TW201813120A - Method for manufacturing semiconductor device and method for manufacturing solar cell - Google Patents

Abstract

The semiconductor element production method according to one embodiment includes a film layer formation step and a diffusion step. In the film layer formation step, an A film and a B film are formed on a semiconductor substrate. The A film is an impurity diffusion composition film that is formed using a composition A that contains an impurity diffusion component. The B film is an air diffusion suppression layer that suppresses the air diffusion of the impurity diffusion component from at least the A film and that is formed using a composition B that contains a polysiloxane. In the diffusion step, the semiconductor substrate on which the A film and the B film are formed is heat treated, and the impurity diffusion component is thereby diffused into the semiconductor substrate. This semiconductor element production method is for use in a solar cell production method.

Description

Method for manufacturing semiconductor element and method for manufacturing solar cell

The present invention relates to a method for manufacturing a semiconductor element and a method for manufacturing a solar cell.

Currently, in the manufacture of semiconductor elements such as solar cells, when an n-type or p-type impurity diffusion layer is formed on a semiconductor substrate, an impurity diffusion source is formed on the semiconductor substrate and the impurities are diffused by thermal diffusion. A method in which components are diffused in a semiconductor substrate. The impurity diffusion source is formed by a chemical vapor deposition (CVD) method or a solution coating method of a liquid impurity diffusion composition.

For example, when a liquid impurity diffusion composition is used, first, a thermal oxide film is formed on the surface of a semiconductor substrate, and then a resist having a predetermined pattern is laminated on the thermal oxide film by a photolithography method. . Then, using the resist as a mask, a portion of the thermally oxidized film not covered by the resist is etched with an acid or an alkali, and thereafter, the resist is peeled off to form a thermally oxidized film. Matte. Next, an n-type or p-type impurity diffusion composition is applied, so that the impurity diffusion composition is adhered to a portion of the mask opening. Thereafter, the impurity diffusion component in the composition is thermally diffused in the semiconductor substrate at 600 ° C. to 1250 ° C. to form an n-type or p-type impurity diffusion layer.

Regarding the manufacture of such semiconductor elements such as solar cells, in recent years, research has been conducted without using the existing photolithography technology, and simply by using a printing method or the like to pattern the impurity diffusion source, thereby manufacturing the patterned sun with the impurity diffusion layer at a low cost. Semiconductor elements such as batteries (for example, refer to Patent Document 1).

In any of the methods, for example, in the case of forming an n-type impurity diffusion layer, it is also necessary to form a mask layer in a region other than the n-type impurity diffusion source on the semiconductor substrate so as not to make the n-type Impurity diffusion component (hereinafter, simply referred to as "n-type impurity") is incorporated into the area where it should diffuse. In this case, after the n-type impurity is diffused in the semiconductor substrate, the mask layer is removed, and if necessary, a mask layer is formed again in a region where the n-type impurity is diffused, and the p-type impurity is diffused into the component (hereinafter , Suitably referred to simply as "p-type impurity") diffused in the area outside the mask layer.

In order to avoid the complexity of such a step, the following technique is also known: after the diffusion of n-type impurities, the calcined film of the n-type impurity diffusion source is directly set as a masking layer to perform the diffusion of p-type impurities (for example, See Patent Document 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-168810 [Patent Document 2] International Publication No. 2015/002132

[Problems to be Solved by the Invention] However, in the case of the method described in Patent Document 2, there is also a problem that if a mask layer is not formed in advance on a portion of a semiconductor substrate on which the impurity diffusion composition is not formed, Then n-type impurities or p-type impurities will be mixed outside the area that should be diffused.

As described above, in the case where n-type and p-type impurity diffusion layers are formed in a semiconductor substrate, a patterned masking layer needs to be formed in order to diffuse a target impurity diffusion component in a desired region in the semiconductor substrate. And it is removed, so there is a problem that the steps become longer, and the manufacturing cost or takt time (step operation time) increases.

The present invention has been made in view of the problems described above, and an object thereof is to provide a semiconductor device that can produce a desired impurity diffusion component (n-type impurity or p-type impurity) in a desired region in a semiconductor substrate with a small number of steps. Method and manufacturing method of solar cell. [Means for solving problems]

The present inventors have found that the problem can be solved by suppressing diffusion of an impurity diffusion component from an impurity diffusion source formed on a semiconductor substrate, thereby completing the present invention.

That is, in order to solve the problems and achieve the object, the method for manufacturing a semiconductor device according to the present invention includes a film layer forming step of forming an A film and a B layer on a semiconductor substrate. The A film uses an impurity-containing diffusion component Impurity diffusion composition film composed of composition A, the layer B is formed using composition B containing polysiloxane, and at least suppresses diffusion in the gas of the impurity diffusion component from the A film A diffusion-inhibiting layer in a gas; and a diffusion step, performing heat treatment on the semiconductor substrate on which the A film and the B layer are formed to diffuse the impurity diffusion component into the semiconductor substrate.

In the method for manufacturing a semiconductor device according to the present invention, as described in the invention, the film layer forming step includes an A film forming step of applying the composition A to a predetermined surface of the semiconductor substrate. Forming the A film; and a B layer forming step, applying the composition B on the A film to form the B layer.

In addition, the method for manufacturing a semiconductor device according to the present invention is the invention described above, wherein the film layer forming step includes a step of combining the A film formed using the composition A in advance and using the composition. The laminated body of the B layer formed on the A film is formed by laminating a predetermined surface of the semiconductor substrate.

In the method for manufacturing a semiconductor element according to the present invention, as described above, the dried layer B has a film thickness of 200 [nm] or more and 2000 [nm] or less.

The method for manufacturing a semiconductor device according to the present invention is the invention described above, wherein the composition A includes a binder resin.

In the method for manufacturing a semiconductor device according to the present invention, as described above, the composition B includes a polysiloxane represented by the following general formula (1).

[Chemical 1] (In the 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 ³ represents an alkyl group having 1 to 6 carbon atoms or a carbon group having 2 to 10 carbon atoms. Alkenyl, multiple R ³ may be the same or different; R ² and R ^{4 each} represent a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and a fluorenyl group having 1 to 6 carbon atoms, and multiple R 3 ² and R ⁴ may be the same or different respectively; among them, any of R ² and R ⁴ must be a hydroxyl group; n and m represent the composition ratio (%) of the components in each bracket, n + m = 100, n: m = 90: 10 to 40: 60; X is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, and 2 to 10 carbon atoms Any of alkenyl, aryl having 6 to 15 carbons, and heteroaryl having 3 to 12 carbons; Y is a hydrogen atom, alkyl having 1 to 6 carbons, and fluorenyl having 1 to 7 carbons Either)

In the method for manufacturing a semiconductor device according to the present invention, as described above, the composition A and the composition B are incompatible with each other.

In addition, the method for manufacturing a semiconductor device according to the present invention is as described above, wherein the composition A includes a binder resin, and the decomposition temperature of the binder resin is lower than the polysiloxane contained in the composition B. Hardening temperature of alkane.

In the method for manufacturing a semiconductor device according to the present invention, as described in the above-mentioned invention, in the film layer forming step, the A film and the B layer are continuously formed without a drying step using a heat treatment.

The method for manufacturing a semiconductor device according to the present invention is the invention described above, wherein the A film and the B layer are formed by a spin coating method.

In the method for manufacturing a semiconductor device according to the present invention, as described above, the A film formation step and the B layer formation step are performed continuously without stopping the rotation in the spin coating method.

In the method for manufacturing a semiconductor device according to the present invention, as described in the invention, the composition A includes a water-soluble binder resin, the composition B includes a solvent, and the water-soluble binder resin is The solubility of the solvent is 0.01 [g / mL] or less at 25 ° C.

In the method for manufacturing a semiconductor device according to the present invention, as described above, the composition A includes a boron compound, polyvinyl alcohol, and water.

In addition, the method for manufacturing a semiconductor device according to the present invention is the invention described above, further comprising forming a conductive type different from the A film on a surface of the semiconductor substrate on the side opposite to the A film. A film forming step of the impurity diffusion composition film. In the diffusion step, heat treatment is performed on the semiconductor substrate on which the impurity diffusion composition film, the A film, and the B layer are formed to diffuse the impurities. The impurity diffusion component of the composition film is diffused in the semiconductor substrate, and the impurity diffusion component from the A film is diffused in the semiconductor substrate, so that the impurity diffusion composition from the impurity is simultaneously formed on the semiconductor substrate. The impurity diffusion layer of the film and the impurity diffusion layer from the A film.

Moreover, the manufacturing method of the solar cell of this invention is equipped with the manufacturing method of the semiconductor element as described in any one of the said invention, It is characterized by the above-mentioned. [Effect of the invention]

According to the present invention, it is possible to reduce the number of steps required for thermally diffusing the impurity diffusion component in the semiconductor substrate, and to prevent contamination of the semiconductor substrate caused by diffusion in the gas of the impurity diffusion component during the thermal diffusion of the impurity diffusion component. (Impurity diffusion components are mixed into or diffused in an undesired region of the semiconductor substrate), and the target impurity diffusion component is efficiently diffused into a desired region of the semiconductor substrate with high purity. As a result, the steps of manufacturing the semiconductor element (and thus the manufacturing of the solar cell) can be shortened and the efficiency can be improved.

Hereinafter, preferred embodiments of a method for manufacturing a semiconductor element and a method for manufacturing a solar cell according to the present invention will be described in detail with reference to the drawings as necessary. The present invention is not limited to these embodiments.

The method for manufacturing a semiconductor element and the method for manufacturing a solar cell of the present invention include: a film layer forming step of forming an A film and a B layer on a semiconductor substrate; and a diffusion step of diffusing an impurity-diffusing component by thermal treatment (thermal diffusion) to The semiconductor substrate on which the A films and B layers are formed. In these manufacturing methods, the A film is an impurity diffusion composition film using the composition A. Composition A is an example of an impurity diffusion composition containing a target impurity diffusion component to be diffused in a semiconductor substrate. On the other hand, the layer B is an example of a diffusion-inhibiting layer in a gas that uses the composition B and suppresses at least the diffusion of the impurity diffusion component from the A film. The composition B is an example of a composition containing a polysiloxane which is preferable for forming a diffusion suppression layer in a gas. Hereinafter, each component contained in these composition A and composition B will be described in detail.

(Composition A) Composition A contains an impurity diffusion component such as an n-type impurity or a p-type impurity and a solvent. In addition, the composition A may contain a binder resin in addition to these, and may contain additives such as a thickener and a surfactant.

(Impurity Diffusion Component) The impurity diffusion component is a component for forming an n-type or p-type impurity diffusion layer in a semiconductor substrate. As the n-type impurity diffusion component, a compound containing an element of group 15 is preferable. As the group 15 element, phosphorus, arsenic, antimony, and bismuth are preferable, and phosphorus is particularly preferable. As the p-type impurity diffusion component, a compound containing an element of Group 13 is preferable. As the Group 13 element, boron, aluminum, and gallium are preferable, and boron is particularly preferable.

Examples of the phosphorus compound include a phosphoric acid ester and a phosphorous acid ester. Examples of the phosphate ester include phosphorus pentoxide, phosphoric acid, polyphosphoric acid, methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, propyl phosphate, Dipropyl phosphate, tripropyl phosphate, butyl phosphate, dibutyl phosphate, tributyl phosphate, phenyl phosphate, diphenyl phosphate, triphenyl phosphate, and the like. Examples of the phosphite include methyl phosphite, dimethyl phosphite, trimethyl phosphite, ethyl phosphite, diethyl phosphite, triethyl phosphite, propyl phosphite, and phosphorous acid. Dipropyl ester, tripropyl phosphite, butyl phosphite, dibutyl phosphite, tributyl phosphite, phenyl phosphite, diphenyl phosphite, triphenyl phosphite, and the like. Among these, in terms of dopability, phosphoric acid, phosphorus pentoxide, or polyphosphoric acid is preferred.

Examples of the boron compound include boric acid, diboron trioxide, methylboronic acid, phenylboronic acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trioctyl borate, and triborate Phenyl esters, etc. Among these, in terms of dopability, boric acid and diboron trioxide are preferred.

(Binder resin) As the binder resin in the composition A, a water-soluble binder resin is particularly preferably used. Here, the water-soluble binder resin refers to a resin that exhibits a solubility of 10% by weight or more with respect to water at 25 ° C.

