WO2019176716A1 - Composition de diffusion d'impuretés , procédé de production de dispositif semi-conducteur l'utilisant, et procédé de fabrication de cellule solaire - Google Patents

Composition de diffusion d'impuretés , procédé de production de dispositif semi-conducteur l'utilisant, et procédé de fabrication de cellule solaire Download PDF

Info

Publication number
WO2019176716A1
WO2019176716A1 PCT/JP2019/009064 JP2019009064W WO2019176716A1 WO 2019176716 A1 WO2019176716 A1 WO 2019176716A1 JP 2019009064 W JP2019009064 W JP 2019009064W WO 2019176716 A1 WO2019176716 A1 WO 2019176716A1
Authority
WO
WIPO (PCT)
Prior art keywords
impurity diffusion
type impurity
diffusion composition
group
carbon atoms
Prior art date
Application number
PCT/JP2019/009064
Other languages
English (en)
Japanese (ja)
Inventor
北田剛
弓場智之
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN201980015220.2A priority Critical patent/CN111771258B/zh
Priority to JP2019514047A priority patent/JP7172994B2/ja
Publication of WO2019176716A1 publication Critical patent/WO2019176716A1/fr

Links

Images

Classifications

    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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 an 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 coating solution containing a boron compound and a hydroxyl group-containing polymer compound such as polyvinyl alcohol is usually applied to the surface of a semiconductor substrate using a spin coating method or a screen printing method. And thermally diffused (see, for example, Patent Document 1).
  • the coating solution to which a polyhydric alcohol as described in Patent Document 2 is added has a problem that it is inferior in impurity diffusion uniformity.
  • the present invention has been made based on the above-described circumstances, and is excellent in storage stability of a coating liquid, and can improve continuous printability during screen printing and can be uniformly diffused into a semiconductor substrate.
  • An object is to provide an impurity diffusion composition.
  • the impurity diffusion composition of the present invention has the following constitution. That is, the impurity diffusion composition of the present invention comprises (A) a polymer containing at least one structure selected from the following general formulas (1) and (2) in the side chain (hereinafter referred to as (A) polymer), and (B) Contains an impurity diffusion component.
  • R 1 to R 14 each independently represents a hydrogen atom or an organic group having 1 to 8 carbon atoms.
  • a 1 represents an integer of 1 to 4
  • a 2 and a 3 each independently represents an integer of 0 to 2.
  • a 2 + a 3 represents an integer of 0 to 3. * Represents a bonding part with a polymer.
  • an impurity diffusion composition that is excellent in storage stability, improves continuous printability during screen printing, and enables uniform diffusion to a semiconductor substrate.
  • the impurity diffusion composition of the present invention may be referred to as (A) a polymer containing at least one structure selected from general formulas (1) and (2) in the side chain (hereinafter, simply referred to as “(A) polymer”). And (B) an impurity diffusion component.
  • R 1 to R 14 each independently represents a hydrogen atom or an organic group having 1 to 8 carbon atoms.
  • a 1 represents an integer of 1 to 4
  • a 2 and a 3 each independently represents an integer of 0 to 2.
  • a 2 + a 3 represents an integer of 0 to 3. * Represents a bonding part with a polymer.
  • the (A) polymer reacts with the (B) impurity diffusion component to form, for example, a complex, thereby forming a uniform coating film when the composition is applied. It is a component that makes it possible. Thereby, it is possible to uniformly diffuse impurities into the semiconductor substrate.
  • the reaction product of (A) the polymer and (B) the impurity diffusing component is soluble in an organic solvent
  • the impurity diffusing agent composition of the present invention may not contain a large amount of water. Therefore, while suppressing deterioration of the performance of the solar cell, it is excellent in the storage stability of the coating liquid, improves continuous printability during screen printing, and enables uniform diffusion to the semiconductor substrate.
  • the polymer in the present invention can contain an oligomer, and specifically refers to a polymer having a degree of polymerization of 2 or more.
  • the degree of polymerization is preferably 2 to 100, more preferably 5 to 50.
  • the content of the polymer (A) in the impurity diffusion composition of the present invention is determined by the coating method and the required resistance value, but is preferably 0.01 to 50% by mass relative to the total amount of the impurity diffusion composition. 1 to 20% by mass is more preferable.
  • Examples of the organic group having 1 to 8 carbon atoms in R 1 to R 14 include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be either unsubstituted or substituted, 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, 3,3-trifluoropropyl group, 3-methoxy-n-propyl group, glycidyl group, 3-glycidoxypropyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, etc.
  • a methyl group of 4 carbon atoms or less, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a t-butyl group is preferable.
  • alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group and the like.
  • the polymer is preferably a polymer made of siloxane or acrylic from the viewpoint of (B) the formation of a complex with an impurity diffusion component and the stability of the formed complex.
  • the polymer (A) is preferably a polymer composed of siloxane, and a partial structure represented by any one of the general formulas (3) and (4) More preferably, the polymer is a polymer composed of siloxane containing at least one of the partial structures represented by any one of the general formulas (5) and (6).
  • R 15 represents an alkylene group having 1 to 8 carbon atoms.
  • R 16 represents 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 alkenyl group having 2 to 10 carbon atoms, and an acyl group having 2 to 6 carbon atoms.
  • R 17 and R 18 are a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an alkyl group having 6 to 15 carbon atoms.
  • X represents at least one structure selected from the general formulas (1) and (2). The proportion of the partial structure represented by any one of the general formulas (3) and (4) in the siloxane structure is 5 to less than 100 mol%.
  • At least one structure selected from the general formulas (1) and (2) is obtained by setting the proportion of the partial structure represented by any one of the general formulas (3) and (4) in the siloxane structure to 5% or more. And (B) the impurity diffusion component sufficiently forms a complex, and the diffusibility of impurities is further improved.
  • R 17 is an aryl group having 6 to 15 carbon atoms, and the proportion of the partial structure represented by any one of the general formulas (5) and (6) in the siloxane structure is 5 to 95 mol%. However, it is more preferable from the viewpoint of masking properties against different impurities and suppression of impurity out-diffusion, and more preferably from 10 to 90 mol% from the viewpoint of peelability of the diffusing agent and mask after thermal diffusion.
  • the proportion of the partial structure represented by any one of the general formulas (5) and (6) in the siloxane structure is set to 5 mol% or more, the crosslinking density between the siloxane skeletons does not become too high, and even a thick film is cracked. Is more suppressed. As a result, cracks are less likely to occur in the firing and thermal diffusion processes, so that the stability of impurity diffusion can be improved.
