TW201829625A - Impurity diffusion composition and semiconductor element production method using impurity diffusion composition - Google Patents

Abstract

An impurity diffusion composition according to one embodiment is for diffusing a desired conductive impurity-diffused component into a semiconductor substrate. The impurity diffusion composition contains a polysiloxane (A) and an impurity-diffused component (B). The polysiloxane (A) contains a carboxyl group and/or a dicarboxylic acid anhydride structure. The impurity diffusion composition is for use in a semiconductor element production method and is particularly suitable for use in the production of solar cells.

Description

Impurity diffusion composition and method of manufacturing semiconductor device using same

The present invention relates to an impurity diffusion composition for diffusing an impurity diffusion component into a semiconductor substrate, and a method of manufacturing a semiconductor device using the same.

Now, in the manufacture of a semiconductor element such as a solar cell, when an n-type or p-type impurity diffusion layer is formed in a semiconductor substrate, an impurity diffusion source is formed on the semiconductor substrate, and impurities are diffused by thermal diffusion. A method of diffusing a component into a semiconductor substrate. The impurity diffusion source is formed by a solution coating method of a chemical vapor deposition (CVD) method or 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 the semiconductor substrate, and then a resist having a predetermined pattern is laminated on the thermal oxide film by photolithography. Then, using the resist as a mask, a portion of the thermal oxide film not covered by the resist is etched by an acid or a base, and then the resist is peeled off to form a thermally oxidized film. The mask. Then, an n-type or p-type impurity diffusion composition is applied to cause the impurity diffusion composition to adhere to the portion of the opening of the mask. Thereafter, the impurity diffusion component in the composition is thermally diffused into the semiconductor substrate at 600 ° C to 1250 ° C to form an n-type or p-type impurity diffusion layer.

In the production of semiconductor elements such as solar cells, in recent years, there has been a strong demand for a method in which an impurity diffusion layer is simply formed on a desired portion of a semiconductor substrate without using a complicated photolithography technique at a conventional height. As such a method, there has been studied a method in which an impurity diffusion composition is applied onto a semiconductor substrate, and the coating film (that is, the impurity diffusion composition film) is locally irradiated with laser light, thereby heating to selectively form an impurity. Diffusion layer (for example, refer to Patent Document 1 and Patent Document 2) [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-114298 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2009-238824

[Problems to be Solved by the Invention] However, in the conventional impurity diffusion composition, when the impurity diffusion component is locally diffused from the impurity diffusion film to the semiconductor substrate by using laser light or the like, the radiation is not irradiated. There is a problem in the cleaning property of the dried film of the impurity diffusion composition remaining on the semiconductor substrate by the light. The "dry film of the impurity diffusion composition" is a portion of the impurity diffusion composition film formed on the semiconductor substrate and which is not irradiated with the laser light, that is, a portion where the laser is not irradiated.

The present invention has been made in view of the above-described facts, and an object of the present invention is to provide a dry film (a laser non-irradiated portion) having an excellent impurity diffusing property to a semiconductor substrate and an impurity diffusion composition remaining on the semiconductor substrate. An impurity diffusion composition excellent in properties and a method for producing a semiconductor device using the same. [Means for solving the problem]

In order to solve the above problems and achieve the object, the impurity diffusion composition of the present invention is characterized by comprising: a polyoxyalkylene oxide (A) and an impurity diffusion component (B), and the polyoxyalkylene oxide (A) contains a carboxyl group and two At least one of the carboxylic anhydride structures.

Further, the impurity-diffusion composition of the present invention is characterized in that the polyoxyalkylene (A) is a polyoxyalkylene represented by the following formula (1).

[Chemical 1] (In the formula (1), R ¹ represents a substituent containing at least one of a carboxyl group and a dicarboxylic anhydride structure, and a plurality of R ^{1 's} may be the same or different; and R ² , R ³ and R ⁴ represent a hydroxyl group or a carbon. Any of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; Each of R ² , R ³ and R ⁴ may be the same or different; n and m represent the composition ratio (%) of the components in each parenthesis, n+m=100, n:m=5:95 to 30:70 )

In addition, the impurity diffusion composition of the present invention is characterized in that R ^{1 in} the above formula (1) is represented by any one of the following formulas (2) to (6). base.