Specifically, as the binder resin in the composition A, the following can be exemplified. Examples include polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polypropylene amidamine resin, polyvinyl pyrrolidone resin, polyethylene oxide resin, acrylamide alkyl sulfonate resin, and cellulose Derivatives, Gelatin, Gelatin Derivatives, Starch, Starch Derivatives, Sodium Alginate Compounds, Sanxian Gum, Guar Gum, Guar Gum Derivatives, Scleroglucan, Stiglucan Derivatives, tragacanth, tragacanth derivatives, dextrin, dextrin derivatives, water-soluble (meth) acrylate resins, water-soluble polybutadiene resins, water-soluble styrene resins , Butyral resin, these copolymers, etc. However, the binder resin in the composition A is not limited to these. The "(meth) acrylic acid" means "acrylic or methacrylic acid".

In the composition A, the binder resin may be used alone or in a combination of two or more. However, in the case where the impurity diffusion component contained in the composition A is a boron compound, the binder resin is more preferable in terms of the formation of the complex with the boron compound and the stability of the formed complex. Those having a 1,2-diol structure or a 1,3-diol structure are preferred, and polyvinyl alcohol is particularly preferred.

The degree of polymerization of the binder resin in the composition A is not particularly limited, and a preferred range of the degree of polymerization is 1,000 or less, and particularly preferably 800 or less. This shows excellent solubility of a hydroxyl group-containing polymer such as polyvinyl alcohol in an organic solvent. On the other hand, the lower limit of the polymerization degree is not particularly limited, and is preferably 100 or more from the viewpoint of ease of handling of the binder resin. In the present invention, the degree of polymerization of the binder resin is obtained as a polystyrene-equivalent number-average degree of polymerization in a gel permeation chromatography (GPC) analysis.

(Solvent) The solvent in the composition A is not particularly limited, and it is preferred that the impurity diffusion component and the binder resin contained in the composition A can be well dissolved or dispersed. Specific examples of such a solvent include water, alcohols, glycols, ethers, ketones, ammoniums, acetates, aromatic or aliphatic hydrocarbons, γ-butyrolactone, N -Methyl-2-pyrrolidone, N, N-dimethylimidazolidone, dimethylsulfinium, propylene carbonate and the like.

Examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, third butanol, 1-methoxy-2-propanol, pentanol, and 4-methyl- 2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-third butoxy-2-propanol, diacetone alcohol, terpine Alcohol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol), etc. Examples of the glycols include ethylene glycol and propylene glycol.

Examples of the ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol third butyl ether, propylene glycol n-butyl ether, and ethylene glycol diethylene glycol. Methyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol n-butyl ether, dipropylene glycol monomethyl ether, diisopropyl ether, di-n-butyl ether , Diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether, and the like.

Examples of the ketones include methyl ethyl ketone, acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptan Ketones, cyclohexanone, cycloheptanone, etc. Examples of the amidines include dimethylformamide and dimethylacetamide.

Examples of the acetates include isopropyl acetate, ethyl acetate, propyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and ethyl acetate. Ester, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, acetic acid 3 -Methyl-3-methoxybutyl ester, butyldiethylene glycol acetate, 1,3-butanediol diacetate, ethyldiethylene glycol acetate, dipropylene glycol methyl ether acetate, Methyl lactate, ethyl lactate, butyl lactate, triethylglycerol, and the like. Examples of the aromatic or aliphatic hydrocarbon include toluene, xylene, hexane, cyclohexane, ethyl benzoate, naphthalene, 1,2,3,4-tetrahydronaphthalene and the like.

In addition, in order to form the B layer stably on the A film, the A film and the B layer are preferably immiscible with each other. That is, the composition A constituting the A film and the composition B constituting the B layer are preferably incompatible with each other. Therefore, the A film preferably has quick-drying properties, and the boiling point of the solvent in the composition A is preferably 150 ° C. or lower. In the present invention, the state of "composition A and composition B being incompatible with each other" means, of course, that the composition B is applied in a layer form to the composition A that is applied in a film form on a certain surface. In the case where the composition A and the composition B are not completely fused with each other, it also means that even if fusion occurs at the interface between the composition A and the composition B, the coating film of the composition A ( The film (A film) and the coating layer (layer B) of the composition B each have a desired thickness and are maintained in a state where they can be distinguished from each other.

From the viewpoints described above, the solvent in the composition A is preferably water, a specific alcohol, a specific ether, a specific ketone, a specific acetate, a specific aromatic or aliphatic hydrocarbon.

Specifically, examples of preferable specific alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, and 1-methoxy-2-propanol. , Pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, and the like. Examples of preferred specific ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethyl ether, and diisopropyl ether. Preferred specific ketones include, for example, methyl ethyl ketone, acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, and cyclopentanone. Preferred specific acetates include, for example, isopropyl acetate, ethyl acetate, propyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate. , Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, and the like. Examples of preferable specific aromatic or aliphatic hydrocarbons include toluene, xylene, hexane, and cyclohexane.

(Additives) Composition A may contain additives such as a thickener and a surfactant, as needed. Hereinafter, this thickener is demonstrated, and this surfactant is demonstrated next.

Examples of the thickener include cellulose, cellulose derivatives, starch, starch derivatives, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polyurethane. Ester resin, polyurea resin, polyimide resin, polyimide resin, epoxy resin, polystyrene resin, polyester resin, synthetic rubber, natural rubber, polyacrylic acid, various acrylic resins, polyethylene glycol , Polyethylene oxide, Polypropylene glycol, Polypropylene oxide, Silicon oil, Sodium alginate, Sanxian gum polysaccharides, Gellan gum polysaccharides, Guar gum polysaccharides, Carrageenan polysaccharides, Locust beans Gum-based polysaccharides, carboxyvinyl polymers, hydrogenated castor oil-based, mixtures of hydrogenated castor oil-based and fatty acid amines waxes, special fatty acids, oxidized polyethylenes, mixtures of oxidized polyethylene and amines, fatty acids It is a polycarboxylic acid, a phosphate ester surfactant, a salt of long-chain polyamidoamine and phosphoric acid, and a special modified polyamidoamine.

The content of the thickener in the composition A is preferably within a range of 0.1% by weight to 10% by weight. When the content of the thickener is within the above range, a sufficient viscosity adjustment effect of the composition A can be obtained.

The viscosity of the composition A is not particularly limited, and can be appropriately changed according to the coating method of the composition A and the film thickness of the composition A. For example, when the coating method of the composition A is a spin coating method, in order to obtain good coating properties of the composition A, the viscosity of the composition A is preferably 300 [mPa × s] or less, and particularly preferably 100 [mPa × s] or less. In addition, in the case of the screen printing method which is one of the preferable printing forms of the composition A, the viscosity of the composition A is preferably 3,000 [mPa × s] or more. This is because a good pattern can be obtained by suppressing bleeding of the printed pattern. A more preferable viscosity of the composition A is 5,000 [mPa × s] or more. The upper limit of the viscosity of the composition A is not particularly limited, and is preferably 100,000 [mPa × s] or less from the viewpoint of the storage stability or operability of the composition A.

Here, when the viscosity is less than 1,000 [mPa × s], it is based on the Japanese Industrial Standards (JIS) Z 8803 (1991) "solution viscosity-measurement method", using an E-type digital viscometer at a speed 5 rpm. In addition, when the viscosity is 1,000 [mPa × s] or more, it is a value measured at 20 rpm using a B-type digital viscometer based on JIS Z 8803 (1991) "solution viscosity-measurement method".

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant can be preferably used. Specific examples of the fluorine-based surfactant include a fluorine-based surfactant including a compound having a fluoroalkyl group or a fluoroalkylene group in at least any portion of a terminal, a main chain, and a side chain. Examples of such a fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, and 1,1,2,2-tetrafluoropropyl Fluorooctylhexyl ether, octaethylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether , Octapropylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis (1,1,2,2,3,3-hexafluoropentyl) ether, perfluorododecylsulfonate Sodium, 1,1,2,2,8,8,9,9,10,10-Decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3 -(Perfluorooctanesulfonamide) propyl] -N, N'-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoro Alkyl-N-ethylsulfonylglycine, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, and the like.

In addition, as commercially available products, there are Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F444, Megafac F475, Megafac F477 (above, manufactured by Dainippon Ink And Chemicals Industrial Co., Ltd.), Eftop EF301, Eftop 303, Eftop 352 ( (Made by Shin Akita Chemical Co., Ltd.), Fluorad FC-430, Fluorad FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Safulon ( Surflon) S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Shaflon ( Surflon SC-105, Surflon SC-106 (made by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (made by Yushang Co., Ltd.), NBX-15, FTX-218, DFX-218 (Manufactured by Neos Co., Ltd.) and other fluorine-based interfacial activities .

Examples of commercially available silicone-based surfactants include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (above, manufactured by Toray Dow Corning Co., Ltd.), BYK067A, BYK310, BYK322, BYK331, BYK333, BYK355 (above, manufactured by BYK-Chemie Japan Co., Ltd.), etc.

When the surfactant is added to the composition A, the content of the surfactant in the composition A is preferably 0.0001% by weight or more and 1% by weight or less.

In addition, as the composition A, a boron compound, polyvinyl alcohol, and water are particularly preferable. For example, a boron compound is contained in the composition A as an impurity diffusion component. Polyvinyl alcohol is contained in the composition A as a binder resin. Water is contained in the composition A as a solvent.

(Composition B) Composition B is a composition for forming layer B as a diffusion suppression layer in a gas, and contains polysiloxane and a solvent. The polysiloxane is a compound having the following properties: in a state where the B layer formed by using the composition B is formed on the A film, when the impurity diffusion component thermally diffuses from the A film to the semiconductor substrate, the impurity is suppressed from diffusing. The components undergo diffusion in the gas. In addition to polysiloxane, composition B may further contain a siloxane copolymer, a siloxane oligomer, silicon dioxide fine particles, and silicone as a compound that suppresses diffusion in a gas. In addition, the composition B may contain a binder resin in addition to these, and may contain additives such as a thickener and a surfactant.

(Polysiloxane) Polysiloxane has a property of suppressing the diffusion of impurities from the impurity diffusion component of the A film, and by this property, it is possible to prevent the diffusion of the impurity diffusion component to an undesired part of the semiconductor substrate. In addition, on the other hand, polysiloxane has the property of suppressing the impurity diffusion component of other conductivity type (for example, p-type with respect to n-type) different from Composition A to be mixed into the A film from the outside. With this, the polysiloxane can also suppress the diffusion of an undesired impurity diffusion component to the coating portion (the film-forming portion of the A film) of the composition A. As the polysiloxane contained in the composition B, a polysiloxane represented by the general formula (1) can be particularly preferably used.

[Chemical 2]

In the general formula (1), R ¹ represents an aryl group having 6 to 15 carbon atoms. Each of R ¹ may be the same or different. R ³ represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Each of R ³ may be the same or different. R ² and R ⁴ represent any of a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Each of R ² and R ⁴ may be the same or different. However, either of R ² and R ⁴ must be a hydroxyl group. n and m represent the composition ratio (%) of the components in each bracket. These n and m are preferably n + m = 100, and n: m = 90: 10 to 40:60.

In addition, the terminal group of the polysiloxane represented by the general formula (1) (for example, X and Y in the general formula (1)) is hydrogen (hydrogen atom), a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and a carbon number. Any of 1 to 6 alkoxy groups, 1 to 6 carbon atoms, and 2 to 10 alkenyl groups.

In the "base" in the present invention, the "carbon number" means the total number of carbons including the group in which the group is further substituted. For example, the number of carbon atoms of the methoxy-substituted butyl group is "5". The polysiloxane represented by the general formula (1) may be a block copolymer or a random copolymer.

The polysiloxane is preferably a unit containing 40 mol% or more of an aryl group having 6 to 15 carbon atoms in terms of Si atom. When the composition B contains such a polysiloxane, the cross-linking density of the polysiloxane skeletons in the layer B containing the composition B does not become too high. Therefore, when the impurity diffusion component is thermally diffused into the semiconductor substrate, although the B layer covers the A film, oxygen will reach the A film. Therefore, the B layer has the effect of not hindering the thermal decomposition of the binder resin in the A film. With this effect, after thermal diffusion, excess residue does not remain on the semiconductor substrate, and good diffusibility of the impurity diffusion component from the A film into the semiconductor substrate can be obtained. Therefore, the good diffusibility of the impurity diffusion component and the diffusion suppression effect in the gas of the impurity diffusion component by the B layer can be achieved.