  • the impurity diffusion layer can be used as a mask for other impurity diffusing agents after the thermal diffusion of the impurities. In order to provide masking properties, it is better that the film thickness after diffusion is large, and the impurity diffusion composition of the present invention can be suitably used even if a thick film is difficult to crack.
  • a thermal decomposition component such as a thickener
  • the proportion of the partial structure represented by any one of the general formulas (3) and (4) in the siloxane structure is, for example, measured by 29 Si-NMR spectrum of polysiloxane, and the peak area of Si bonded to X and X It can be determined from the ratio of the peak areas of Si not bonded.
  • the proportion of the partial structure represented by any one of the general formulas (5) and (6) in the siloxane structure is determined by, for example, measuring the 29 Si-NMR spectrum of polysiloxane and the peak area of Si bonded with an aryl group. It can be determined from the ratio of the peak areas of Si to which no aryl group is bonded.
  • Examples of the alkylene group having 1 to 8 carbon atoms in R 15 include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a heptylene group, and an octylene group.
  • the aryl group having 6 to 15 carbon atoms in R 17 and R 18 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 alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the acyloxy group having 2 to 6 carbon atoms are all unsubstituted in R 16 , R 17 and R 18 . , Either of which can be selected, and can be selected according to the characteristics of the composition.
  • alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms are the same as those in R 1 to R 14 .
  • 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.
  • acyloxy group having 2 to 6 carbon atoms include an acetoxy group, a propionyloxy group, an acryloyloxy group, and the like.
  • organosilane used as the raw material of the unit having R 15 , R 16 and X having a partial structure represented by any one of the general formulas (3) and (4) include TMSOX (trimethoxysilyloxetane, Toagosei ( Co.), TESOX (triethoxysilyloxetane, Toagosei Co., Ltd.) is preferable.
  • organosilane used as a raw material for the unit having R 17 and R 18 having the partial structure represented by any one of the general formulas (5) and (6) include phenyltrimethoxysilane, phenyltriethoxysilane, p- Hydroxyphenyltrimethoxysilane, p-tolyltrimethoxysilane, p-styryltrimethoxysilane, p-methoxyphenyltrimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane 1-naphthyltriethoxysilane and 2-naphthyltriethoxysilane are preferable, and phenyltrimethoxysilane, p-tolyltrimethoxysilane, and p-methoxyphen
  • the structure of the general formula (1) or (2) can be expressed by the ring opening of the oxetane structure in the organosilane used as a raw material.
  • the structure of the general formula (1) or (2) and the (B) impurity diffusion component sufficiently form a complex, and good diffusibility can be obtained.
  • the ring opening rate of oxetane is preferably 5% or more.
  • Various conditions for the hydrolysis reaction such as the content of the acid catalyst, the reaction temperature, the reaction time, etc. can be appropriately set in consideration of the reaction scale, the size, shape, etc. of the reaction vessel. It is preferable that an acid catalyst and water are added to the organosilane compound over 1 to 180 minutes, and then reacted at 20 to 110 ° C. for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed.
  • the reaction temperature is more preferably 30 to 130 ° C.
  • 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 does not contain atoms other than silicon, hydrogen, carbon, oxygen, nitrogen, and phosphorus as much as possible from the viewpoint of doping, and acid catalysts of phosphoric acid, formic acid, acetic acid, and various carboxylic acids are used. Is preferred. Of these, phosphoric 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 compound used in the hydrolysis reaction.
  • the solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. In addition, two or more solvents may be combined, or the reaction may be performed without solvent.
  • diethylene glycol methyl ethyl ether diethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, diacetone alcohol, propylene glycol monomethyl ether acetate, 3-methoxy -3-methyl-1-butanol, dipropylene glycol monomethyl ether, dipropylene glycol-n-butyl ether, ⁇ -butyrolactone, diethylene glycol monoethyl ether acetate, butyl diglycol acetate, ethyl acetoacetate, N-methyl-2-pyrrolidone, N, N-dimethylimidazolidinone, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacete DOO, diisobutyl ketone, propylene glycol t- butyl ether, can be
  • 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 compound. 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.
  • Polymer made of acrylic As a polymer, the polymer which consists of an acryl each including the partial structure shown by General formula (7) and the partial structure shown by General formula (8) is also preferable.
  • R 19 and R 21 each independently represents a hydrogen atom, a halogen, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms.
  • R 20 represents an alkylene group having 1 to 8 carbon atoms.
  • R 22 represents an alkyl group having 1 to 4 carbon atoms.
  • X represents at least one structure selected from the general formulas (1) and (2). a 4 and a 5 represent an integer of 0 or 1, and at least one of a 4 and a 5 is 1. The proportion of the partial structure represented by the general formula (7) in the acrylic structure is 5 to less than 100 mol%.
  • Examples of the alkyl group having 1 to 4 carbon atoms in R 19 and R 21 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group.
  • Examples of the fluoroalkyl group having 1 to 4 carbon atoms include a trifluoromethyl group and a 3,3,3-trifluoropropyl group.
  • Examples of the alkylene group having 1 to 8 carbon atoms in R 20 include a methylenemethylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a heptylene group, and an octylene group.
  • Examples of the alkyl group having 1 to 4 carbon atoms in R 22 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group.
  • acrylic monomer used as a raw material for the unit having R 19 , R 20 and X having a partial structure represented by the general formula (7) include (3-ethyloxetane-3-yl) methyl acrylate (Osaka Organic Chemical Industry) Co., Ltd.).
  • a specific example of the acrylic monomer that is a raw material of the unit having R 21 and R 22 having the partial structure represented by the general formula (8) includes acrylic acid.
  • the radical polymerization initiator include azobisisobutyronitrile.
  • the solvent is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. In addition, two or more solvents may be combined, or the reaction may be performed without solvent. Specific examples of the solvent include those similar to the siloxane polymerization.
  • the (B) impurity diffusion component is a component for forming an impurity diffusion layer in the semiconductor substrate.
  • the p-type impurity diffusion component is preferably a compound containing an element belonging to Group 13, particularly preferably a boron compound.
  • boron compounds include boric acid, diboron trioxide, methyl boronic acid, phenyl boronic acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trioctyl borate, triphenyl borate and the like. it can.
  • the n-type impurity diffusion component is preferably a compound containing a Group 15 element, and more preferably a phosphorus compound.