[Chemical 2] (In the general formulae (2) to (6), R ⁵ , R ⁷ , R ⁸ and R ⁹ represent a divalent organic group having 1 to 20 carbon atoms; and R ⁶ represents a hydrogen atom or an alkane having 1 to 3 carbon atoms; R ¹⁰ , R ¹¹ and R ¹² represent a single bond, a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or the like. a carbonyl group, an ether group, an ester group, a decylamino group, an aromatic group having 6 to 16 carbon atoms or a divalent group having any of these; the hydrogen atom of the group may be an alkyl group having 1 to 10 carbon atoms , an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, a hydroxyl group, an amine group, a carboxyl group or a thiol group; h, j, k and l An integer representing 0 to 3)

Further, the impurity diffusion composition of the present invention is characterized in that the content of the impurity diffusion component (B) is 0.1% by mass or more and 20% by mass or less.

Further, the impurity diffusion composition of the present invention is characterized in that the impurity diffusion component (B) contains a compound selected from the group consisting of phosphoric acid, phosphorus pentoxide, polyphosphoric acid, phosphoric acid ester, boron oxide, and boric acid. And one or more of boric acid ester, boronic acid, and boronic acid ester.

Further, the impurity diffusion composition of the present invention is characterized in that the impurity diffusion component (B) contains one or more selected from the group consisting of boric acid, hydrocarbylboronic acid, boric acid ester, and hydrocarbyl borate, and further contains water. And water soluble binders.

Further, the impurity diffusion composition of the present invention is the invention according to the invention, characterized in that the water-soluble binder is polyvinyl alcohol.

Further, the method for producing a semiconductor device of the present invention includes a film forming step of applying the impurity diffusion composition according to any one of the inventions described above to a semiconductor substrate to form an impurity diffusion composition film; The layer forming step of diffusing the impurity diffusion component from the impurity diffusion composition film into the semiconductor substrate to form an impurity diffusion layer.

Further, the method for producing a semiconductor device of the present invention includes a film forming step of applying the impurity diffusion composition according to any one of the inventions described above to a semiconductor substrate to form an impurity diffusion composition film; In the layer forming step, the impurity diffusion composition film is irradiated with laser light, and the impurity diffusion component is diffused from the impurity diffusion composition film into the semiconductor substrate to form an impurity diffusion layer.

Further, the method of manufacturing a semiconductor device of the present invention is characterized by comprising: a film forming step of applying the impurity diffusion composition according to any one of the inventions described above to a semiconductor substrate to form an impurity diffusion composition film; a forming step of irradiating a part of the impurity diffusion composition film with laser light, diffusing a part of the impurity diffusion component from the impurity diffusion composition film into the semiconductor substrate to form an impurity diffusion layer; and removing the step by The portion of the impurity diffused in the film of the impurity that is not irradiated with the laser light is removed by an acid or a base. [Effects of the Invention]

According to the present invention, it is possible to provide an impurity diffusion composition excellent in cleaning property of a dried film having excellent impurity diffusibility to a semiconductor substrate and having an impurity diffusion composition remaining on a semiconductor substrate, and a semiconductor using the same The manufacturing method of the component.

Hereinafter, preferred embodiments of the impurity diffusion composition of the present invention and a method for producing a semiconductor device using the same will be described in detail with reference to the drawings. Furthermore, the invention is not limited by the embodiments.

The impurity diffusion composition of the present invention is a composition for forming a desired conductivity type (n-type, p-type) impurity diffusion layer on a semiconductor substrate when a semiconductor element such as a solar cell is manufactured, and contains a polyoxyalkylene oxide. (A) Diffusion component (B) with impurities. In the impurity diffusion composition, the polyoxyalkylene (A) contains at least one of a carboxyl group and a dicarboxylic anhydride structure. Hereinafter, each component contained in the impurity diffusion composition of the present invention will be described in detail.

(Polyoxane (A)) The polyoxyalkylene (A) in the present invention is a polyoxyalkylene containing at least one of a carboxyl group and a dicarboxylic anhydride structure. Since the polyoxyalkylene (A) has such a configuration, when it is contained in the impurity diffusion composition, the impurity diffusion composition can maintain excellent impurity diffusibility to the semiconductor substrate. Further, the polyoxyalkylene (A) can improve the cleaning property by an acid or a base of the dried film of the impurity diffusion composition remaining on the semiconductor substrate after the diffusion of the impurity diffusion component to the semiconductor substrate.