In addition, the thickening of the B layer can further suppress the occurrence of cracks in the B layer. Therefore, it is not easy in the B layer in the steps of calcination of the B layer and thermal diffusion of the impurity diffusion component from the A film to the semiconductor substrate. Cracks occur. As a result, the layer B can sufficiently protect the impurity diffusion layer in the semiconductor substrate from the influence of other impurity diffusion components (covering property), and can improve the stability of thermal diffusion of the impurity diffusion components into the semiconductor substrate. In order to maintain the hiding property of the B layer, it is preferable that the film thickness of the B layer after thermal diffusion of the impurity diffusion component is large. Therefore, the composition B of the present invention, which is less prone to cracking even in a thick layer in the B layer, can be preferably used.

In addition, as for the layer B, even when a thermal decomposition component such as a thickener is added to the composition B, it can be buried by the reflow effect of the polysiloxane contained in the composition B Voids generated by thermal decomposition. As a result, a dense B layer with few voids can be formed. Such a dense B layer is not easily affected by the environment when the impurity diffusion component is thermally diffused from the A film into the semiconductor substrate, and a high covering property that sufficiently protects the impurity diffusion layer in the semiconductor substrate from other impurity diffusion components can be obtained. .

On the other hand, in the polysiloxane, the unit containing an aryl group having 6 to 15 carbon atoms is preferably 90 mol% or less in terms of Si atom. Thereby, the peeling residue of the A film after the impurity diffusion component is diffused can be eliminated from the semiconductor substrate. It is considered that the residue of the A film is a carbide that remains before the organic matter is completely decomposed and volatilized. In the case where the residue of such A film remains on the semiconductor substrate, not only the impurity of the impurity diffusion component in the semiconductor substrate is hindered, but also the contact resistance between the electrode formed later and the semiconductor substrate (such as the impurity diffusion layer) is increased, As a result, the efficiency of the solar cell is reduced. It is considered that if the unit containing an aryl group having 6 to 15 carbon atoms exceeds 90 mole% in terms of Si atoms in the polysiloxane, the composition in the B layer is completely decomposed and volatilized before the organic components of the A film are completely decomposed and volatilized. The film of B becomes too dense, and therefore residues of the film A are easily generated.

That is, n and m in the general formula (1) are preferably n: m = 90: 10 to 40:60. In addition, in the general formula (1), when R ³ is an alkyl group, by setting the carbon number of the alkyl group to 6 or less, it is possible to suppress the occurrence of residues of the A film, and fully utilize the R ¹ Reflow effect from aryl.

In addition, in order to obtain the above-mentioned effect, the film thickness of the layer B after drying is more preferably 200 [nm] or more and 2000 [nm] or less. When the film thickness of the B layer after drying is 200 [nm] or more, the diffusion suppression effect or hiding property in the gas of the B layer is further improved. On the other hand, when the film thickness of the B layer after drying is 2000 [nm] or less, oxygen can easily reach the A film through the B layer, so the diffusibility of the impurity diffusion component from the A film to the semiconductor substrate is further improved. . The film thickness is a value measured by Surfcom 1400D (manufactured by Tokyo Precision Co., Ltd.).

Furthermore, in order to obtain good diffusibility of the impurity diffusion component as described above, it is preferable that the decomposition temperature of the binder resin contained in the composition A is lower than the curing temperature of the polysiloxane contained in the composition B. Accordingly, when the impurity diffusion component is thermally diffused, the polysiloxane in the layer B will not be hardened during the temperature rising process until the temperature of the A film reaches the decomposition temperature of the binder resin contained in the composition A. Therefore, the crosslink density of the polysiloxane skeletons in the B layer does not become too high. In this regard, when the impurity diffusion component is thermally diffused, although the B layer covers the A film, oxygen will reach the A film, so the B layer will not prevent the binder resin in the A film from thermally decomposing. As a result, after the thermal diffusion of the impurity diffusion component, the excess residue of the A film will not remain on the semiconductor substrate, and the good diffusion property of the impurity diffusion component can be obtained. Therefore, the good diffusion property and the B layer can be achieved. The coexistence of the diffusion suppression effect in the gas of the impurity diffusion component brought about.

The aryl group having 6 to 15 carbon atoms as R ¹ in the general formula (1) may be any of an unsubstituted substance and a substituted substance, and may be selected according to the characteristics of the composition B. Specific examples of the aryl group having 6 to 15 carbon atoms include phenyl, p-tolyl, m-tolyl, o-tolyl, p-hydroxyphenyl, p-styryl, p-methoxyphenyl, and naphthalene base. Among these, phenyl, p-tolyl, and m-tolyl are particularly preferred.

The alkyl group having 1 to 6 carbon atoms and the alkenyl group having 2 to 10 carbon atoms as R ³ in the general formula (1) may be either an unsubstituted product or a substituted product, and may be based on the characteristics of the composition B. Make your selection.

Specific examples of the alkyl group having 1 to 6 carbon atoms as R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, n-hexyl, and trifluoromethyl. , 3,3,3-trifluoropropyl, 3-methoxy-n-propyl, glycidyl, 3-glycidoxypropyl, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanate Propyl. Among these, methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl are preferable from the viewpoint of easily eliminating residues of the A film.

Specific examples of the alkenyl group having 2 to 10 carbon atoms as R ³ include vinyl, 1-propenyl, 1-butenyl, 2-methyl-1-propenyl, and 1,3-butane Alkenyl, 3-methoxy-1-propenyl, 3-propenyloxypropyl, 3-methacryloxypropyl. Among these, from the viewpoint of easily eliminating the residue of the A film, particularly preferred are a vinyl group having 4 or less carbon atoms, a 1-propenyl group, a 1-butenyl group, a 2-methyl-1-propenyl group, and 1, 3-butadienyl, 3-methoxy-1-propenyl.

R ² and R ⁴ in the general formula (1) may be an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms and a fluorenyl group having 1 to 6 carbon atoms. The characteristics of the composition B are selected. Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a third butoxy group. Specific examples of the fluorenyloxy group having 1 to 6 carbon atoms include ethynyloxy, propylfluorenyloxy, propylenefluorenyloxy, and benzyloxy.

In the general formula (1), X represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, and an olefin having 2 to 10 carbon atoms. Any of a aryl group, an aryl group having 6 to 15 carbon atoms, and a heteroaryl group having 3 to 12 carbon atoms. Y represents any of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a fluorenyl group having 1 to 7 carbon atoms.

(Solvent) The solvent contained in the composition B is not particularly limited. In order to stably form the B layer on the A film, a solvent that does not make the A film and the B layer compatible is preferable. That is, it is preferred that the solvent contained in the composition B is such that the composition A and the composition B are not miscible. For this reason, the composition A contains a water-soluble binder resin, and the solubility of the water-soluble binder resin in the composition A with respect to the solvent in the composition B is preferably 0.01 [g / mL] or less at 25 ° C. By combining the water-soluble adhesive resin in the composition A and the solvent in the composition B, when the composition B is used, the A film formed on the semiconductor substrate (the solvent is volatile, and the solvent is not substantially contained) When the B layer is formed thereon, the A film and the composition B are mixed to such an extent that they do not hinder film formation. Therefore, the B layer is easily and stably formed on the A film.

In the case of using particularly preferred polyvinyl alcohol as the water-soluble binder resin in the composition A, specific examples of the solvent of the composition B satisfying the above conditions include γ-butyrolactone, 2, 2 , 4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol), terpineol, 3-methyl-3-methoxybutanol, dimethylformamide, 2-butane Alcohol, diethylene glycol monomethyl ether, and the like. Among these, γ-butyrolactone, terpineol, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol) are preferred.

(Binder Resin, Thickener, and Surfactant) The binder resin and the thickener can be used in the composition without particular limitation as long as they exhibit a solubility of 10% by weight or more with respect to the solvent of the composition B. B. As the binder resin of the composition B, polyvinyl butyral or (meth) acrylate resin is particularly preferred. As the thickener of Composition B, polyethylene oxide, polypropylene oxide, and silicone oil are particularly preferred. The surfactant of the composition B is the same as those suitably contained in the composition A. When it is added to the composition B, the content is 0.0001% to 1% by weight of the surfactant contained in the composition A. %.

When using a polysiloxane or a siloxane derivative in the composition B, for the purpose of improving the hiding property of the B layer, silicon dioxide particles may be added to the composition B. In this case, it is preferable that the silicon dioxide particles have an average particle diameter of 150 [nm] or less.

(Other Additives) In addition to the above, the composition B may contain a compound that forms a stable bond with an impurity diffusion component or an impurity element. Composition B improves the hiding property of layer B by including these compounds. Specifically, in the case where the impurity diffusion component contained in the composition A is phosphorus, the additive contained in the composition B is preferably a gallium or aluminum compound. When the impurity diffusion component contained in the composition A is boron, as the additive contained in the composition B, a compound containing phosphorus, tantalum, niobium, arsenic, or antimony is preferable. By forming a stable bond between the additive in the composition B and the impurity diffusion component or the impurity element, the diffusion of the undesired impurity into the semiconductor substrate such as a silicon wafer can be suppressed, so that the impurity diffusion component in the semiconductor substrate can be realized. Good spread without pollution.

(Method for Forming A Film and B Layer) A method for forming the A film and B layer in the present invention will be described. This formation method is one in which an A film containing the composition A and a B layer containing the composition B are formed on the surface of the semiconductor substrate. As the method for forming the A film and the B layer, a known method can be used, and the following coating method can be preferably used: the composition A is coated on the surface of the semiconductor substrate to form the A film, and the composition B is coated A layer B is formed on this A film. Specific examples of the coating method for forming the A film and the B layer include a spin coating method, an inkjet method, a slit coating method, and a screen printing method.

In the method for forming the A film and the B layer using the coating method, in order to form the B layer stably on the A film, for example, the following steps may be performed: the composition A is applied to form a film on the surface of the semiconductor substrate to form the A film After drying, the composition B is applied to form a film on the dried A film to form a B layer. However, in this forming method, since the coating step and the drying step for forming the A film and the B layer are performed alternately, the total number of steps increases. In order to achieve the purpose of reducing the number of steps required for the formation of the A film and the B layer, and thereby reducing the manufacturing cost or the tact time of the semiconductor element (and thus the solar cell), the step of forming the A film and the step of forming the B layer are preferred Continuously without going through a drying step using heat treatment. In this respect, as the coating method of the composition A and the composition B, a spin coating method or an inkjet method that can continuously form the A film and the B layer as described above can be preferably used.

In the case where the coating of the composition A and the coating of the composition B are continuously performed by a spin coating method, it is more preferable that the composition A is not dropped after being dropped on a semiconductor substrate surface such as a silicon wafer. The composition B is continuously dropped by the rotation in the coating method (specifically, the rotation of the semiconductor substrate). Thereby, the A film and the B layer can be sequentially and sequentially formed on the surface of the semiconductor substrate. Therefore, the formation of the A film and the formation of the B layer on the A film can be performed in one step. As a result, the number of steps required to form the A film and the B layer can be reduced. In addition, the spin coating method is easy to form a uniform film, so it also has the advantage that the A film is uniformly formed on the target region where the target impurity diffusion component is diffused on the surface of the semiconductor substrate, and the A film is uniformly formed on the A film. It is easy to achieve the purpose of reducing the number of steps by forming layer B as a mask.

In order to apply the coating method to the method of coating and forming the composition A and the composition B, it is necessary to make the boiling point of each solvent contained in the composition A and the composition B or the composition A and Each viscosity of the composition B is suitable for the process using a coating method. For example, when the composition A and the composition B are coated into a film by a spin coating method, the boiling point of the solvent contained in the composition A is preferably 30 ° C or higher and 150 ° C or lower. The boiling point of the solvent contained in the composition B is preferably 30 ° C or higher and less than 280 ° C, and more preferably 70 ° C or higher and less than 200 ° C. In the case where the composition A and the composition B are coated into a film by the inkjet method, the boiling point of each solvent contained in the composition A and the composition B is preferably 100 ° C or higher and less than 280 ° C, and more preferably It is 120 ° C or higher and less than 200 ° C.