  • Phosphorus compounds include diphosphorus pentoxide, phosphoric acid, polyphosphoric acid, methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, propyl phosphate, dipropyl phosphate, phosphoric acid Phosphoric esters such as tripropyl, butyl phosphate, dibutyl phosphate, tributyl phosphate, phenyl phosphate, diphenyl phosphate, triphenyl phosphate, methyl phosphite, dimethyl phosphite, trimethyl phosphite, Ethyl phosphate, diethyl phosphite, triethyl phosphite, propyl phosphite, dipropyl phosphite, tripropyl phosphite, butyl phosphite, dibutyl pho
  • the amount of the (B) impurity diffusion component contained in the impurity diffusion composition can be arbitrarily determined according to the resistance value required for the semiconductor substrate, but is 0.1 to 10% by mass with respect to the total amount of the impurity diffusion composition. Is preferred.
  • the impurity diffusion composition of the present invention preferably contains a solvent.
  • the solvent can be used without any particular limitation, but is preferably a solvent having a boiling point of 100 ° C. or higher from the viewpoint of further improving printability when using a screen printing method, a spin coat printing method, or the like.
  • the boiling point is 100 ° C. or more, for example, when the impurity diffusion composition is printed on a printing plate used in the screen printing method, it is possible to suppress the impurity diffusion composition from being dried and fixed on the printing plate.
  • the content of the solvent having a boiling point of 100 ° C. or higher is preferably 20% by weight or more with respect to the total amount of the solvent.
  • the impurity diffusion composition of the present invention may contain a surfactant. By containing the surfactant, coating unevenness is improved, and a more uniform coating film can be obtained.
  • a surfactant a fluorine-based surfactant or a silicone-based surfactant is preferably used. When added, the content of the surfactant is preferably 0.0001 to 1% by weight in the impurity diffusion composition.
  • the impurity diffusion composition of the present invention preferably contains a thickener for viscosity adjustment. Thereby, it can apply
  • the thickener preferably has a 90% thermal decomposition temperature of 400 ° C. or less from the viewpoint of dense film formation and residue reduction. Specifically, polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, and acrylate resin are preferable, and polyethylene oxide, polypropylene oxide, and acrylate resin are particularly 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.
  • the content of these thickeners is preferably 3% by weight or more and 20% by weight or less in the impurity diffusion composition. By being in this range, a sufficient viscosity adjusting effect can be easily obtained, and at the same time, a denser film can be formed.
  • the impurity diffusion composition of the present invention preferably contains a thixotropic agent imparting thixotropy from the viewpoint of screen printability.
  • imparting thixotropy means increasing the ratio ( ⁇ 1 / ⁇ 2 ) of the viscosity at the time of low shear stress ( ⁇ 1 ) and the viscosity at the time of high shear stress ( ⁇ 2 ).
  • a thixotropic agent By containing a thixotropic agent, the pattern accuracy of screen printing can be further increased. The reason is as follows.
  • Impurity diffusion compositions containing thixotropic agents are low in viscosity at high shear stress, so screen clogging is unlikely to occur during screen printing, and high viscosity at low shear stress, so that bleeding immediately after printing and pattern line width increase Is less likely to occur.
  • the viscosity of the 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 viscosity of the diffusion composition is preferably 5,000 mPa ⁇ s or more. This is because blurring of the print pattern can be suppressed and a good pattern can be obtained.
  • a more preferable viscosity is 10,000 mPa ⁇ s or more. Although there is no particular upper limit, 100,000 mPa ⁇ s or less is preferable from the viewpoint of storage stability and handleability.
  • the viscosity is less than 1,000 mPa ⁇ s, it is a value measured at a rotational speed of 20 rpm using an E-type digital viscometer based on JIS Z 8803 (1991) “Solution Viscosity—Measurement Method”
  • 1,000 mPa ⁇ s or more it is a value measured at a rotation speed of 20 rpm using a B-type digital viscometer based on JIS Z 8803 (1991) “Solution Viscosity—Measurement Method”.
  • the thixotropy can be determined from the ratio of viscosities at different rotational speeds obtained by the above viscosity measurement method.
  • the ratio ( ⁇ 2 / ⁇ 20 ) of the viscosity ( ⁇ 20 ) at a rotational speed of 20 rpm and the viscosity ( ⁇ 2 ) at a rotational speed of 2 rpm is defined as thixotropy.
  • the thixotropy is preferably 2 or more, and more preferably 3 or more.
  • the solid content concentration of the impurity diffusion composition of the present invention is not particularly limited, but is preferably in the range of 1% by weight to 90% by weight. If it is lower than this concentration range, the coating film thickness becomes too thin and it is difficult to obtain desired doping properties and mask properties. If it is higher than this concentration range, the storage stability may be lowered.
  • a first embodiment of a method for manufacturing a semiconductor device of the present invention includes a step of applying an impurity diffusion composition of the present invention to a semiconductor substrate to form an impurity diffusion composition film, and impurities from the impurity diffusion composition film. A step of diffusing and forming an impurity diffusion layer in the semiconductor substrate.
  • the second embodiment of the method for manufacturing a semiconductor device of the present invention includes a step of applying an n-type impurity diffusion composition to a semiconductor substrate to form an n-type impurity diffusion composition film, and a p-type after the step.
  • the third embodiment of the method for producing a semiconductor device of the present invention is a p-type impurity diffusion composition on one surface of a semiconductor substrate, and (B) the impurity diffusion of the present invention wherein the impurity diffusion component is a boron compound.
  • a method of manufacturing a semiconductor element comprising: forming a p-type impurity diffusion layer and an n-type impurity diffusion layer simultaneously on the semiconductor substrate by heating the semiconductor substrate.
  • the fourth embodiment of the method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor device using a plurality of semiconductor substrates, and includes the following steps (a) to (c): In the processes (c) and (c), a set of two semiconductor substrates are arranged so that the surfaces on which the first conductivity type impurity diffusion composition films are formed face each other.
  • B heating the semiconductor substrate on which the first conductivity type impurity diffusion composition film is formed, diffusing the first conductivity type impurity into the semiconductor substrate, and forming a first conductivity type impurity diffusion layer; Forming step.
  • C heating the semiconductor substrate in an atmosphere having a gas containing a second conductivity type impurity, diffusing the second conductivity type impurity on the other surface of the semiconductor substrate, Forming a diffusion layer;
  • FIG. 1 shows an example of a first embodiment of a method for manufacturing a semiconductor device of the present invention.