By the polyoxyalkylene (A) having at least one of a carboxyl group and a dicarboxylic anhydride structure, at least one of a carboxyl group and a dicarboxylic anhydride structure in the polyoxyalkylene (A) is affinity with an acidic or alkaline cleaning liquid. Sexuality is improved. That is, when the dried film containing the polyoxane (A)-containing impurity diffusion composition in the present invention is washed, the solubility of the dried film in the cleaning liquid is improved by the polyoxyalkylene (A). Therefore, the cleanability of the dried film by an acid or a base can be improved.

The polyoxyalkylene (A) having at least one of a carboxyl group and a dicarboxylic anhydride structure as described above is preferably a polyoxyalkylene represented by the following formula (1).

[Chemical 3]

In the above formula (1), R ¹ represents a substituent containing at least one of a carboxyl group and a dicarboxylic anhydride structure. A plurality of R ^{1 's} may be the same or different. R ² , R ³ and R ⁴ represent a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms or a carbon number. Any of 6 to 15 aryl groups. The plurality of R ² , R ³ and R ⁴ may be the same or different. n and m represent the composition ratio (%) of the components in each parenthesis. The n and m are n+m=100, and n:m=5:95 to 30:70.

The n and m are "n: m = 5: 95 to 30: 70", and the content ratio of the component derived from the organic decane having a carboxyl group in the polyoxyalkylene (A) is relative to the organic origin. The molar ratio of the Si atom of the Si atom of the entire aralkyl polyoxyalkylene (A) is 5 mol% or more and 30 mol% or less.

When n is 5 or more, the cleaning property of the dried film of the impurity-diffusing composition by an acid or a base can be improved. As a result, the cleaning treatment can be performed in a shorter period of time, in which the dried film of the impurity diffusion composition is removed from the semiconductor substrate. Further, by n being 30 or less, the impurity diffusibility from the impurity-diffusion composition film to the semiconductor substrate can be improved. The polyoxyalkylene (A) represented by the formula (1) may be a block copolymer or a random copolymer.

With respect to the content of the carboxyl group in the polyoxyalkylene (A), for example, a ²⁹ Si-nuclear magnetic resonance (NMR) spectrum of the polyoxyalkylene (A) can be measured, and the peak area of the Si atom bonded to the carboxyl group can be determined. The ratio of the peak area of the Si atom to which the carboxyl group is not bonded is determined. Further, when the Si atom and the carboxyl group are not directly bonded, the ¹ H-NMR spectrum is used to calculate the total polyoxane (A) based on the integral ratio of the peak derived from the carboxyl group to the other peaks other than the stanol group. The content of the carboxyl group in the combination of the calculated result and the result of the ²⁹ Si-NMR spectrum can be used to calculate the content of the carboxyl group indirectly bonded to the Si atom.

With respect to the content of the dicarboxylic anhydride structure in the polyoxyalkylene (A), for example, the ²⁹ Si-NMR spectrum of the polyoxyalkylene (A) can be measured, and the peak area of the Si atom bonded to the structure of the dicarboxylic anhydride is not The ratio of the peak areas of the Si atoms of the dicarboxylic anhydride structure is determined. Further, in the case where the Si atom and the dicarboxylic anhydride structure are not directly bonded, the ¹ H-NMR spectrum is used to calculate the polyfluorene oxygen based on the integral ratio of the peak derived from the structure of the dicarboxylic anhydride to the other peaks other than the stanol group. The content of the dicarboxylic anhydride structure in the entire alkane (A) can be calculated by combining the calculated results with the results of the ²⁹ Si-NMR spectrum, whereby the content of the dicarboxylic anhydride structure indirectly bonded to the Si atom can be calculated.

R ¹ in the formula (1) is particularly preferably a group represented by any one of the following formulas (2) to (6). Thereby, further good cleaning property by acid or alkali of the dried film of the impurity diffusion composition can be obtained.

[Chemical 4]

In the general formulae (2) to (6), R ⁵ , R ⁷ , R ⁸ and R ^{9 each} represent a divalent organic group having 1 to 20 carbon atoms. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹⁰ , R ¹¹ and R ^{12 each} represent a single bond, a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, a carbonyl group, An ether group, an ester group, a decylamino group, an aromatic group having 6 to 16 carbon atoms, or a divalent group having any of these. The hydrogen atom of the group may be an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, a hydroxyl group or an amine. Substituted by a base, a carboxyl group or a thiol group. h, j, k, and l represent integers of 0 to 3.