On the other hand, as a method of forming the A film including the composition A and the B layer including the composition B on the surface of the semiconductor substrate, a lamination method can also be preferably used. As an example of the method of forming the A film and the B layer using the lamination method, the following two methods can be cited.

For example, in the first method, the A film formed on the film by using the composition A in advance is transferred to the surface of the semiconductor substrate by lamination. Thereafter, the B layer formed on the film using the composition B in advance was transferred to the surface of the A film on the semiconductor substrate surface by lamination. Thereby, the A film and the B layer are formed on the semiconductor substrate.

In the second method, a layered body of the B layer formed on the film using the composition B and an A film formed on the B layer using the composition A is formed in advance, and a film layer on which the layered body is formed is formed. The laminated body is transferred onto the semiconductor substrate surface by pressing on the semiconductor substrate surface. Thereby, the A film and the B layer are formed on the semiconductor substrate.

(Each method of manufacturing semiconductor element and solar cell) Each method of manufacturing the semiconductor element and solar cell of the present invention will be described below using representative examples. The method for manufacturing a semiconductor device according to the present invention includes a film layer forming step and a diffusion step. The film layer forming step is a step of forming an A film and a B layer on the semiconductor substrate. The A film is an impurity diffusion composition film using the composition A containing the impurity diffusion component, and the B layer is made of polysilicon. It is a gas diffusion-inhibiting layer made of the composition B of oxane and suppressing at least the diffusion of the impurity diffusion component from the A film. The diffusion step is a step of heat-treating the semiconductor substrate on which the A film and the B layer are formed to diffuse the impurity diffusion component from the A film into the semiconductor substrate. The method for manufacturing a solar cell of the present invention includes a method for manufacturing such a semiconductor element.

In each of these manufacturing methods, as the semiconductor substrate to be used, for example, n-type single crystal silicon, polycrystalline silicon having a impurity concentration of 10 ¹⁵ [atoms / cm ³ ] to 10 ¹⁶ [atoms / cm ³ ], and mixed materials such as germanium can be cited. Crystalline silicon substrate with other elements like carbon and carbon. Alternatively, a semiconductor substrate other than p-type crystalline silicon or silicon may be used. Such a semiconductor substrate is preferably a substantially quadrangle having a thickness of 50 [μm] to 300 [μm] and an outer shape of 100 [mm] to 250 [mm] on one side. In addition, in order to remove the slice damage or the natural oxide film of the semiconductor substrate, it is preferable to etch the surface of the semiconductor substrate with a hydrofluoric acid solution, an alkali solution or the like in advance.

(Embodiment 1) First, the manufacturing method of the semiconductor element by Embodiment 1 of this invention is demonstrated. FIG. 1 is a diagram showing an example of a method of manufacturing a semiconductor device according to the first embodiment of the present invention. In the method for manufacturing a semiconductor device according to the first embodiment, the film layer forming step includes an A film forming step and a B layer forming step using a coating method.

Specifically, as shown in FIG. 1, first, an A film forming step is performed (step ST101). In this step ST101, the composition A is applied on a predetermined surface of the semiconductor substrate 1 (for example, one of both end surfaces in the thickness direction of the semiconductor substrate 1) by the coating method described above to form the A film 2. At this time, it may be formed in advance on the surface of the semiconductor substrate 1 opposite to the surface on which the A film 2 is formed (the coating surface of the composition A) (the other surface of both ends in the thickness direction of the semiconductor substrate 1). Protective film. The protective film may be formed by a method such as a CVD (chemical vapor deposition) method or a spin-on glass (SOG) method. For example, as this protective film, a well-known thing, such as a silicon oxide film and a silicon nitride film, is mentioned.

Then, as shown in FIG. 1, a layer B formation step is performed (step ST102). In this step ST102, the composition B is applied to the A film 2 formed on the predetermined surface of the semiconductor substrate 1 by the step ST102 by the coating method, thereby forming the B layer 3.

In the film layer forming step in the first embodiment, steps ST101 and ST102 shown in FIG. 1 are continuously performed. That is, the A film 2 and the B layer 3 are sequentially and sequentially formed on the semiconductor substrate 1 without going through a drying step using a heat treatment.

After the A film 2 and the B layer 3 are sequentially formed on the semiconductor substrate 1 as described above, a drying step of drying the A films 2 and the B layer 3 may be performed. In this drying step, the composition A before drying constituting the A film 2 and the composition B before drying constituting the B layer 3 are dried. In this drying step, the composition A and the composition B are preferably dried for 30 seconds to 30 minutes using a hot plate and an oven in a range of 50 ° C to 200 ° C.

In addition, as the coating method used in the A film forming step (step ST101) and the B layer forming step (step ST102), as described above, the spin coating method, inkjet method, slit coating method, The screen printing method and the like are preferably a spin coating method or an inkjet method.

For example, when the A film 2 and the B layer 3 are formed by the spin coating method, it is preferable that steps ST101 and ST102 shown in FIG. 1 do not stop the rotation in the spin coating method (specifically, semiconductors). The rotation of the substrate 1 is performed continuously.

After the step ST102 is completed, as shown in FIG. 1, a diffusion step is performed (step ST103). In this step ST103, the semiconductor substrate 1 on which the A film 2 and the B layer 3 are formed is heat-treated to diffuse the impurity diffusion component into the semiconductor substrate 1. At this time, the target impurity diffusion component contained in the composition A is thermally diffused from the A film 2 into the semiconductor substrate 1. As a result, a target conductivity type (n-type or p-type) impurity diffusion layer 4 is formed on the semiconductor substrate 1. At the same time, the B layer 3 suppresses the diffusion of the gas from the target impurity diffusion component of the A film 2, and suppresses the impurity diffusion component of another conductivity type different from the composition A from entering the A film 2 from the outside.

As a method of the heat treatment in this step ST103, for example, a known method such as electric heating, infrared heating, laser heating, or microwave heating can be used. The time and temperature of the heat treatment can be appropriately set so that diffusion characteristics such as the concentration of the impurity diffusion component and the diffusion depth diffused in the semiconductor substrate 1 become desired.

The gas environment for the heat treatment is not particularly limited, and a mixed gas environment such as nitrogen, oxygen, argon, helium, xenon, neon, and krypton is preferred. Among them, a mixed gas of nitrogen and oxygen is more preferred, and a mixed gas of nitrogen and oxygen with an oxygen content of 5 vol% or less is particularly preferred. In addition, in step ST103, if necessary, before forming the impurity diffusion layer 4, the A film 2 is calcined in a range of 200 ° C to 750 ° C.

After the step ST103 is completed, as shown in FIG. 1, a removing step is performed (step ST104). In this step ST104, the A film 2 and the B layer 3 on the semiconductor substrate 1 are removed by a known etching method. The material used in this etching method is not particularly limited. For example, it is preferable to include at least one of hydrogen fluoride, ammonium, phosphoric acid, sulfuric acid, and nitric acid as an etching component, and water or an organic solvent as a component other than the etching component . Through the above steps, a target-type impurity-type impurity diffusion layer 4 can be formed in the semiconductor substrate 1. In this way, the semiconductor device 100 according to the first embodiment can be manufactured.

(Embodiment 2) Next, the manufacturing method of the semiconductor element by Embodiment 2 of this invention is demonstrated. FIG. 2A is a diagram showing an example of a method of manufacturing a semiconductor device according to the second embodiment of the present invention. The method for manufacturing a semiconductor device according to the second embodiment includes a film forming step of forming an impurity diffusion composition film having a conductivity type different from that of the A film on a semiconductor substrate, and a film layer forming step of forming an A film and a B layer on the semiconductor substrate. And a diffusion step to diffuse the impurity diffusion component in the semiconductor substrate. In the method for manufacturing a semiconductor device according to the second embodiment, the film layer forming step includes an A film forming step and a B layer forming step using a coating method.

Specifically, as shown in FIG. 2A, first, a film formation step is performed (step ST201). In this step ST201, an impurity diffusion composition film 15 having a conductivity type different from that of the A film 12 is formed on the surface of the semiconductor substrate 11 opposite to the A film 12 (see step ST202 in FIG. 2A) described later. The formation surface of the impurity diffusion composition film 15 is, for example, one of both end surfaces in the thickness direction of the semiconductor substrate 11. The impurity diffusion composition film 15 can be formed by applying the impurity diffusion composition having a conductivity type different from that of the composition A to the surface of the semiconductor substrate 11 by the coating method. The impurity diffusion composition constituting the impurity diffusion composition film 15 can be used without limitation as long as it contains an impurity diffusion component having a conductivity type different from that of the composition A and can be formed into a film by the coating method.

After forming the impurity diffusion composition film 15 on the surface of the semiconductor substrate 11 as described above, a drying step of drying the impurity diffusion composition film 15 may be performed. In addition, firing of the impurity diffusion composition film 15 may be performed in a range of 200 ° C to 750 ° C.

After the step ST201 is completed, as shown in FIG. 2A, an A film forming step is performed (step ST202). In this step ST202, the composition A is applied to a predetermined surface of the semiconductor substrate 11 (the other surface of the both ends in the thickness direction of the semiconductor substrate 11 in the second embodiment) by the coating method described above, so that A film 12 is formed. As shown in FIG. 2A, the formation surface of the A film 12 is a surface of the semiconductor substrate 11 opposite to the impurity diffusion composition film 15.

Then, as shown in FIG. 2A, a layer B formation step is performed (step ST203). In this step ST203, the composition B is applied to the outer surface of the A film 12 formed on the predetermined surface of the semiconductor substrate 11 in the step ST202 by the coating method, thereby forming the B layer 13.

In the film layer forming step in the second embodiment, steps ST202 and ST203 shown in FIG. 2A are continuously performed. That is, the A film 12 and the B layer 13 are sequentially and sequentially formed on the surface of the semiconductor substrate 11 without going through a drying step using a heat treatment. At this time, the coating methods used in steps ST202 and ST203 are the same as those of the first embodiment (spin coating method or inkjet method). After the A film 12 and the B layer 13 are sequentially formed on the surface of the semiconductor substrate 11 as described above, the drying step of drying the A films 12 and the B layer 13 may be performed in the same manner as in the first embodiment.

After the step ST203 is completed, as shown in FIG. 2A, a diffusion step is performed (step ST204). In step ST204, the semiconductor substrate 11 on which the impurity diffusion composition film 15, the A film 12, and the B layer 13 are formed is heat-treated by the same method as in the first embodiment to diffuse the impurities from the impurity diffusion composition film 15. The components are diffused in the semiconductor substrate 11, and the impurity diffusion components from the A film 12 are diffused in the semiconductor substrate 11. At this time, the target impurity diffusion component contained in the impurity diffusion composition film 15 is thermally diffused from the impurity diffusion composition film 15 into the semiconductor substrate 11. At the same time, the target impurity diffusion component contained in the A film 12 (composition A) is thermally diffused from the A film 12 into the semiconductor substrate 11. Thereby, the impurity diffusion layer 16 from the impurity diffusion composition film 15 and the impurity diffusion layer 14 from the A film 12 are simultaneously formed on the semiconductor substrate 11. The impurity diffusion layer 16 is a target of the first conductivity type (n-type or p-type). The impurity diffusion layer 14 is a target of the second conductivity type (a conductivity type different from the first conductivity type). As shown in FIG. 2A, the impurity diffusion layers 16 and the impurity diffusion layers 14 are formed on both sides in the thickness direction in the semiconductor substrate 11.

After the step ST204 is completed, as shown in FIG. 2A, a removing step is performed (step ST205). In this step ST205, the impurity diffusion composition film 15 formed on one surface of the semiconductor substrate 11 and the A film 12 and the B layer 13 formed on the other surface are formed by the same etching method as in the first embodiment. Remove. Through the above steps, an impurity diffusion layer 16 of the first conductivity type can be formed on one surface side of the semiconductor substrate 11, and an impurity diffusion layer 14 of the second conductivity type can be formed on the other surface side. In this way, the semiconductor device 200 according to the second embodiment can be manufactured. This semiconductor element 200 is suitable as a semiconductor element for a double-sided light-receiving solar cell.