  • a p-type impurity diffusion composition film 12 is formed on a semiconductor substrate 11.
  • the semiconductor substrate for example, an n-type single crystal silicon having an impurity concentration of 10 15 to 10 16 atoms / cm 3 , polycrystalline silicon, and a crystalline silicon substrate mixed with other elements such as germanium and carbon are used. Can be mentioned. It is also possible to use p-type crystalline silicon or a semiconductor other than silicon.
  • the semiconductor substrate is preferably a substantially quadrangular 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.
  • 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 method for applying the impurity diffusion composition include spin coating, screen printing, ink jet printing, slit coating, spray coating, letterpress printing, and intaglio printing.
  • the impurity diffusion composition film 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 impurity diffusion composition film after drying is preferably 100 nm or more from the viewpoint of impurity diffusivity, and preferably 3 ⁇ m or less from the viewpoint of residues after etching.
  • impurities are diffused into the semiconductor substrate 11 to form a p-type impurity diffusion layer 13.
  • the impurity diffusion method 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 diffusion layer having a surface impurity concentration of 10 19 to 10 21 can be formed by heat diffusion for 1 to 120 minutes at 800 ° C. to 1200 ° C.
  • 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 12 formed on the surface of the semiconductor substrate 11 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.
  • the p-type impurity diffusion composition film is used to form the p-type impurity diffusion layer.
  • the present embodiment is not limited to this, and the n-type impurity diffusion composition film is used.
  • the present invention can also be applied to the case where an n-type impurity diffusion layer is formed using the above-described method.
  • the solar cell obtained in one example of this embodiment is a single-sided power generation type solar cell.
  • a passivation layer 16 is formed on the front surface, and a passivation layer 17 is formed on the back surface.
  • Each known material can be used for the passivation layer.
  • These layers may be a single layer or a plurality of layers.
  • an aluminum oxide layer is particularly preferable. This also serves as an electrode.
  • passivation layers can be formed by a vapor deposition method such as a plasma CVD method, an ALD (atomic layer deposition) method, or a coating method.
  • a vapor deposition method such as a plasma CVD method, an ALD (atomic layer deposition) method, or a coating method.
  • the passivation layer 16 is formed on a part of the light receiving surface, and the passivation layer 17 is formed on the entire back surface.
  • a contact electrode 18 is formed on a portion of the light receiving surface where the passivation layer 16 does not exist.
  • the electrode can be formed by applying heat treatment after applying the electrode forming paste.
  • FIG. 2A shows an example of the second embodiment of the method for manufacturing a semiconductor device of the present invention.
  • an n-type impurity diffusion composition film 24 is formed on the semiconductor substrate 21 in a pattern.
  • Examples of the method for forming the n-type impurity diffusion composition film include screen printing, ink jet printing, slit coating, spray coating, letterpress printing, and intaglio printing.
  • the coating film After forming the coating film by these methods, it is preferable to dry the n-type impurity diffusion composition film 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 n-type impurity diffusion composition film after drying is preferably 200 nm or more in consideration of the masking property for p-type impurities, and preferably 5 ⁇ m or less from the viewpoint of crack resistance.
  • a p-type impurity diffusion composition film 22 is formed using the n-type impurity diffusion composition film 24 as a mask.
  • the p-type impurity diffusion composition film may be formed on the entire surface, or may be formed only on the portion where there is no n-type impurity diffusion composition film. Moreover, you may apply
  • 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 After forming the coating film by these methods, it is preferable to dry the p-type impurity diffusion composition film 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 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.
  • the n-type impurity diffusion component in the n-type impurity diffusion composition film 24 and the p-type impurity diffusion component in the p-type impurity diffusion composition film 22 are simultaneously formed into a semiconductor.
  • An n-type impurity diffusion layer 25 and a p-type impurity diffusion layer 23 are formed by diffusing into the substrate 21.
  • impurity diffusion composition coating method examples include the same methods as described above.
  • the n-type impurity diffusion composition film 24 and the p-type impurity diffusion composition film 22 formed on the surface of the semiconductor substrate 21 are removed by a known etching method.
  • n-type and p-type impurity diffusion layers can be formed in the semiconductor substrate.
  • 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. It is also possible to do this. That is, the p-type impurity diffusion composition is applied instead of the n-type impurity diffusion composition in FIG. 2A (a), and the p-type impurity diffusion composition is applied and diffused in FIG. 2A (b). It is also possible to apply an n-type impurity diffusion composition.
  • the solar cell obtained in one example of this embodiment is a back junction solar cell.
  • a protective film 26 is formed on the entire surface of the semiconductor substrate 21 having the n-type impurity diffusion layer 25 and the p-type impurity diffusion layer 23 formed on the back surface.
  • the protective film 26 is patterned by an etching method or the like to form a protective film opening 26a.
  • the n-type contact electrode 29 and the p-type contact are formed by applying a pattern of electrode paste to the region including the opening 26a and baking it by a stripe coating method or a screen printing method. Electrode 28 is formed. Thereby, the back junction solar cell 20 is obtained.
  • FIG. 3A shows an example of the third embodiment of the method for manufacturing a semiconductor device of the present invention.
  • a p-type impurity diffusion composition film 32 is formed on a semiconductor substrate 31 using the p-type impurity diffusion composition of the present invention.
  • an n-type impurity diffusion composition film 34 is formed on the surface of the semiconductor substrate 31 opposite to the surface on which the p-type impurity diffusion composition film 32 is formed.
  • the p-type impurity diffusion composition film 32 and the n-type impurity diffusion composition film 34 are simultaneously diffused into the semiconductor substrate 31, and the p-type impurity diffusion layer 33 and the n-type impurity diffusion layer 33 are diffused.
  • An impurity diffusion layer 35 is formed.
  • impurity diffusion composition coating method examples include the same methods as described above.
  • the p-type impurity diffusion composition film 32 and the n-type impurity diffusion composition film 34 formed on the surface of the semiconductor substrate 31 are removed by a known etching method.
  • n-type and p-type impurity diffusion layers can be formed in the semiconductor substrate.
  • a process can be simplified compared with the conventional method.