Next, an organic decane compound containing at least one of a carboxyl group and a dicarboxylic anhydride structure will be specifically described. The organodecane compound is a raw material of a polysiloxane (A) containing at least one of a carboxyl group and a dicarboxylic anhydride structure. The polyoxyalkylene (A) represented by the formula (1) can be obtained by hydrolysis and condensation by appropriately selecting an organodecane compound described below.

Examples of the organodecane compound having a carboxyl group include a ureido group-containing organodecane compound represented by the following formula (7) or an urethane group-containing organodecane represented by the following formula (8). Compound. As the organodecane compound having a carboxyl group, two or more kinds of these compounds may be used.

[Chemical 5]

In the general formula (7) and the general formula (8), R ¹³ , R ¹⁵ and R ¹⁹ represent a divalent organic group having 1 to 20 carbon atoms. R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹⁶ , R ¹⁷ and R ¹⁸ represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an anthracenyl group having 2 to 6 carbon atoms, and a carbon number of 6 to 6 Any of the 15 aryl groups. The R ¹⁶ , R ¹⁷ and R ¹⁸ may be the same or different. Here, at least one of R ¹⁶ , R ¹⁷ and R ¹⁸ is an alkoxy group having 1 to 6 carbon atoms.

Preferable examples of R ¹³ and R ^{1 9} in the general formula (7) and the general formula (8) include a methylene group, an exoethyl group, an exopropyl group, an exobutyl group, a phenyl group, and a -CH. _a hydrocarbon group such as ₂ -C ₆ H ₄ -CH ₂ -, -CH ₂ -C ₆ H ₄ -. Among these, from the viewpoint of heat resistance, R ¹³ and R ¹⁹ preferably have a stretching phenyl group, -CH ₂ -C ₆ H ₄ -CH ₂ -, -CH ₂ -C ₆ H ₄ - or the like. A hydrocarbon group of an aromatic ring.

From the viewpoint of reactivity, R ¹⁴ in the formula (7) is preferably hydrogen or a methyl group. Further, specific examples of R ¹⁵ in the general formula (7) and the general formula (8) include a hydrocarbon group such as a methylene group, an exoethyl group, an exo-propyl group, an exo-butyl group, and a pentyl group, or an oxy group. Methylene, oxyethyl, oxy-n-propyl, oxy-n-butyl, oxy-n-pentyl and the like. Among these, from the viewpoint of easiness of synthesis, R ^{15 is} preferably a methylene group, an ethyl group, an exopropyl group, a n-butyl group, an oxymethylene group, an oxyethyl group, or an oxy group. N-propyl, oxy-n-butyl.

In the general formula (7) and R ¹⁶ , R ¹⁷ and R ¹⁸ in the formula (8), examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. Among these, from the viewpoint of easiness of synthesis, the alkyl group as R ¹⁶ , R ¹⁷ and R ¹⁸ is preferably a methyl group or an ethyl group. Further, examples of the R ¹⁶ , R ¹⁷ and R ¹⁸ include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group and the like. Among these, from the viewpoint of easiness of synthesis, the alkoxy group as R ¹⁶ , R ¹⁷ and R ¹⁸ is preferably a methoxy group or an ethoxy group. Further, examples of the substituent of the substituent of R ¹⁶ , R ¹⁷ and R ¹⁸ include a methoxy group and an ethoxy group. Specifically, 1-methoxypropyl, methoxyethoxy, etc. are mentioned.

The urea group-containing organodecane compound represented by the formula (7) can be borrowed from the aminocarboxylic acid compound represented by the following formula (9) and the isocyanate group-containing organodecane compound represented by the following formula (11). It is obtained by a known urealation reaction. Further, the urethane group-containing organodecane compound represented by the formula (8) may be a hydroxycarboxylic acid compound represented by the following formula (10) and an isocyanate group represented by the following formula (11). The organodecane compound is obtained by a known urethanation reaction.

[Chemical 6]

In the general formulae (9) to (11), R ¹³ , R ¹⁵ and R ¹⁹ represent a divalent organic group having 1 to 20 carbon atoms. R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹⁶ , R ¹⁷ and R ¹⁸ represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an anthracenyl group having 2 to 6 carbon atoms, and a carbon number of 6 to 6 Any of the 15 aryl groups. The plurality of R ¹³ ~ R ¹⁹ is preferably, for example, in the above general formula (7), the formula (8) R ¹³ ~ R ¹⁹ as described.