In the second embodiment, when the semiconductor substrate 11 on which the impurity diffusion composition film 15 and the A film 12 having different conductivity types are formed is subjected to heat treatment (step ST204 shown in FIG. 2A), the layer B 13 has the following functions: The target impurity diffusion component is suppressed from diffusing into the gas from the A film 12, and the impurity diffusion component (the conductivity type different from the A film 12) is inhibited from entering into the A film 12 from the impurity diffusion composition film 15. Thereby, an n-type impurity or a p-type impurity can be diffused in a desired region in the semiconductor substrate 11.

Next, a method for manufacturing a solar cell according to a second embodiment of the present invention will be described. 2B is a diagram showing an example of a method for manufacturing a solar cell according to the second embodiment of the present invention. FIG. 2B illustrates a step after manufacturing the semiconductor element 200 (see FIG. 2A) that can be used in manufacturing the solar cell according to the second embodiment.

The method for manufacturing a solar cell according to the second embodiment includes a method for manufacturing a semiconductor element 200 shown in FIG. 2A. That is, after the semiconductor element 200 is manufactured as described above, a solar cell (a double-sided light-receiving solar cell) according to the second embodiment can be manufactured by a known method.

For example, in the method for manufacturing a solar cell according to the second embodiment, following the manufacturing steps of the semiconductor element 200 shown in FIG. 2A, a passivation layer forming step is performed as shown in FIG. 2B (step ST301). In step ST301, a passivation layer 17 is formed on the light receiving surface and the back surface of the semiconductor substrate 11, respectively. As a material of the passivation layer 17, a known material can be used. The passivation layer 17 may be a single layer or a plurality of layers. For example, as the passivation layer 17, there are those in which a thermal oxide layer, an aluminum oxide layer, a SiNx layer, and an amorphous silicon layer are laminated. The passivation layer 17 can be formed by a vapor deposition method such as a plasma CVD method or an atomic layer deposition (ALD) method or a coating method.

In the second embodiment, the passivation layer 17 is formed in a part of each of the light receiving surface and the back surface of the semiconductor substrate 11. In the semiconductor element 200, the light-receiving surface is a surface on the semiconductor substrate 11 side of the first conductivity-type impurity diffusion layer 16. The back surface is a surface on the semiconductor substrate 11 side of the second conductivity type impurity diffusion layer 14.

After the step ST301 is completed, as shown in FIG. 2B, an electrode forming step is performed (step ST302). In this step ST302, electrodes 18 and 19 are formed on the light-receiving surface and the back surface of the semiconductor substrate 11 in portions where the passivation layer 17 does not exist, respectively. The electrodes 18 and 19 can be formed by applying an electrode-forming paste to each of the exposed portions of the impurity diffusion layer 16 or the impurity diffusion layer 14 in the semiconductor substrate 11 and then forming electrodes on the exposed portions. The forming paste is heat-treated. Through the above steps, a double-sided light-receiving solar cell 250 according to the second embodiment can be manufactured.

(Embodiment 3) Next, the manufacturing method of the semiconductor element by Embodiment 3 of this invention is demonstrated. FIG. 3A is a diagram showing an example of a method of manufacturing a semiconductor device according to the third embodiment of the present invention. The method for manufacturing a semiconductor device according to the third embodiment includes a film forming step of forming an impurity diffusion composition film having a conductivity type different from that of the A film on a semiconductor substrate, and a film layer forming step of forming an A film and a B layer on the semiconductor substrate. And a diffusion step to diffuse the impurity diffusion component in the semiconductor substrate. In the method for manufacturing a semiconductor device according to the third embodiment, the film layer forming step includes an A film forming step and a B layer forming step using a coating method.

In the third embodiment, a manufacturing method suitable for the case of manufacturing a semiconductor element for a back-bonded solar cell is exemplified. In a semiconductor device for a backside-bonded solar cell, a p-type impurity diffusion layer and an n-type impurity diffusion layer are formed on the back surface of the surface opposite to the light-receiving surface in the solar cell.

Specifically, as shown in FIG. 3A, first, a film formation step is performed (step ST401). In this step ST401, an impurity-diffuse composition film 25 having a conductivity type different from that of the A film 22 described later is formed on a predetermined surface (the back surface of the solar cell) of the semiconductor substrate 21. At this time, the impurity diffusion composition of the first conductivity type different from the composition A is applied on the back surface of the semiconductor substrate 21 to form a pattern of the impurity diffusion composition film 25. The formation of this pattern can be performed by a suitable one selected from the coating methods such as a screen printing method and an inkjet method. The impurity diffusion composition constituting the impurity diffusion composition film 25 can be used without limitation as long as it contains the impurity diffusion component of the first conductivity type and can be formed into a film by the coating method.

After the pattern of the impurity diffusion composition film 25 is formed on the back surface of the semiconductor substrate 21 as described above, a drying step of drying the impurity diffusion composition film 25 may be performed. In addition, firing of the impurity diffusion composition film 25 may be performed in a range of 200 ° C to 750 ° C.

After the step ST401 is completed, as shown in FIG. 3A, a first diffusion step is performed (step ST402). In step ST402, the semiconductor substrate 21 on which the pattern of the impurity diffusion composition film 25 is formed is heat-treated by the same method as in the first embodiment, so that the impurities of the first conductivity type contained in the impurity diffusion composition film 25 are processed. The diffusion component is diffused in the semiconductor substrate 21. At this time, the impurity diffusion component of the first conductivity type is thermally diffused from the pattern of the heat-treated impurity diffusion composition film 25 into the semiconductor substrate 21. Thereby, the impurity diffusion layer 26 of the 1st conductivity type which is a target on the back surface side of the semiconductor substrate 21 is formed along the pattern of the impurity diffusion composition film 25. As shown in FIG.

After the step ST402 is completed, as shown in FIG. 3A, an A film forming step is performed (step ST403). In this step ST403, the composition A is coated on the back surface (the surface on the same side as the impurity diffusion composition film 25) of the semiconductor substrate 21 by the coating method described above, so that the A film 22 is formed. At this time, using the pattern of the impurity diffusion composition film 25 as a mask, the composition A is applied on the back surface of the semiconductor substrate 21. Thereby, the A film 22 is formed on the back surface of the semiconductor substrate 21 so as to cover the impurity diffusion composition film 25 without contacting the impurity diffusion layer 26 under the pattern.

Then, as shown in FIG. 3A, a layer B formation step is performed (step ST404). In this step ST404, the composition B is applied to the outer surface of the A film 22 formed in the step ST403 by the coating method, thereby forming the B layer 23.

In the film layer forming step in the third embodiment, steps ST403 and ST404 shown in FIG. 3A are continuously performed. That is, the A film 22 and the B layer 23 are sequentially and sequentially formed on the back surface of the semiconductor substrate 21 without going through a drying step using a heat treatment. In this case, the coating methods used in steps ST403 and ST404 are the same as those in the first embodiment (spin coating method or inkjet method). After the A film 22 and the B layer 23 are sequentially formed on the back surface of the semiconductor substrate 21 as described above, a drying step of drying the A films 22 and the B layer 23 may be performed in the same manner as in the first embodiment.

After the step ST404 is completed, as shown in FIG. 3A, a second diffusion step is performed (step ST405). In step ST405, the semiconductor substrate 21 having the impurity diffusion composition film 25, the A film 22, and the B layer 23 formed thereon is heat-treated by the same method as in the first embodiment to diffuse the impurity diffusion component from the A film 22 to Semiconductor substrate 21. At this time, the impurity diffusion component of the second conductivity type (conductivity type different from the first conductivity type) contained in the A film 22 (composition A) is thermally diffused from the A film 22 to the undesired portion in the back portion of the semiconductor substrate 21. In the exposed portion covered by the pattern of the impurity diffusion composition film 25. Thereby, an impurity diffusion layer 24 from the A film 22 is formed in the exposed portion in the back surface of the semiconductor substrate 21. The impurity diffusion layer 24 is a target of the second conductivity type.

After the step ST405 is completed, as shown in FIG. 3A, a removing step is performed (step ST406). In step ST406, the pattern of the impurity diffusion composition film 25, the A film 22, and the B layer 23 formed on the back surface of the semiconductor substrate 21 are removed by the same etching method as in the first embodiment. Through the above steps, the target impurity diffusion layer 26 of the first conductivity type and the impurity diffusion layer 24 of the second conductivity type can be formed on the back surface side of the semiconductor substrate 21. In this way, the semiconductor element 300 according to the third embodiment can be manufactured. This semiconductor element 300 is suitable as a semiconductor element for a back-bonded solar cell.

In the third embodiment, when the second-conductivity-type impurity diffusion layer 24 is formed (step ST405 shown in FIG. 3A), the B layer 23 suppresses the target second-conductivity-type impurity diffusion component from flowing into the gas from the A film 22. diffusion. Therefore, it is possible to prevent the impurity diffusion component diffused in the gas from the A film 22 on the light-receiving surface of the semiconductor substrate 21 (the side opposite to the surface (back surface) on which the two types of impurity diffusion layers 24 and the impurity diffusion layers 26 are formed). Surface).

Next, a method for manufacturing a solar cell according to a third embodiment of the present invention will be described. 3B is a diagram showing an example of a method for manufacturing a solar cell according to a third embodiment of the present invention. FIG. 3B illustrates a step after manufacturing the semiconductor element 300 (see FIG. 3A) that can be used in manufacturing the solar cell according to the third embodiment.

The method for manufacturing a solar cell according to the third embodiment includes a method for manufacturing a semiconductor element 300 shown in FIG. 3A. That is, after the semiconductor element 300 is manufactured as described above, a solar cell (a back-bonded solar cell) according to the third embodiment can be manufactured by a known method.

For example, in the method for manufacturing a solar cell according to the third embodiment, following the manufacturing steps of the semiconductor element 300 shown in FIG. 3A, a passivation layer forming step is performed as shown in FIG. 3B (step ST501). In step ST501, a passivation layer 27 is formed on the back surface of the semiconductor substrate 21. As a material of the passivation layer 27, a known material can be used. The passivation layer 27 may be a single layer or a plurality of layers. For example, as the passivation layer 27, there are those in which a thermal oxidation layer, an aluminum oxide layer, a SiNx layer, and an amorphous silicon layer are laminated. The passivation layer 27 can be formed by a vapor deposition method such as a plasma CVD method, an atomic layer deposition (ALD) method, or a coating method. In the third embodiment, the passivation layer 27 is formed on a part of the back surface of the semiconductor substrate 21 (the surface on one side where the two kinds of impurity diffusion layers 24 and the impurity diffusion layer 26 are formed).

After the step ST501 ends, as shown in FIG. 3B, an electrode forming step is performed (step ST502). In this step ST502, the electrode 28 and the electrode 29 are formed on each part of the back surface of the semiconductor substrate 21 where the passivation layer 27 does not exist. The electrodes 28 and 29 can be formed by applying an electrode-forming paste to each of the exposed portions of the impurity diffusion layer 26 or the impurity diffusion layer 24 on the back surface of the semiconductor substrate 21 and then applying the electrode formation paste to the exposed portions. The paste for electrode formation is heat-treated. Through the above steps, the back-bonded solar cell 350 according to the third embodiment can be manufactured.

Each method of manufacturing a semiconductor element and a solar cell according to the present invention is not limited to the first to third embodiments, and deformations such as various design changes may be applied based on the knowledge of a person having ordinary skill in the art, and the deformations may be applied. Embodiments are also included in the scope of the present invention. For example, in the first to third embodiments, the film layer forming step including the A film forming step and the B layer forming step using the coating method is exemplified, but the present invention is not limited to this. The film layer forming step may be a lamination method including a step of laminating a laminated body of the A film formed using the composition A in advance and the B layer formed on the A film using the composition B on a semiconductor. It is formed on a predetermined surface of the substrate.

In addition, the method for manufacturing a semiconductor device of the present invention can also be extended to photovoltaic devices such as solar cells, or semiconductor devices formed by patterning an impurity diffusion layer on a semiconductor substrate surface, such as a transistor array or a diode array, and a photovoltaic diode. Polar body array, converter, etc. [Example]

Hereinafter, the present invention will be described in more detail by taking examples. The present invention is not limited to the following examples. In addition, in the following examples, the abbreviations used in the compounds used are defined as follows.