  • 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 solar cell obtained in one example of this embodiment is a double-sided power generation type solar cell.
  • a passivation layer 36 is formed on each of the light receiving surface and the back surface.
  • the material used for the passivation layer As the material used for the passivation layer, the layer configuration, and the formation method, the same applies as in the first embodiment.
  • the passivation layer 36 is formed in a partial region of the light receiving surface and the back surface.
  • the p-type contact electrode 38 and the n-type contact electrode 39 are formed on the light-receiving surface and the back surface, respectively, in the portions where the passivation layer 36 does not exist.
  • the electrode can be formed by applying heat treatment after applying the electrode forming paste.
  • FIG. 4 shows an example of the fourth embodiment of the method for manufacturing a semiconductor device of the present invention.
  • Step (a) As shown in FIG. 4A, a first conductivity type impurity diffusion composition is applied to one surface of a semiconductor substrate 41 to form a first conductivity type impurity diffusion composition film.
  • the first conductivity type is assumed to be p-type
  • the second conductivity type is assumed to be n-type. That is, the first conductivity type impurity diffusion composition film is a p-type impurity diffusion composition film.
  • the first conductivity type and the second conductivity type may be reversed.
  • FIG. 4A illustrates an embodiment in which the p-type impurity diffusion composition is applied to the entire surface of one surface of the semiconductor substrate
  • the p-type impurity diffusion composition may be partially applied.
  • Examples of the method for applying and baking the impurity diffusion composition include the same methods as described above.
  • a pair of semiconductor substrates 41 each having a p-type impurity diffusion composition film 42 formed on one surface are formed into a pair.
  • the diffusion board has a groove for placing the semiconductor substrate. There are no particular restrictions on the size and pitch of the grooves of the diffusion board.
  • the diffusion board may be inclined with respect to the horizontal direction.
  • the material of the diffusion board is not particularly limited as long as it can withstand the diffusion temperature, but quartz is preferable.
  • the diffusion board 110 on which the semiconductor substrate 41 is disposed is heated in the diffusion furnace 100 to diffuse p-type impurities into the semiconductor substrate 41, thereby forming a p-type impurity.
  • An impurity diffusion layer 43 is formed.
  • the p-type impurity diffusion composition film of the semiconductor substrate does not disappear. It is difficult to reach the surface opposite to the surface on which is formed. Therefore, it is possible to suppress so-called out diffusion in which impurities are diffused in a portion different from the target portion in the semiconductor substrate.
  • Examples of the diffusion method of the impurity diffusion composition include the same methods as described above.
  • a semiconductor substrate having a p-type impurity diffusion composition film formed on one surface is heated at a temperature lower than the heat treatment temperature during diffusion and in an atmosphere containing oxygen. It is preferable to remove at least a part of organic components such as the binder resin in the p-type impurity diffusion composition film by the treatment. By removing at least part of the organic component such as the binder resin in the p-type impurity diffusion composition film, the concentration of the impurity component in the p-type impurity diffusion composition film on the semiconductor substrate can be increased, It is easy to improve the diffusibility of p-type impurities.
  • the n-type impurity diffusion layer 45 is formed by heating the semiconductor substrate while flowing a gas containing n-type impurities.
  • gas containing n-type impurities is POCl 3 gas.
  • POCl 3 gas and bubbling N 2 gas or nitrogen / oxygen mixed gas to the POCl 3 solution can be obtained by heating the POCl 3 solution.
  • gas such as BBr 3 or BCl 3 can be used.
  • the heating temperature is preferably 750 ° C. to 1050 ° C., more preferably 800 ° C. to 1000 ° C.
  • the gas atmosphere is not particularly limited, but is preferably a mixed gas atmosphere such as nitrogen, oxygen, argon, helium, xenon, neon, krypton, more preferably a mixed gas of nitrogen and oxygen, containing oxygen Particularly preferred is a mixed gas of nitrogen and oxygen having a rate of 5% by volume or less.
  • the process time for changing the gas atmosphere can be shortened, it is preferable to perform the process (c) with the same gas atmosphere as the process (b).
  • the ratio of nitrogen and oxygen in the gas atmosphere in step (b) is preferably the same as the ratio of nitrogen and oxygen in the gas atmosphere in step (c).
  • step (B) After the step (b), the heat treatment product layer of the p-type impurity diffusion composition film remains on the p-type impurity diffusion layer.
  • the step (c) is preferably performed using this as a mask against a gas containing n-type impurities. By doing so, it is possible to suppress the mixing of n-type impurities into the p-type impurity diffusion layer.
  • step (b) or the step (c) may be performed first, and the step (c) may be performed simultaneously with the step (b).
  • the step (c) is preferably performed after the step (b).
  • Performing the step (c) continuously after the step (b) means performing the step (c) following the step (b).
  • the heating temperature when forming the n-type impurity diffusion layer in the step (c) is 50 to 200 ° C. higher than the heating temperature when forming the p-type impurity diffusion layer in the step (b). A low temperature is preferred.
  • the heating temperature when forming the n-type impurity diffusion layer in the step (c) is 50 to 200 ° C. lower than the heating temperature when forming the p-type impurity diffusion layer in the step (b).
  • the first conductivity type is p-type because the heating temperature is lower when diffusing with a gas containing n-type impurities than when diffusing with a gas containing p-type impurities.
  • the second conductivity type is preferably n-type.
  • the manufacturing method of the solar cell of the present invention includes the manufacturing method of the semiconductor element of the present invention, and specifically, the first conductivity type impurity diffusion layer and the second conductivity type obtained by the above-described steps. Forming an electrode on each impurity diffusion layer of the semiconductor substrate on which the impurity diffusion layer is formed; Details are described by taking a single-sided power generation solar cell in FIG. 1, a back junction solar cell in FIG. 2, and a double-sided power generation solar cell in FIG.
  • the method for manufacturing a semiconductor element and the method for manufacturing a solar cell of the present invention are not limited to the above-described embodiments, and various modifications such as design changes can be added based on the knowledge of those skilled in the art. Embodiments to which such modifications are added are also included in the scope of the present invention.
  • the impurity diffusion composition of the present invention is also applied to 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 do.
  • GBL ⁇ -butyrolactone
  • PGMEA Propylene glycol monomethyl ether acetate
  • PVA Polyvinyl alcohol
  • TMSOX Trimethoxysilyloxetane (manufactured by Toagosei Co., Ltd.)