Other specific examples of the organodecane compound having a carboxyl group include a compound represented by the formula (12).

[Chemistry 7]

In the formula (12), R ²⁰ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an anthracenyl group having 2 to 6 carbon atoms, and a carbon number of 6 Any of the aryl groups of -15. The plurality of R ^20s may be the same or different. q represents an integer of 1 to 3. r represents an integer of 2-20.

Specific examples of the organic decane compound having a dicarboxylic anhydride structure include an organodecane compound represented by any one of the following formulas (13) to (15). As the organodecane compound having a dicarboxylic anhydride structure, two or more of these compounds may be used.

[化8]

In the general formulae (13) to (15), R ²² , R ²³ and R ²⁴ represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or the like. Any one of a fluorenyl group having 2 to 6 carbon atoms and an aryl group having 6 to 15 carbon atoms. Here, at least one of R ²² , R ²³ and R ²⁴ is an alkoxy group having 1 to 6 carbon atoms.

R ²¹ , R ²⁵ and R ^{26 each} represent a single bond, a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a carbonyl group. An ether group, an ester group, a decylamino group, an aromatic group having 6 to 16 carbon atoms, or a divalent group having any of these. The hydrogen atom of the group may be an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, a hydroxyl group or an amine. Substituted by a base, a carboxyl group or a thiol group. h, j, k, and l represent integers of 0 to 3.

Specific examples of R ²¹ , R ²⁵ and R ²⁶ include -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -O-, -C ₃ H ₆ OCH ₂ CH ( OH) CH ₂ O ₂ C-, -CO-, -CO ₂ -, -CONH-, and the organic groups listed below.

[Chemistry 9]

Specific examples of the organodecane compound represented by the formula (13) include 3-trimethoxydecylpropyl succinic anhydride, 3-triethoxydecylpropyl succinic anhydride, and 3-triphenyloxy group. Nonylalkyl succinic anhydride and the like. Specific examples of the organodecane compound represented by the formula (14) include 3-trimethoxydecylpropylcyclohexyldicarboxylic anhydride. Specific examples of the organodecane compound represented by the formula (15) include 3-trimethoxydecylpropyl phthalic anhydride.

An organic decane compound other than the organodecane compound containing at least one of a carboxyl group and a dicarboxylic anhydride structure may be used in combination as a raw material of the polysiloxane (A) having at least one of a carboxyl group and a dicarboxylic anhydride structure.

Examples of such an organic decane compound include tetrafunctional decane, trifunctional decane, difunctional decane, and monofunctional decane. Examples of the tetrafunctional decane include tetramethoxy decane, tetraethoxy decane, tetraethoxy decane, and tetraphenoxy decane. Examples of the trifunctional decane include methyltrimethoxydecane, methyltriethoxydecane, methyltriisopropoxydecane, methyltri-n-butoxydecane, and ethyltrimethoxydecane. Ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, n-propyltrimethoxydecane, n-propyltriethoxydecane, n-butyltrimethoxydecane , n-butyl triethoxy decane, n-hexyl trimethoxy decane, n-hexyl triethoxy decane, decyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-methyl Acryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, phenyltrimethoxydecane, phenyl Triethoxy decane, p-hydroxyphenyl trimethoxy decane, 1-(p-hydroxyphenyl)ethyltrimethoxynonane, 2-(p-hydroxyphenyl)ethyltrimethoxynonane, 4-hydroxy-5 -(p-hydroxyphenylcarbonyloxy)pentyltrimethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxydecane, 3,3, 3-trifluoropropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-shrinkage Glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, [(3-Ethyl-3-oxetanyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxy Baseline, 3-mercaptopropyltrimethoxydecane, 1-naphthyltrimethoxydecane, 1-naphthyltriethoxydecane, 1-naphthyltri-n-propoxydecane, 2-naphthyltrimethoxy Decane, 1-mercaptotrimethoxydecane, 9-fluorenyltrimethoxydecane, 9-phenanthryltrimethoxydecane, 9-fluorenyltrimethoxydecane, 2-mercaptotrimethoxydecane, 1-oxime Trimethoxy decane, 2-mercaptotrimethoxydecane, 5-decyltrimethoxydecane, and the like. Examples of the difunctional decane include dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl diethoxy decane, di-n-butyl dimethoxy decane, and diphenyl. Dimethoxyoxane, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)methyldiethoxydecane, bis(1-naphthyl) Dimethoxydecane, di(1-naphthyl)diethoxydecane, and the like. Examples of the monofunctional decane include trimethyl methoxy decane, tri-n-butyl ethoxy decane, (3-glycidoxypropyl) dimethyl methoxy decane, and (3-glycidol). Oxypropyl) dimethyl ethoxy decane, and the like. Two or more kinds of these organic decanes can also be used.