"B ₂ O ₃ " is boron trioxide. "PVA" is polyvinyl alcohol. "GBL" is γ-butyrolactone. "MMB" is 3-methoxy-3-methyl-1-butanol. "PGME" is propylene glycol monomethyl ether. "DMF" is N, N-dimethylformamide. "MeTMS" is methyltrimethoxysilane. "PhTMS" is phenyltrimethoxysilane.

FIG. 4 is a diagram for each evaluation of peelability, diffusibility, diffusion uniformity, and barrier properties in Examples of the present invention. FIG. 5 is a diagram illustrating evaluation of diffusibility in a gas in an example of the present invention. Each evaluation in the present embodiment will be described with reference to FIGS. 4 and 5 as appropriate.

(Peelability Evaluation) Peelability evaluation is evaluation of the peelability of the A film from the semiconductor substrate surface. In the peelability evaluation, a silicon wafer 31 (see FIG. 4), which is an example of a semiconductor substrate, is an n-type silicon wafer (ELECTRONICS AND MATERIALS CORPORATION) with a texture processing of 156 mm × 156 mm. Co., Ltd., resistance value 0.5 [Ω · cm] -6.0 [Ω · cm]). This silicon wafer 31 was immersed in a 5% by weight aqueous solution of hydrofluoric acid for 1 minute, washed with water, and dried by a blower.

Next, by a known spin coating method, the composition A is coated on the silicon wafer 31 so that the film thickness after drying becomes about 500 nm, thereby preparing an A film 32 shown in a state a1 in FIG. 4. Then, by a known spin coating method, the composition B is applied onto the A film 32 so that the film thickness after drying becomes about 500 nm, thereby forming the B layer 33 shown in the state a1 in FIG. 4. Thereafter, the silicon wafer 31 was pre-baked at 150 ° C. for 1 minute. In this way, as shown in state a1 of FIG. 4, an impurity-diffused composition-coated substrate 30 having an A film 32 and a B layer 33 on the surface of the n-type silicon wafer 31 is obtained as shown in state a1 of FIG.

Next, the obtained impurity-diffusing composition-coated substrate 30 was placed in a diffusion furnace, and maintained at 900 ° C. for 30 minutes under an environment of nitrogen: oxygen = 99: 1 (volume ratio) to allow the impurity-diffusing component to self-extract The A film 32 is thermally diffused into the silicon wafer 31. After thermal diffusion, the impurity diffusion composition-coated substrate 30 was immersed in a 5% by weight aqueous solution of hydrofluoric acid at 23 ° C. for 1 minute, and the A film 32 and the B layer 33 were peeled from the silicon wafer 31. After peeling, the silicon wafer 31 was immersed in pure water for cleaning, and the surface of the silicon wafer 31 was visually observed to observe the residue of the A film 32 attached to the surface (hereinafter referred to as "surface attachment"). ) Yes or no.

In the peelability evaluation of this example, in each of the silicon wafers 31 to be evaluated, the surface attachments were visually confirmed after immersion for 1 minute, and those who could not remove the surface attachments even after wiping with waste cotton were judged as "poor ( worse). " After 1 minute of immersion, the surface attachment was visually recognized, but was removed by wiping with waste cotton, and it was judged to be "bad". Those who could not visually confirm surface attachment during immersion for more than 30 seconds and within 1 minute were judged to be "good". Those who could not visually confirm surface attachment during immersion within 30 seconds were judged as "excellent". From the viewpoint of the manufacturing cycle time, the combination of the silicon wafer 31 and the A film 32 can be used even if the peelability is good, but it is preferable that the peelability is excellent.

(Diffusion Evaluation) The diffusivity evaluation evaluates the diffusivity of the impurity diffusion component from the A film into the semiconductor substrate. In the diffusivity evaluation, the diffusive silicon wafer 31 used in the peelability evaluation was subjected to p / n determination using a p / n determination machine, and a four-probe type surface resistance measuring device RT-70V (Naipu) was used. (Manufactured by Napson Co., Ltd.), the surface resistance of the diffusion portion of the impurity diffusion component in the silicon wafer 31 was measured, and the obtained measurement value was set to the sheet resistance value. The sheet resistance value is an index of the diffusivity of an impurity diffusion component in a semiconductor substrate. A small sheet resistance value means that the diffusion amount of the impurity diffusion component is large. In the diffusivity evaluation of this embodiment, if the sheet resistance value is 40 [Ω / □] to 60 [Ω / □], it is determined as excellent. If the sheet resistance value is 60 [Ω / □] to 80 [Ω / □], it is judged as good. If the chip resistance value is 80 [Ω / □] to 100 [Ω / □], it is judged as bad. If the chip resistance value exceeds 100 [Ω / □], it is judged as bad.

(Evaluation of Diffusion Uniformity) The diffusion uniformity evaluation evaluates the uniformity of the diffusion of the impurity diffusion component from the A film into the semiconductor substrate. In the diffusion uniformity evaluation, a secondary ion mass spectrometer IMS7f (manufactured by Camera) was used for the diffused silicon wafer 31 used in the measurement of the sheet resistance value to analyze the diffusion components of impurities The surface concentration distribution of the diffused portion was measured. Based on the obtained surface concentration distribution, the surface concentration at 10 points at intervals of 100 μm was read, and “standard deviation / average” was calculated as a ratio of the average to the standard deviation. In the diffusivity evaluation of this example, if the "standard deviation / average" is 0.3 or less, it is determined to be excellent. When the "standard deviation / average" exceeds 0.3 or 0.6, it is judged as good. If the "standard deviation / average" exceeds 0.6 or 1.0, it is judged as bad. If the "standard deviation / average" exceeds 1.0, it is judged as "worse". The unevenness of the surface concentration of the impurity diffusion component significantly affects the power generation efficiency, so it is best to be excellent.

(Evaluation of barrier properties) The evaluation of barrier properties is an evaluation of the barrier properties of the B layer with respect to the impurity diffusion component. In the barrier property evaluation, a silicon wafer 41 is prepared separately from the silicon wafer 31 used in the impurity diffusion composition-coated substrate 30 (see state a1 in FIG. 4) for the evaluation, as shown in state b1 in FIG. 4. The impurity diffusion composition film 45 having a conductivity type different from that of the A film 32 is formed on the surface of the silicon wafer 41. Specifically, an impurity diffusion composition having a conductivity type different from that of the A film 32 is applied to the silicon wafer 41 by a known spin coating method so that the film thickness after drying becomes about 500 nm. The impurity diffusion composition is referred to as an n-type composition A-3 or a p-type composition A-1 described later. After coating, the silicon wafer 41 is pre-baked at 140 ° C. for 5 minutes, whereby an impurity diffusion composition film 45 is formed on the surface of the silicon wafer 41. In this way, the impurity-diffused composition-coated substrate 40 as shown in the state b1 of FIG. 4 was obtained.

Next, as shown in a state c1 of FIG. 4, it is assumed that the impurity diffusion composition-coated substrate 30 as a silicon wafer for evaluation is separated from the impurity diffusion composition-coated substrate 40 of a different conductivity type by a distance of 3 mm. The opposite state is placed in the electric furnace. At this time, the B-layer 33 of the impurity diffusion composition coating substrate 30 and the impurity diffusion composition film 45 of the impurity diffusion composition coating substrate 40 are provided so as to face each other. Then, under an environment of nitrogen: oxygen = 99: 1 (volume ratio), it is maintained at 900 ° C. for 30 minutes, so that the impurity diffusion component is thermally diffused from the A film 32 into the silicon wafer 31, and the impurity diffusion component is self-diffusion The impurity diffusion composition film 45 is thermally diffused into the silicon wafer 41. Thereby, as shown in the state d1 of FIG. 4, an impurity diffusion layer 34 is formed on the silicon wafer 31 of the impurity diffusion composition-coated substrate 30, and is formed on the silicon wafer 41 of the impurity diffusion composition-coated substrate 40 Impurity diffusion layer 46.

After thermal diffusion, each of the impurity diffusion composition-coated substrate 30 and the impurity diffusion composition-coated substrate 40 were immersed in a 5% by mass aqueous hydrofluoric acid solution at 23 ° C. Thereby, the A film 32 and the B layer 33 are removed from the silicon wafer 31, and the hardened impurity diffusion composition film 45 is removed from the silicon wafer 41 (refer to the state d1 and the state e1 in FIG. 4).

Subsequently, the silicon wafer 31 for evaluation was measured for the surface concentration distribution of phosphorus atoms and boron atoms using a secondary ion mass spectrometer IMS7f (manufactured by Camera). The low surface concentration of the heterogeneous impurities in the surface of the silicon wafer 31 (the surface on the side where the impurity diffusion layer 34 is formed) means that the B layer 33 diffuses the impurities in the gas with respect to the impurity diffusion composition film 45 on the opposite side. High barrier. The “heterogeneous impurity” described here is an impurity diffusion component of a conductivity type different from that of the impurity diffusion layer 34 in the silicon wafer 31, and is included in the impurity diffusion composition film 45. In the barrier property evaluation of this example, if the obtained surface concentration of a phosphorus atom or a boron atom was 10 ¹⁷ or less, it was judged to be excellent. When the surface concentration exceeds 10 ¹⁷ and 10 ¹⁸ or less, it is determined to be good. If the surface concentration exceeds 10 ¹⁸ , it is judged as bad.

(Evaluation of Diffusivity in Gas) The evaluation of diffusivity in gas evaluates the function of suppressing the diffusion in the gas of the impurity diffusion component caused by the B layer. In the gas diffusivity evaluation, an impurity diffusion composition-coated substrate 30 for evaluation shown in a state a2 in FIG. 5 and a silicon wafer 51 shown in a state b2 in FIG. 5 (when no coating film is applied) are prepared. , And as shown in the state c2 of FIG. 5, make these opposite faces. At this time, the impurity diffusion composition-coated substrate 30 and the B layer 33 and the silicon wafer 51 are provided so as to face each other. Thereafter, the impurity diffusion component is thermally diffused from the A film 32 to the silicon wafer 31 in the same manner as the method for evaluating the barrier property, whereby the impurity is formed in the silicon wafer 31 of the impurity diffusion composition-coated substrate 30. The diffusion layer 34 then removes the A film 32 and the B layer 33 from the silicon wafer 31 (see the state d2 and the state e2 in FIG. 5).

In the gas diffusivity evaluation of this example, a secondary ion mass spectrometer IMS7f (manufactured by Camera) was used for the uncoated silicon wafer 51 on the opposite side, and The surface concentration distribution was measured. The low surface concentration of the phosphorus atom or the boron atom in the silicon wafer 51 on the opposite side means that there is less diffusion in the gas of the impurity diffusion component from the A film 32. When the surface concentration of the obtained phosphorus atom or boron atom is 10 ¹⁷ or less, it is judged as excellent. When the surface concentration exceeds 10 ¹⁷ and 10 ¹⁸ or less, it is determined to be good. If the surface concentration exceeds 10 ¹⁸ , it is judged as bad.

(Tap Time Evaluation) The tact time evaluation is an evaluation of the time required to form the A film and the B layer on the semiconductor substrate. In this embodiment, the tact time is the time required from the start of the step of forming the A film 32 on the silicon wafer 31 to the end of the step of forming the B layer 33 on the A film 32. In the tact time evaluation of this embodiment, if the tact time is less than 30 seconds, it is determined to be good. If the cycle time is more than 30 seconds, it is judged as bad.

(Measurement of weight average molecular weight of polysiloxane) The weight average molecular weight of polysiloxane is a GPC (HLC-8220GPC manufactured by Tosoh Corporation) after filtering the sample with a membrane filter having a pore size of 0.45 μm It is calculated | required by polystyrene conversion. At this time, the developing solvent was tetrahydrofuran, and the developing speed was 0.4 [mL / min]. The column was TSKgel SuperHM-H manufactured by Tosoh Corporation.

<Example 1> (Production of Composition A) In the production of Composition A in Example 1, 20.8 g of PVA (manufactured by Wako Pure Chemical Industries, Ltd., 500) and 144 g of PVA were placed in a 500 mL three-necked flask. The water was heated to 80 ° C while stirring. After stirring for 1 hour, 231.6 g of MMB (Kuraray Co., Ltd.) and 3.6 g of B ₂ O _{3 were added} , and the mixture was stirred at 80 ° C for 1 hour. Next, the obtained solution was cooled to 40 ° C, and then 0.12 g of a fluorine-based surfactant (Megafac F477, manufactured by Dainippon Ink And Chemicals Industrial Co., Ltd.) was added thereto, and stirred. 30 minutes. As a result, a composition A-1 was obtained as the composition A of Example 1.