  • PhTMS phenyltrimethoxysilane
  • OXE-10 (3-ethyloxetane-3-yl) methyl acrylate.
  • the viscosity at 2 rpm and 20 rpm was measured, and the ratio of the viscosity at 2 rpm to the viscosity at 20 rpm was defined as the TI value.
  • the viscosity immediately after the preparation of the impurity diffusion composition and the viscosity after storage for 7 days at 25 ° C. were measured and used as an index of storage stability. A viscosity increase rate of 5% or less was judged as excellent (A), a value exceeding 5% and within 10% was judged good (B), and a value exceeding 10% was judged bad (C).
  • the impurity diffusion composition to be measured was applied to the silicon wafer by a known 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 adhering can be confirmed visually after immersion for 1 minute, but bad (C) can be removed by rubbing with a waste cloth. Good (B) ), And those on which surface deposits could not be visually confirmed within 30 seconds were regarded as excellent (A). Although good (B) can be used from the viewpoint of production tact, excellent (A) is preferable.
  • the silicon wafer after diffusion of impurities used for peelability evaluation is determined by p / n using a p / n determiner, and the surface resistance is measured by a four-probe type surface resistance measuring device RT-
  • the sheet resistance was measured using 70V (manufactured by Napson Corporation).
  • the sheet resistance value is an index of impurity diffusivity, and a smaller resistance value means a larger amount of impurity diffusion.
  • the p-type impurity diffusion compositions of the examples and comparative examples were applied to the silicon wafer 51 by a known coating method so that the pre-baked film thickness was about 500 nm. After the application, the silicon wafer was pre-baked at 140 ° C. for 5 minutes to prepare a p-type impurity diffusion composition film 52.
  • an n-type impurity diffusing composition (OCD T-1, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is separated by a known coating method so that the pre-baked film thickness is about 500 nm.
  • the silicon wafer 61 was applied. After the application, the silicon wafer was pre-baked at 140 ° C. for 5 minutes to prepare an n-type impurity diffusion composition coating film 64.
  • the p-type impurity diffusion layer 53 was formed on the silicon wafer 51, and the n-type impurity diffusion layer 65 was formed on the silicon wafer 61, respectively.
  • each silicon wafer was immersed in a 5 wt% hydrofluoric acid aqueous solution at 23 ° C. for 1 minute to peel the cured diffusing agent ((e) of FIG. 5).
  • the surface concentration distribution of the phosphorus element was measured on the silicon wafer 51 by using a secondary ion mass spectrometer IMS7f (manufactured by Camera).
  • 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 or less, excellent (A), 10 17 and above 10 18 or less are good (B), 10 18 and 10 19 or less are not bad (C) Those exceeding 10 19 were judged as bad (D).
  • a semiconductor substrate made of n-type single crystal silicon having a side of 156 mm was prepared, and both surfaces were subjected to alkali etching in order to remove slice damage and natural oxides.
  • innumerable irregularities having a typical width of about 40 to 100 ⁇ m and a depth of about 3 to 4 ⁇ m were formed on both surfaces of the semiconductor substrate, and this was used as a coated substrate.
  • a screen printer (Microtech TM-750 type) a screen mask with 175 openings with a width of 200 ⁇ m and a length of 13.5 cm formed at a pitch of 600 ⁇ m (SUS Co., 400 mesh) , A wire diameter of 23 ⁇ m) was used to form a stripe pattern.
  • the substrate is heated in air at 140 ° C. for 5 minutes and further at 230 ° C. for 30 minutes, so that the thickness is about 1.5 ⁇ m, the width is about 210 ⁇ m, the pitch is 600 ⁇ m, the length A 13.5 cm pattern was formed.
  • the line width is measured at 10 points at an equal interval for any one line, and the standard deviation of the coating width is within 12.5 ⁇ m, excellent (A), and the one with more than 12.5 ⁇ m and within 15 ⁇ m is good (B), those exceeding 15 ⁇ m and within 17.5 ⁇ m were judged as bad (C), and those exceeding 17.5 ⁇ m and within 20 ⁇ m were judged as worst (D).
  • Example 1 (1) (A) Synthesis of Polymer A sulfuric acid aqueous solution prepared by charging 55.64 g (0.2 mol) of TMSOX and 67.75 g of GBL in a 500 mL three-necked flask and dissolving 0.11 g of sulfuric acid in 18 g of water while stirring at 40 ° C. Was added over 30 minutes. After completion of dropping, the mixture was stirred at 40 ° C. for 1 hour, then heated to 70 ° C. and stirred for 30 minutes. Thereafter, the temperature of the oil bath was raised to 115 ° C.
  • the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 1 hour (the internal temperature was 100 to 110 ° C.).
  • the obtained solution was cooled in an ice bath to obtain a polysiloxane (TMSOX (100)) solution.
  • the solid content concentration of the polysiloxane solution was 40.0% by weight.
  • Example 2 (1) (A) Polymer synthesis A 500 mL three-necked flask was charged with 55.64 g (0.2 mol) of TMSOX, 39.658 g (0.2 mol) of KBM-103 (phenyltrimethoxysilane), and 163.2 g of GBL. While stirring at 40 ° C., a sulfuric acid aqueous solution in which 0.22 g of sulfuric acid was dissolved in 36 g of water was added over 30 minutes. After completion of dropping, the mixture was stirred at 40 ° C. for 1 hour, then heated to 70 ° C. and stirred for 30 minutes. Thereafter, the temperature of the oil bath was raised to 115 ° C.
  • the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 1 hour (the internal temperature was 100 to 110 ° C.).
  • the obtained solution was cooled in an ice bath to obtain a polysiloxane (TMSOX (50) / PhTMS (50)) solution.
  • the solid content concentration of the polysiloxane solution was 40.3% by weight.
  • Example 3 An impurity diffusion composition was obtained in the same manner as in Example 2 except that the composition of polysiloxane was (TMSOX (5) / PhTMS (95)). The solid content concentration of the polysiloxane solution was 40.6% by weight. Using the resulting impurity diffusion composition, the viscosity, TI value, storage stability, peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all were good. .
  • Example 4 An impurity diffusion composition was obtained in the same manner as in Example 2 except that the composition of polysiloxane was (TMSOX (95) / PhTMS (5)). The solid content concentration of the polysiloxane solution was 40.0% by weight. Using the resulting impurity diffusion composition, the viscosity, TI value, storage stability, peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all were good. .
  • Example 5 (1) (A) Polymer synthesis 18.2 g of propylene glycol monomethyl ether acetate was introduced into a 500 mL three-necked flask and the temperature was raised to 100 ° C. Then, 5.1 g of OXE-10, 2.1 g of acrylic acid, 0.36 g of azobisisobutyronitrile, and 13.60 g of propylene glycol monomethyl ether acetate were dropped into the flask from the dropping funnel over 2 hours. And stirring was continued at 100 ° C. for another 10 hours. The obtained solution was cooled to obtain an acrylic (OXE-10 (50) / acrylic acid (50)) solution.
  • Example 6 A thickener shown in Table 1 was added to the impurity diffusion composition prepared in Example 1 so as to have a predetermined weight% concentration with respect to the entire solution, and a rotation / revolution mixer ARE-310 (Sinky Corp.) (Agitated: 15 minutes, defoamed: 1 minute). The viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printability, and screen continuous printability were measured using the obtained solution, all were good as shown in Table 2.
