.
  • application of the p-type impurity diffusion composition is performed. Is also possible.
  • the method for manufacturing a solar cell of the present invention includes a step of manufacturing a semiconductor element by the method for manufacturing a semiconductor element of the present invention.
  • the process can be simplified as compared with the conventional method as described above.
  • a method for producing the solar cell of the present invention from the semiconductor element obtained by the method for producing a semiconductor element of the present invention a known method can be used. Specific examples thereof include the method described with reference to FIG.
  • the solar cell obtained by the method for manufacturing a solar cell of the present invention since n-type impurities are prevented from being mixed into the p-type impurity diffusion region, the power generation efficiency due to the mixing of the n-type impurities into the p-type impurity diffusion region is reduced. It is possible to suppress the occurrence of defects such as “decrease”.
  • the p-type impurity diffusion composition of the present invention is used in photovoltaic devices such as solar cells, and semiconductor devices that pattern impurity diffusion regions on the surface of semiconductors, such as transistor arrays, diode arrays, photodiode arrays, and transducers. Can also be deployed.
  • ⁇ -BL ⁇ -butyrolactone
  • MeTMS methyltrimethoxysilane
  • PhTMS phenyltrimethoxysilane
  • DMeDMS dimethoxydimethylsilane.
  • the impurity diffusion composition to be measured was applied to the silicon wafer by a known spin coating method so that the pre-baked film thickness was about 500 nm. After coating, the silicon wafer was pre-baked at 140 ° C. for 5 minutes.
  • Each silicon wafer after thermal diffusion was immersed in a 5 wt% hydrofluoric acid aqueous solution at 23 ° C. for 1 minute to peel off the diffusing agent and the mask. After peeling, the silicon wafer was immersed in pure water and washed, and the presence or absence of a residue was observed by visual inspection of the surface. Surface deposits can be confirmed visually after immersion for 1 minute, and those that cannot be removed by rubbing with waste are inferior. Those that can be visually confirmed after immersion for 1 minute can be removed by rubbing with waste. bad (impossible), more than 30 seconds, the surface deposits could not be visually confirmed within 1 minute, good (good), those in which the surface deposits could not be visually confirmed within 30 seconds, excellent (excellent) . Although good (good) can be used from the viewpoint of production tact, it is preferable to be excellent.
  • the silicon wafer after diffusion used for peelability evaluation is determined by p / n using a p / n determination device, and the surface resistance is measured by a four-probe type surface resistance measuring device RT-70V (Napson Sheet resistance value).
  • the sheet resistance value is an index of impurity diffusivity, and a smaller resistance value means a larger amount of impurity diffusion.
  • a sheet resistance value of 40 to 70 ( ⁇ / ⁇ ) is excellent, 71 to 100 ( ⁇ / ⁇ ) is good (good), and 101 ( ⁇ / ⁇ ) or more is bad. It was.
  • the surface concentration distribution of impurities was measured using a secondary ion mass spectrometer IMS7f (manufactured by Camera) on the silicon wafer after diffusion used for sheet resistance measurement. 10 points of surface concentration are read from the obtained surface concentration distribution at intervals of 100 ⁇ m, and the ratio between the average and the standard deviation is calculated as “standard deviation / average”, and the “standard deviation / average” is 0.3 or less. Excellent (excellent), above 0.3 and below 0.6 (good), above 0.6 and below 1.0 bad (impossible), above 1.0 above (inferior) ). The variation in the surface concentration of the impurities greatly affects the power generation efficiency, and thus is most preferably excellent.
  • a p-type impurity diffusion composition is applied to the n-type silicon wafer 61 by a known spin coating method so that the pre-baked film thickness is about 500 nm.
  • a film 62 was formed.
  • the n-type silicon wafer was pre-baked at 140 ° C. for 5 minutes to prepare a p-type impurity diffusion composition-coated substrate.
  • an n-type impurity diffusive composition (OCD T-1, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is prepared by a known spin coating method so that the pre-baked film thickness becomes about 500 nm.
  • the n-type impurity diffusion composition film 64 was formed by coating the n-type silicon wafer 61. After the formation, the n-type silicon wafer was pre-baked at 140 ° C. for 5 minutes to prepare an n-type impurity diffusion composition coated substrate.
  • the p-type impurity diffusion composition-coated substrate and the n-type impurity diffusion composition-coated substrate were placed in an electric furnace facing each other with an interval of 5 mm.
  • each n-type silicon wafer was immersed in a 5% by weight hydrofluoric acid aqueous solution at 23 ° C. for 1 minute to peel the cured diffusing agent (FIG. 6 (e)).
  • the surface concentration distribution of the phosphorus element was measured using a secondary ion mass spectrometer IMS7f (manufactured by Camera) for the p-type impurity diffusion composition coated substrate thermally diffused and peeled.
  • a lower phosphorus element surface concentration means a higher barrier property to the diffusing phosphorus element from the facing n-type impurity diffusion composition.
  • the surface concentration of the obtained phosphorus element is 10 17 atoms / cm 3 or less, it is excellent (excellent), 10 17 atoms / cm 3 is higher than 10 18 atoms / cm 3 and 10 18 atoms / cm 3 or less is good (good), 10 18 atoms. Those exceeding / cm 3 were judged as bad (impossible).
  • Example 1 (1) Synthesis of polysiloxane solution In a 1000 mL three-necked flask, 164.93 g (1.21 mol) of KBM-13 (Shin-Etsu Chemical Co., Ltd., MeTMS) and 204.93 KBM-103 (Shin-Etsu Chemical Co., Ltd., PhTMS) were added. 07 g (1.21 mol) and 363.03 g of ⁇ -BL were charged, and an aqueous formic acid solution in which 0.1.215 g of formic acid was dissolved in 130.76 g of water was added over 30 minutes while stirring at 40 ° C. After completion of dropping, the mixture was stirred at 40 ° C. for 1 hour, then heated to 70 ° C.
  • the viscosity of the p-type impurity diffusion composition A obtained above was the result shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, and barrier property were measured using the obtained p-type impurity diffusion composition A, all showed good results as shown in Table 2.
  • Impurity diffusion composition B was obtained in the same manner as Example 1. Using the resulting impurity diffusion composition B, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results. In addition, the weight average molecular weight (Mw) of the polysiloxane in the used polysiloxane solution was 2300.
  • Impurity diffusion composition C was obtained in the same manner as in Example 1. Using the resulting impurity diffusion composition C, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results.
  • the weight average molecular weight (Mw) of the polysiloxane in the used polysiloxane solution was 2500.
  • Impurity diffusion composition D was obtained in the same manner as in Example 1.
  • the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured using the obtained impurity diffusion composition D, all showed good results as shown in Table 2.
  • the weight average molecular weight (Mw) of the polysiloxane in the used polysiloxane solution was 3100.
  • Impurity diffusion composition E was obtained in the same manner as Example 1. Using the resulting impurity diffusion composition E, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results. In addition, the weight average molecular weight (Mw) of the polysiloxane in the used polysiloxane solution was 3400.
  • Examples 1 to 5 those having an aryl group ratio of 40 mol% or more in the polysiloxane were excellent in diffusion uniformity, and those having an aryl group ratio of 80 mol% or less showed particularly good peelability. As for the barrier property, all of Examples 1 to 5 showed good results.
  • Example 6 An impurity diffusion composition F was obtained in the same manner as in Example 1 except that MeTMS was changed to PhTMS in the raw material for obtaining the p-type impurity diffusion component. Using the obtained impurity diffusion composition F, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured, and as shown in Table 2, all showed good results.
  • Example 7 Impurity diffusion composition G was obtained in the same manner as in Example 1 except that MeTMS was changed to DMeDMS (manufactured by Shin-Etsu Chemical Co., Ltd.) as a raw material for obtaining a p-type impurity diffusion component. Using the obtained impurity diffusion composition G, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results.
  • Example 8 In preparation of the p-type impurity diffusion composition, the polysiloxane solution synthesized in (1) above was changed to 10.03 g, and the p-type impurity solution A synthesized in (2) was changed to 22.89 g. Obtained an impurity diffusion composition K in the same manner as in Example 1. Using the resulting impurity diffusion composition K, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results.
  • Impurity diffusion composition L was obtained in the same manner as in Example 1 except that it was changed to MeTMS (5 mol%) / PhTMS (95 mol%). Using the resulting impurity diffusion composition L, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results.
  • Impurity diffusion composition M was obtained in the same manner as in Example 1 except that it was changed to MeTMS (20 mol%) / PhTMS (80 mol%). Using the obtained impurity diffusion composition M, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results.
  • Impurity diffusion composition N was obtained in the same manner as in Example 1 except that it was changed to MeTMS (50 mol%) / PhTMS (50 mol%). Using the resulting impurity diffusion composition N, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results.
  • Impurity diffusion composition O was obtained in the same manner as in Example 1 except that it was changed to MeTMS (80 mol%) / PhTMS (20 mol%). Using the resulting impurity diffusion composition O, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results.
  • Impurity diffusion composition P was obtained in the same manner as in Example 1 except that it was changed to MeTMS (95 mol%) / PhTMS (5 mol%). Using the obtained impurity diffusion composition P, the peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all showed good results.
  • Impurity diffusion composition H was obtained in the same manner as in Example 1 except that boric acid was used as the p-type impurity diffusion component. The solubility of boric acid in the polysiloxane solution A was low, and white precipitation occurred. Using the obtained impurity diffusion composition H, the peelability, sheet resistance value, diffusion uniformity, and barrier property were measured. As shown in Table 2, the sheet resistance value was high and the diffusion uniformity was poor. It was.