(Production of composition B) In the production of composition B in Example 1, 164.93 g (1.21 mol) of KBM-13 (methyltrimethoxysilane) and 204.07 g (1.21) were put into a 500 mL three-necked flask. mol) of KBM-103 (phenyltrimethoxysilane) and 363.03 g of GBL (manufactured by Mitsubishi Chemical Corporation) were added at 40 ° C while stirring for 30 minutes to dissolve 4.50 g of formic acid in 130.76 g of An aqueous solution made from water. After completion of the dropwise addition, the obtained solution was stirred at 40 ° C for 1 hour, and then heated to 70 ° C and stirred for 30 minutes. Thereafter, the oil bath was heated to 115 ° C. One hour after the start of the temperature increase, the internal temperature of the solution reached 100 ° C, and the solution was heated and stirred for one hour (the internal temperature was 100 ° C to 110 ° C). The solution obtained in this manner was cooled with an ice bath to obtain a polysiloxane solution (PhTMS (50) / MeTMS (50)). "PhTMS (50) / MeTMS (50)" means that the ratio of PhTMS to MeTMS in polysiloxane is 50:50. The same applies to the following.

The solid content concentration of the obtained polysiloxane solution was 39.8% by weight, and the weight average molecular weight (Mw) was 2900. In a solution of polysiloxane (4.39 g) and GBL (12.55 g) synthesized as described above, add a silicone surfactant (BYK333) so that it is 300 ppm relative to the entire solution, and stir well To make it even. As a result, a composition B-1 was obtained as the composition B of Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 1, an n-type silicon wafer (ELECTRONICS AND MATERIALS CORPORATION) with a texture processing of 156 mm × 156 mm was produced. Co., Ltd., resistance value 0.5 [Ω · cm] -6.0 [Ω · cm]) was immersed in a 5% by weight aqueous solution of hydrofluoric acid for 1 minute, washed with water, and dried by a blower. Next, the composition A-1 was coated on the n-type silicon wafer by a known spin coating method so that the film thickness after drying became about 500 nm, thereby forming an A film. Then, the composition B-1 was applied to the A film by a known spin coating method so that the film thickness after drying became about 500 nm, thereby forming a B layer. In this way, the silicon wafer for evaluation of Example 1 was obtained.

In Example 1, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 1, as shown in Table 2 described below, these evaluation items were particularly good.

<Example 2> (Production of composition A) In the production of composition A in Example 2, a composition A-1 was obtained in the same manner as in Example 1.

(Production of Composition B) In the production of Composition B in Example 2, 59.49 g (0.30 mol) of phenyltrimethoxysilane and 165.57 g (0.70 mol (in terms of SiO ₂ conversion) were put into a 500 mL three-necked flask. )) PL-2L-IPA (silica dioxide IPA dispersion made by Fuso Chemical Co., Ltd. silicon dioxide average particle diameter 17 nm silicon dioxide concentration 25.4 wt%), 133.07 g of PGME, at room temperature, while stirring An aqueous formic acid solution in which 3.04 g of formic acid was dissolved in water (16.20 g) required for the hydrolysis of the monomer was added over 30 minutes. Next, the three-necked flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and thereafter, the oil bath was heated to 130 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution in the three-necked flask reached 100 ° C, and the solution was heated and stirred for 3 hours (the internal temperature was 100 ° C to 118 ° C). In the reaction at this time, a total of 147.3 g of methanol, IPA, water, and formic acid were distilled as by-products.

In the PGME solution of the polysiloxane (PhTMS (100) / MeTMS (0)) obtained as described above, PGME was added so that the solid content concentration of the polysiloxane became 40% by weight. As a result, a composition B-2 was obtained as the composition B of Example 2.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 2, a composition B-2 was used in place of the composition B-1, except that a composition B-2 was obtained. The silicon wafer for evaluation of Example 2.

In Example 2, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 2, as shown in Table 2, these evaluation items were all good.

<Example 3> (Production of Composition A) In the production of Composition A in Example 3, PGME (KHneochem Co., Ltd.) was used instead of MMB as a solvent. A composition A-2 was obtained in the same manner as in Example 1.

(Production of Composition B) In the production of Composition B in Example 3, Composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 3, a composition A-2 was used in place of the composition A-1, except that a composition A-2 was obtained. The silicon wafer for evaluation of Example 3.

In Example 3, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 3, as shown in Table 2, these evaluation items were particularly good.

<Example 4> (Production of Composition A) In the production of Composition A in Example 4, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Example 4, a composition B-2 was obtained in the same manner as in Example 2.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 4, a composition B-2 was used in place of the composition B-1, except that a composition B-2 was obtained. The silicon wafer for evaluation of Example 4.

In Example 4, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 4, as shown in Table 2, these evaluation items were all good.

<Example 5> (Composition A) In Example 5, as the composition A, PBF (a paste containing p-type impurities, manufactured by Tokyo Yingka Kogyo Co., Ltd.) was used.

(Production of Composition B) In the production of Composition B in Example 5, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 5, except that PBF was used instead of the composition A-1, a film of Example 5 was obtained in the same manner as in Example 1. Evaluation silicon wafer.

In Example 5, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 5, as shown in Table 2, these evaluation items were particularly good.

<Example 6> (Composition A) In Example 6, as the composition A, PBF (a paste containing p-type impurities, manufactured by Tokyo Yingka Kogyo Co., Ltd.) was used.

(Production of Composition B) In the production of Composition B in Example 6, a composition B-2 was obtained in the same manner as in Example 2.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 6, except that PBF was used instead of the composition A-1, a film of Example 6 was obtained in the same manner as in Example 2. Evaluation silicon wafer.

In Example 6, each of the evaluations of peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was performed using the obtained evaluation silicon wafer. As a result, in Example 6, as shown in Table 2, these evaluation items were all good.

<Example 7> (Production of Composition A) In the production of Composition A in Example 7, 6 g of phosphoric acid (H ₃ PO ₄ , manufactured by Wako Pure Chemical Industries, Ltd.) was added to a 500 mL three-necked flask. ), 193 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of water, and stirred at room temperature for 30 minutes to obtain a composition A-3.

(Production of Composition B) In the production of Composition B in Example 7, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 7, a composition A-3 was used in place of the composition A-1, except that a composition A-3 was obtained. The silicon wafer for evaluation of Example 7.

In Example 7, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 7, as shown in Table 2, the diffusibility and the uniformity of diffusion were good, and the peelability, the barrier property, and the diffusibility in gas were particularly good.

<Example 8> (Production of Composition A) In the production of Composition A in Example 8, a composition A-3 was obtained in the same manner as in Example 7.

(Production of Composition B) In the production of Composition B in Example 8, a composition B-2 was obtained in the same manner as in Example 2.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 8, a composition A-3 was used in place of the composition A-1, except that a composition A-3 was obtained. The silicon wafer for evaluation of Example 8.

In Example 8, each of the evaluations of peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was performed using the obtained evaluation silicon wafer. As a result, in Example 8, as shown in Table 2, these evaluation items were all good.

<Example 9> (Production of composition A) In the production of composition A in Example 9, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) The production of Composition B in Example 9 was performed in the same manner as in Example 1 except that the composition of polysiloxane was set to PhTMS (40) / MeTMS (60). Composition B-3 was obtained. The weight average molecular weight (Mw) of the polysiloxane solution used was 3,100.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 9, a composition B-3 was used in place of the composition B-1, except that a composition B-3 was obtained. The silicon wafer for evaluation of Example 9.

In Example 9, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 9, as shown in Table 2, these evaluation items were particularly good.

<Example 10> (Production of composition A) In the production of composition A in Example 10, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Example 10, the composition of polysiloxane was set to PhTMS (90) / MeTMS (10), except that the composition was the same as that of Example 1. Composition B-4 was obtained. The weight average molecular weight (Mw) of the polysiloxane solution used was 2,300.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 10, a composition B-4 was used in place of the composition B-1, except that a composition B-4 was obtained. The silicon wafer for evaluation of Example 10.

In Example 10, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 10, as shown in Table 2, these evaluation items were particularly good.

<Example 11> (Production of Composition A) In the production of Composition A in Example 11, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Example 11, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 11, the composition A-2 was applied so that the film thickness after drying was about 500 nm by a known spin coating method. It is laid on the same silicon wafer as in the first embodiment to form an A film. Then, by a known spin coating method, the composition B-1 was applied onto the A film so that the film thickness after drying became about 200 nm, thereby forming a B layer. In this manner, the silicon wafer for evaluation of Example 11 was obtained.

In Example 11, each evaluation of peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was performed using the obtained evaluation silicon wafer. As a result, in Example 11, as shown in Table 2, these evaluation items were particularly good.

<Example 12> (Production of composition A) In the production of composition A in Example 12, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Example 12, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 12, the composition A-2 was applied so that the film thickness after drying was about 500 nm by a known spin coating method. It is laid on the same silicon wafer as in the first embodiment to form an A film. Then, by a known spin coating method, the composition B-1 was applied on the A film so that the film thickness after drying became about 2000 nm, thereby forming a B layer. In this manner, the silicon wafer for evaluation of Example 12 was obtained.

In Example 12, each evaluation of peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was performed using the obtained evaluation silicon wafer. As a result, in Example 12, as shown in Table 2, these evaluation items were particularly good.

<Example 13> (Production of Composition A) In the production of Composition A in Example 13, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Example 13, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Example 13, an A film (film thickness of about 500 nm) formed on the film using the composition A-2 was laminated by lamination. Transfer on a silicon wafer. Thereafter, the B layer (film thickness of about 500 nm) formed on the film using the composition B-1 was transferred by lamination to a silicon wafer on which the A film was formed. Thereby, the A film and the B layer are formed on the silicon wafer. In this manner, the silicon wafer for evaluation of Example 13 was obtained.

In Example 13, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Example 13, as shown in Table 2, these evaluation items were particularly good.

<Comparative Example 1> (Production of Composition A) In the production of Composition A in Comparative Example 1, 2% by weight of tributyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to Composition B-1 to obtain Composition A-4.

(Production of Composition B) In the production of Composition B in Comparative Example 1, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 1, a composition A-4 was used in place of the composition A-1, except that a composition A-4 was obtained. The silicon wafer for evaluation of Comparative Example 1.

In Comparative Example 1, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 1, as shown in Table 2, peelability, diffusibility, and diffusion uniformity were poor.

<Comparative Example 2> (Production of Composition A) In the production of Composition A in Comparative Example 2, a composition A-4 was obtained in the same manner as in Comparative Example 1.

(Production of Composition B) In the production of Composition B in Comparative Example 2, a composition B-2 was obtained in the same manner as in Example 2.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 2, a composition A-4 was used in place of the composition A-1, except that a composition A-4 was obtained. The silicon wafer for evaluation of Comparative Example 2.

In Comparative Example 2, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 2, as shown in Table 2, peelability, diffusibility, and diffusion uniformity were poor.

<Comparative Example 3> (Production of Composition A) In the production of Composition A in Comparative Example 3, a composition A-1 was obtained in the same manner as in Example 1.

(Production of Composition B) In the production of Composition B in Comparative Example 3, a 5% by weight PGME solution of an acrylic resin (KC-7000 manufactured by Kyoeisha Chemical Co., Ltd.) was prepared. Thus, a composition B-5 was obtained as a composition B of Comparative Example 3.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 3, a composition B-5 was used instead of the composition B-1. The silicon wafer for evaluation of Comparative Example 3.

In Comparative Example 3, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 3, as shown in Table 2, these evaluation items were all inferior.

<Comparative Example 4> (Composition A) In Comparative Example 4, as the composition A, PBF (a paste containing p-type impurities, manufactured by Tokyo Yingka Kogyo Co., Ltd.) was used.

(Production of Composition B) In the production of Composition B in Comparative Example 4, a composition B-5 was obtained in the same manner as in Comparative Example 3.

(Production of Silicon Wafer for Evaluation) In the production of silicon wafer for evaluation in Comparative Example 4, except that PBF was used in place of Composition A-1, a film of Comparative Example 4 was obtained in the same manner as in Comparative Example 3. Evaluation silicon wafer.

In Comparative Example 4, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 4, as shown in Table 2, these evaluation items were all inferior.