  • Example 7 The thickener shown in Table 1 was added to the impurity diffusion composition prepared in Example 2 so as to have a predetermined weight% concentration with respect to the entire solution, and a rotation / revolution mixer ARE-310 (Sinky Corp.) (Agitated: 15 minutes, defoamed: 1 minute). The viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printability, and screen continuous printability were measured using the obtained solution, all were good as shown in Table 2.
  • Example 8 The thickener shown in Table 1 was added to the impurity diffusion composition prepared in Example 3 so as to have a predetermined weight% concentration with respect to the entire solution, and a rotation / revolution mixer ARE-310 (Sinky Corp.) (Agitated: 15 minutes, defoamed: 1 minute). The viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printability, and screen continuous printability were measured using the obtained solution, all were good as shown in Table 2.
  • Example 9 A thickener described in Table 1 was added to the impurity diffusion composition prepared in Example 4 so as to have a predetermined weight% concentration with respect to the entire solution, and a rotation / revolution mixer ARE-310 (Sinky Corp.) (Agitated: 15 minutes, defoamed: 1 minute). The viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printability, and screen continuous printability were measured using the obtained solution, all were good as shown in Table 2.
  • Example 10 A thickener described in Table 1 was added to the impurity diffusion composition prepared in Example 5 so as to have a predetermined weight% concentration with respect to the entire solution, and a rotation / revolution mixer ARE-310 (Sinky Corp.) (Agitated: 15 minutes, defoamed: 1 minute). The viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printability, and screen continuous printability were measured using the obtained solution, all were good as shown in Table 2.
  • Example 11 An impurity diffusion composition was obtained in the same manner as in Example 2 except that the composition of polysiloxane was (TMSOX (10) / PhTMS (90)). The solid content concentration of the polysiloxane solution was 40.0% by weight. Using the resulting impurity diffusion composition, the viscosity, TI value, storage stability, peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all were good. .
  • Example 12 An impurity diffusion composition was obtained in the same manner as in Example 2 except that the composition of polysiloxane was (TMSOX (90) / PhTMS (10)). The solid content concentration of the polysiloxane solution was 40.2% by weight. Using the resulting impurity diffusion composition, the viscosity, TI value, storage stability, peelability, sheet resistance value, diffusion uniformity, and barrier properties were measured. As shown in Table 2, all were good. .
  • Example 13 A thickener described in Table 1 was added to the impurity diffusion composition prepared in Example 11 so as to have a predetermined weight% concentration with respect to the entire solution, and a rotation / revolution mixer ARE-310 (Sinky Corp.) (Agitated: 15 minutes, defoamed: 1 minute). The viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printability, and screen continuous printability were measured using the obtained solution, all were good as shown in Table 2.
  • Example 14 The thickener shown in Table 1 was added to the impurity diffusion composition prepared in Example 12 so as to have a predetermined weight% concentration with respect to the entire solution, and a rotation / revolution mixer ARE-310 (Sinky Corp.) (Agitated: 15 minutes, defoamed: 1 minute). The viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printability, and screen continuous printability were measured using the obtained solution, all were good as shown in Table 2.
  • Comparative Example 1 A 500 mL three-necked flask was charged with 20.8 g of PVA (manufactured by Wako Pure Chemical Industries, degree of polymerization 500) and 144 g of water, heated to 80 ° C. with stirring, and stirred for 1 hour. Thereafter, 231.6 g of GBL and 3.6 g of boric acid were added and stirred at 80 ° C. for 1 hour. After cooling to 40 ° C., BYK-333 was added so as to be 300 ppm with respect to the entire solution, and sufficiently stirred to obtain a uniform impurity diffusion composition.
  • PVA manufactured by Wako Pure Chemical Industries, degree of polymerization 500
  • the thickeners shown in Table 1 were added so as to have a predetermined weight% concentration with respect to the whole solution, and dissolved using a rotation / revolution mixer ARE-310 (manufactured by Shinky Co., Ltd.) (stirring). : 15 minutes, defoaming: 1 minute).
  • the viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printability, and screen continuous printability were measured using the obtained solution, as shown in Table 2, storage stability, barrier property, screen The result was inferior to continuous printability.
  • Comparative Example 2 A 500 mL three-necked flask was charged with 20.8 g of trimethylolpropane, 231.6 g of GBL, and 3.6 g of boric acid, and stirred at 80 ° C. for 1 hour. After cooling to 40 ° C., BYK-333 was added so as to be 300 ppm with respect to the entire solution, and sufficiently stirred to obtain a uniform impurity diffusion composition. Thereafter, the thickeners shown in Table 1 were added so as to have a predetermined weight% concentration with respect to the whole solution, and dissolved using a rotation / revolution mixer ARE-310 (manufactured by Shinky Co., Ltd.) (stirring). : 15 minutes, defoaming: 1 minute).
  • ARE-310 manufactured by Shinky Co., Ltd.
  • the viscosity, TI value, and storage stability of the obtained solution were the results shown in Table 2. Further, when the peelability, sheet resistance value, diffusion uniformity, barrier property, screen printing property, and screen continuous printing property were measured using the obtained solution, as shown in Table 2, the diffusion uniformity and barrier property were inferior. As a result.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Le but de la présente invention est de fournir une composition de diffusion d'impuretés qui assure une excellente stabilité au stockage d'une solution de revêtement, et qui peut améliorer l'imprimabilité continue pendant l'impression par sérigraphie et pour permettre la diffusion uniforme sur un substrat semi-conducteur. Afin d'atteindre l'objectif ci-dessus, une composition de diffusion d'impuretés de la présente invention contient : (A) un polymère (ci-après appelé polymère (A)) ayant, dans une chaîne latérale, au moins une structure choisie parmi les formules générales (1) et (2) ; et (B) un composant de diffusion d'impuretés. (Dans Les formules générales (1) et (2), R1 à R14 représentent chacun Indépendamment un atome d'hydrogène ou un groupe organique ayant 1 à 8 atomes de carbone. a1 représente un nombre entier de 1 à 4, et a2 et a3 représentent chacun indépendamment un nombre entier de 0 à 2. a2+a3 représente un nombre entier de 0 à 3. * Indique un site de liaison à un polymère.)
PCT/JP2019/009064 2018-03-16 2019-03-07 Composition de diffusion d'impuretés , procédé de production de dispositif semi-conducteur l'utilisant, et procédé de fabrication de cellule solaire WO2019176716A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201980015220.2A CN111771258B (zh) 2018-03-16 2019-03-07 杂质扩散组合物、使用了该杂质扩散组合物的半导体元件的制造方法及太阳能电池的制造方法
JP2019514047A JP7172994B2 (ja) 2018-03-16 2019-03-07 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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018048818 2018-03-16
JP2018-048818 2018-03-16