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Abstract

L'objet de la présente invention est de proposer une composition de diffusion d'impuretés de type p qui présente une excellente diffusivité dans des substrats semi-conducteurs, tout en présentant des propriétés de barrière suffisantes contre des impuretés de type n. Afin d'atteindre l'objet décrit ci-dessus, la présente invention possède la configuration suivante. À savoir, une composition de diffusion d'impuretés de type p qui contient (A) un polysiloxane et (B) un composant de diffusion d'impuretés de type p ayant une liaison Si-O-B.
PCT/JP2016/078193 2015-09-29 2016-09-26 COMPOSITION DE DIFFUSION D'IMPURETÉS DE TYPE p, PROCÉDÉ DE FABRICATION D'ÉLÉMENT SEMI-CONDUCTEUR L'UTILISANT, ET PROCÉDÉ DE FABRICATION DE CELLULE SOLAIRE Ceased WO2017057238A1 (fr)

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JP2016560609A JP6772836B2 (ja) 2015-09-29 2016-09-26 ｐ型不純物拡散組成物、それを用いた半導体素子の製造方法および太陽電池の製造方法
KR1020187006711A KR20180063056A (ko) 2015-09-29 2016-09-26 p형 불순물 확산 조성물, 그것을 사용한 반도체 소자의 제조 방법 및 태양 전지의 제조 방법

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JP7647100B2 (ja) * 2019-09-26 2025-03-18 東レ株式会社 不純物拡散組成物、それを用いた半導体素子の製造方法および太陽電池の製造方法
CN113314674A (zh) * 2020-02-26 2021-08-27 东丽先端材料研究开发（中国）有限公司 用于太阳能电池或半导体的可印刷p型掺杂浆料以及掺杂方法

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