<Comparative Example 5> (Production of Composition A) In the production of Composition A in Comparative Example 5, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) The production of Composition B in Comparative Example 5 was performed in the same manner as in Example 1 except that the composition of polysiloxane was set to PhTMS (30) / MeTMS (70). Composition B-6 was obtained. The weight average molecular weight (Mw) of the polysiloxane solution used was 3,400.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 5, a composition B-6 was used in place of the composition B-1, except that a composition B-6 was obtained. The silicon wafer for evaluation of Comparative Example 5.

In Comparative Example 5, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 5, as shown in Table 2, these evaluation items were all good.

<Comparative Example 6> (Production of Composition A) In the production of Composition A in Comparative Example 6, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) The production of Composition B in Comparative Example 6 was performed in the same manner as in Example 1 except that the composition of polysiloxane was set to PhTMS (95) / MeTMS (5). Composition B-7 was obtained. The weight average molecular weight (Mw) of the polysiloxane solution used was 2,200.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 6, a composition B-7 was used instead of the composition B-1. The silicon wafer for evaluation of Comparative Example 6.

In Comparative Example 6, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 6, as shown in Table 2, these evaluation items were all good.

<Comparative Example 7> (Production of Composition A) In the production of Composition A in Comparative Example 7, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Comparative Example 7, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 7, the composition A-2 was applied so that the film thickness after drying was about 500 nm by a known spin coating method. It is laid on the same silicon wafer as in the first embodiment to form an A film. Then, the composition B-1 was applied to the A film by a known spin coating method so that the film thickness after drying became about 100 nm, thereby forming a B layer. In this way, the silicon wafer for evaluation of Comparative Example 7 was obtained.

In Comparative Example 7, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 7, as shown in Table 2, barrier properties and diffusibility in gas were poor.

<Comparative Example 8> (Production of Composition A) In the production of Composition A in Comparative Example 8, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Comparative Example 8, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 8, the composition A-2 was applied so that the film thickness after drying was about 500 nm by a known spin coating method. It is laid on the same silicon wafer as in the first embodiment to form an A film. Next, a known spin coating method was used to apply the composition B-1 on the A film so that the film thickness after drying became about 3000 nm, thereby forming a B layer. In this way, the silicon wafer for evaluation of Comparative Example 8 was obtained.

In Comparative Example 8, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 8, as shown in Table 2, peelability, diffusibility, and diffusion uniformity were poor.

<Comparative Example 9> (Production of Composition A) In the production of Composition A in Comparative Example 9, 2% by weight of B ₂ O ₃ was added to Composition B-2 to obtain Composition A-5.

(Production of Composition B) In the production of Composition B in Comparative Example 9, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) Production of the silicon wafer for evaluation in Comparative Example 9 was carried out in the same manner as in Example 1 except that the composition A-5 was used instead of the composition A-1. The silicon wafer for evaluation of Comparative Example 9.

In Comparative Example 9, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 9, as shown in Table 2, peelability, diffusibility, and diffusion uniformity were poor.

<Comparative Example 10> (Production of Composition A) In the production of Composition A in Comparative Example 10, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Comparative Example 10, except that DMF was used instead of GBL, Composition B-8 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 10, a composition B-8 was used in place of the composition B-1, except that a composition B-8 was obtained. The silicon wafer for evaluation of Comparative Example 10.

In Comparative Example 10, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 10, as shown in Table 2, these evaluation items were all inferior.

<Comparative Example 11> (Production of Composition A) In the production of Composition A in Comparative Example 11, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Comparative Example 11, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 11, a drying step using a heat treatment was provided between the step of forming the A film and the step of forming the B layer. The silicon wafer for evaluation of Comparative Example 11 was obtained in the same manner as in Example 1 described above.

In Comparative Example 11, each of the peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was evaluated using the obtained evaluation silicon wafer. As a result, in Comparative Example 11, as shown in Table 2, all of these evaluation items were good, but the cycle time was inferior to that of Example 1 in comparison with Example 1.

<Comparative Example 12> (Production of Composition A) In the production of Composition A in Comparative Example 12, a composition A-2 was obtained in the same manner as in Example 3.

(Production of Composition B) In the production of Composition B in Comparative Example 12, a composition B-1 was obtained in the same manner as in Example 1.

(Production of Silicon Wafer for Evaluation) In the production of the silicon wafer for evaluation in Comparative Example 12, a step of stopping the rotation in the spin coating method is provided between the step of forming the A film and the step of forming the B layer. Other than that, the evaluation silicon wafer of Comparative Example 12 was obtained in the same manner as in Example 1.

In Comparative Example 12, each evaluation of peelability, diffusivity, diffusion uniformity, barrier properties, and diffusibility in gas was performed using the obtained evaluation silicon wafer. As a result, in Comparative Example 12, as shown in Table 2, all of these evaluation items were good, but the cycle time was inferior to that of Example 1 in comparison with Example 1.

Various information concerning the composition A and the composition B in each of the above-mentioned Examples 1 to 13 are shown in Table 1A. Various information related to the composition A and the composition B in each of the comparative examples 1 to 12 are shown in Table 1B. In Tables 1A and 1B, the "name" in the "composition A" column indicates the name of the composition A used in the formation of the A film. The "composition" in the "composition A" column indicates the impurities (impurity diffusion component), the binder resin, and the solvent contained in the composition A. The "forming method" in the column of "composition A" indicates the method for forming the A film using composition A. The "name" in the "composition B" column indicates the name of the composition B used in the formation of the B layer. The "composition" in the "composition B" column indicates a diffusion inhibitor and a solvent in the gas contained in the composition B. Specifically, the polysiloxane as a diffusion inhibitor in a gas is shown as a raw organosilane, a molar ratio of an aryl group in R ¹ to an alkyl group in R ³ in the general formula (1), Film thickness after drying. In addition, other additives are shown. The "forming method" in the "composition B" column indicates a method for forming the B layer using the composition B.

[Table 1A]

[Table 1B]

[Table 2] [Industrial availability]

As described above, the method for manufacturing a semiconductor element and the method for manufacturing a solar cell of the present invention are useful for reducing the number of steps for manufacturing a semiconductor element and a solar cell, and are particularly suitable for the required impurity diffusion component in a semiconductor substrate. Efficient diffusion of the area.

1‧‧‧ semiconductor substrate

2‧‧‧A film

3‧‧‧B floor

4‧‧‧ Impurity diffusion layer

11‧‧‧ semiconductor substrate

12‧‧‧A film

13‧‧‧B Floor

14‧‧‧ Impurity diffusion layer

15‧‧‧ Impurity diffusion composition film

16‧‧‧ Impurity diffusion layer

17‧‧‧ passivation layer

18, 19‧‧‧ electrodes

21‧‧‧semiconductor substrate

22‧‧‧A film

23‧‧‧B Floor

24‧‧‧ Impurity diffusion layer

25‧‧‧ Impurity diffusion composition film

26‧‧‧ Impurity diffusion layer

27‧‧‧ passivation layer

28, 29‧‧‧ electrodes

30‧‧‧ Impurity diffusion composition coated substrate

31‧‧‧ silicon wafer

32‧‧‧A film

33‧‧‧B Floor

34‧‧‧ Impurity diffusion layer

40‧‧‧ Impurity diffusion composition coated substrate

41, 51‧‧‧ silicon wafers

45‧‧‧ Impurity diffusion composition film

46‧‧‧ Impurity diffusion layer

100, 200, 300‧‧‧ semiconductor components

250, 350‧‧‧ solar cells

FIG. 1 is a diagram showing an example of a method of manufacturing a semiconductor device according to the first embodiment of the present invention. FIG. 2A is a diagram showing an example of a method of manufacturing a semiconductor device according to the second embodiment of the present invention. 2B is a diagram showing an example of a method for manufacturing a solar cell according to the second embodiment of the present invention. FIG. 3A is a diagram showing an example of a method of manufacturing a semiconductor device according to the third embodiment of the present invention. 3B is a diagram showing an example of a method for manufacturing a solar cell according to a third embodiment of the present invention. FIG. 4 is a diagram illustrating evaluations of peelability, diffusivity, diffusion uniformity, and barrier properties in Examples of the present invention. FIG. 5 is a diagram illustrating evaluation of diffusibility in a gas in an example of the present invention.

Claims (15)

A method for manufacturing a semiconductor element, comprising: a film layer forming step of forming an A film and a B layer on a semiconductor substrate, wherein the A film is an impurity diffusion composition film formed using a composition A containing an impurity diffusion component; The B layer is a diffusion suppressing layer in a gas that uses a composition B containing polysiloxane and suppresses at least the diffusion of the impurity diffusion component gas from the A film; and a diffusion step, The semiconductor substrate on which the A film and the B layer are formed is heat-treated to diffuse the impurity diffusion component into the semiconductor substrate. The method for manufacturing a semiconductor device according to item 1 of the scope of patent application, wherein the film layer forming step includes: an A film forming step of applying the composition A to a predetermined surface of the semiconductor substrate to form the film; The A film; and a B layer forming step, applying the composition B on the A film to form the B layer. The method for manufacturing a semiconductor device according to item 1 of the scope of patent application, wherein the film layer forming step includes the following steps: the A film formed using the composition A in advance and the composition B using The laminated body of the B layer formed on the A film is formed by laminating a predetermined surface of the semiconductor substrate. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the dried film thickness of the layer B is 200 nm or more and 2000 nm or less. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the composition A includes an adhesive resin. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the composition B includes a polysiloxane represented by the following general formula (1), (In the 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 ³ represents an alkyl group having 1 to 6 carbon atoms or a carbon group having 2 to 10 carbon atoms. Alkenyl, multiple R ³ may be the same or different; R ² and R ^{4 each} represent a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and a fluorenyl group having 1 to 6 carbon atoms, and multiple R 3 ² and R ⁴ may be the same or different respectively; among them, any of R ² and R ⁴ must be a hydroxyl group; n and m represent the composition ratio (%) of the components in each bracket, n + m = 100, n: m = 90: 10 to 40: 60; X is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, and 2 to 10 carbon atoms Any of alkenyl, aryl having 6 to 15 carbons, and heteroaryl having 3 to 12 carbons; Y is a hydrogen atom, alkyl having 1 to 6 carbons, and fluorenyl having 1 to 7 carbons Either). The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the composition A and the composition B are incompatible with each other. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the composition A includes a binder resin, and the decomposition temperature of the binder resin is lower than the composition B The hardening temperature of the polysiloxane contained in. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein in the film layer forming step, the A film and the substrate are continuously formed without a drying step using heat treatment.列 B layer. The method for manufacturing a semiconductor device according to item 2 of the scope of patent application, wherein the A film and the B layer are formed by a spin coating method. The method for manufacturing a semiconductor device according to claim 10, wherein the A film forming step and the B layer forming step are performed continuously without stopping the rotation in the spin coating method. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the composition A includes a water-soluble binder resin, the composition B includes a solvent, and the water-soluble The solubility of the binder resin with respect to the solvent is 0.01 g / mL or less at 25 ° C. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the composition A includes a boron compound, polyvinyl alcohol, and water. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, further comprising forming a surface on the side of the semiconductor substrate opposite to the A film from the A film. A film forming step of an impurity diffusion composition film having a different conductivity type from the film, in the diffusion step, heat-treating the semiconductor substrate on which the impurity diffusion composition film, the A film, and the B layer are formed, The impurity diffusion component from the impurity diffusion composition film is diffused in the semiconductor substrate, and the impurity diffusion component from the A film is diffused in the semiconductor substrate, so as to simultaneously form the semiconductor substrate on the semiconductor substrate. The impurity diffusion layer of the impurity diffusion composition film and the impurity diffusion layer from the A film. A method for manufacturing a solar cell, comprising a method for manufacturing a semiconductor element, the method for manufacturing the semiconductor element includes: a film layer forming step of forming an A film and a B layer on a semiconductor substrate; the A film is made of impurities The impurity diffusion composition film composed of the composition A that diffuses the component, the layer B is made of the composition B containing polysiloxane, and is a gas that suppresses at least the impurity diffusion component from the A film A medium diffusion-inhibiting layer in a medium-diffused gas; and a diffusion step of heat-treating the semiconductor substrate on which the A film and the B layer are formed to diffuse the impurity diffusion component in the semiconductor substrate.