Publications (1)

Publication Number Publication Date
WO2019176716A1 true WO2019176716A1 (fr) 2019-09-19

Family

ID=67907777

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/009064 WO2019176716A1 (fr) 2018-03-16 2019-03-07 Composition de diffusion d'impuretés , procédé de production de dispositif semi-conducteur l'utilisant, et procédé de fabrication de cellule solaire

Country Status (4)

Country Link
JP (1) JP7172994B2 (fr)
CN (1) CN111771258B (fr)
TW (1) TW201946116A (fr)
WO (1) WO2019176716A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021060182A1 (fr) * 2019-09-26 2021-04-01 東レ株式会社 Composition de diffusion d'impuretés, procédé de fabrication d'élément semi-conducteur l'utilisant et procédé de fabrication de cellule solaire

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012088610A (ja) * 2010-10-21 2012-05-10 Toray Ind Inc ネガ型感光性樹脂組成物およびそれを用いた硬化膜
WO2012090708A1 (fr) * 2010-12-28 2012-07-05 東亞合成株式会社 Procédé de préparation d'une solution de polysiloxane réactif
WO2012105163A1 (fr) * 2011-01-31 2012-08-09 東京応化工業株式会社 Composition de formation d'un film contenant du silicium, procédé de fabrication d'une couche à diffusion d'impuretés et cellule solaire
WO2015002132A1 (fr) * 2013-07-04 2015-01-08 東レ株式会社 Composition de diffusion d'impuretés et procédé de production d'un élément à semiconducteur
JP2017103379A (ja) * 2015-12-03 2017-06-08 東レ株式会社 不純物拡散組成物、およびそれを用いた半導体素子の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6772836B2 (ja) * 2015-09-29 2020-10-21 東レ株式会社 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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012088610A (ja) * 2010-10-21 2012-05-10 Toray Ind Inc ネガ型感光性樹脂組成物およびそれを用いた硬化膜
WO2012090708A1 (fr) * 2010-12-28 2012-07-05 東亞合成株式会社 Procédé de préparation d'une solution de polysiloxane réactif
WO2012105163A1 (fr) * 2011-01-31 2012-08-09 東京応化工業株式会社 Composition de formation d'un film contenant du silicium, procédé de fabrication d'une couche à diffusion d'impuretés et cellule solaire
WO2015002132A1 (fr) * 2013-07-04 2015-01-08 東レ株式会社 Composition de diffusion d'impuretés et procédé de production d'un élément à semiconducteur
JP2017103379A (ja) * 2015-12-03 2017-06-08 東レ株式会社 不純物拡散組成物、およびそれを用いた半導体素子の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021060182A1 (fr) * 2019-09-26 2021-04-01 東レ株式会社 Composition de diffusion d'impuretés, procédé de fabrication d'élément semi-conducteur l'utilisant et procédé de fabrication de cellule solaire

Also Published As

Publication number Publication date
CN111771258B (zh) 2024-08-09
TW201946116A (zh) 2019-12-01
JPWO2019176716A1 (ja) 2021-02-04
CN111771258A (zh) 2020-10-13
JP7172994B2 (ja) 2022-11-16

Similar Documents

Publication Publication Date Title
JP6361505B2 (ja) 不純物拡散組成物および半導体素子の製造方法
US9870924B2 (en) Diffusion agent composition, method of forming impurity diffusion layer, and solar cell
JP5666267B2 (ja) 塗布型拡散剤組成物
CN107210201B (zh) p型杂质扩散组合物、使用其的半导体元件的制造方法以及太阳能电池及其制造方法
CN113169248B (zh) 半导体元件的制造方法和太阳能电池的制造方法
JP6099437B2 (ja) 拡散剤組成物、及び不純物拡散層の形成方法
CN114342101A (zh) 杂质扩散组合物、使用了该杂质扩散组合物的半导体元件的制造方法及太阳能电池的制造方法
JP7172994B2 (ja) 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
JP2017103379A (ja) 不純物拡散組成物、およびそれを用いた半導体素子の製造方法
JP6310649B2 (ja) 不純物拡散成分の拡散方法、及び太陽電池の製造方法
JP2022130317A (ja) 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
WO2016121641A1 (fr) Composition de diffusion d'impuretés, procédé de fabrication d'élément à semi-conducteur la mettant en œuvre, et cellule solaire
KR102124920B1 (ko) 마스크 페이스트 조성물, 이것을 사용해서 얻어지는 반도체 소자 및 반도체 소자의 제조 방법
CN108028188B (zh) p型杂质扩散组合物、使用其的半导体元件的制造方法及太阳能电池的制造方法
JP2024132877A (ja) ｐ型不純物拡散組成物またはｎ型不純物拡散組成物、およびそれを用いた太陽電池の製造方法
JP2023061892A (ja) 太陽電池の製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019514047

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19767468

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19767468

Country of ref document: EP

Kind code of ref document: A1