The method for producing the polyoxyalkylene (A) having at least one of a carboxyl group and a dicarboxylic anhydride structure is not particularly limited, and a known method such as partial condensation of an organic decane compound can be used. For example, a method in which a reaction solvent, water, and an optional catalyst are added to the organodecane mixture and heated and stirred at 50 to 150 ° C for 0.5 to 100 hours is exemplified. In the production method, in the heating and stirring, a by-product of hydrolysis (an alcohol such as methanol) or a condensation by-product (water) may be distilled off by distillation as needed. Here, the term "partial condensation" means that Si-OH remains in a part of the obtained polysiloxane (A) without condensing all of the Si-OH of the hydrolyzate. As long as it is a normal condensation condition to be described later, Si-OH is usually partially left. In the present invention, the amount of remaining Si-OH is not limited.

The reaction solvent is not particularly limited, and usually the same as the solvent described below can be used. The amount of the reaction solvent added is preferably 10 parts by weight or more and 1500 parts by weight or less based on 100 parts by weight of the monomer such as organic decane. Further, the amount of water used in the hydrolysis reaction is preferably 0.5 mol or more and 5 mol or less with respect to the hydrolyzable group 1 mol.

The catalyst to be added as needed is not particularly limited, and an acid catalyst can be preferably used. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or an anhydride thereof, and an ion exchange resin. The amount of such a catalyst added is preferably 0.01 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the monomer such as organodecane.

Further, from the viewpoint of storage stability of the impurity-free diffusion composition, the catalyst may be removed from the polyoxane solution after hydrolysis or partial condensation as needed. The method for removing the catalyst is not particularly limited, and at least one of the treatment using water washing and the ion exchange resin is preferably carried out from the viewpoint of ease of handling and removability. The water washing refers to a method in which a polyoxyalkylene solution is diluted with a suitable hydrophobic solvent, washed with water several times to obtain an organic layer, and the obtained organic layer is concentrated by an evaporator or the like. The treatment by the ion exchange resin refers to a method of bringing the polyoxane solution into contact with an appropriate ion exchange resin.

The content of the polysiloxane (A) containing at least one of a carboxyl group and a dicarboxylic anhydride structure in the impurity diffusion composition of the present invention is preferably 0.1% by mass or more and 90% by mass or less based on the impurity-diffusion composition. More preferably, it is 0.1 mass% or more and 50 mass% or less. When the content of the polyoxyalkylene (A) is within the above range, excellent impurity diffusibility and cleanability of the impurity diffusion composition can be obtained.

In the "base" in the present invention, the "carbon number" means a total carbon number which also includes a group which is further substituted for the base. For example, the alkyl group having 1 to 10 carbon atoms means that the total number of carbon atoms in the alkyl group (including the substituent in the case of having a substituent) is 1 or more and 10 or less.

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

As the phosphorus compound, for example, a phosphate or a phosphite can be exemplified. Examples of the phosphate ester include phosphorus pentoxide, phosphoric acid, polyphosphoric acid, methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, and 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 them, in terms of doping property, phosphoric acid, phosphorus pentoxide or polyphosphoric acid is preferred.

Examples of the boron compound include boric acid, borate, halide, hydrocarbylboronic acid, boric acid ester, and hydrocarbyl borate. Specifically, examples of the boric acid include boric acid, boron oxide, and the like. Examples of the borate include ammonium borate and the like. Examples of the halide include boron trifluoride, boron trichloride, boron tribromide, and boron triiodide. Examples of the hydrocarbyl boric acid include methyl hydrocarbyl borate and phenyl hydrocarbyl borate. Examples of the boric acid esters include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trioctyl borate, and triphenyl borate. Examples of the hydrocarbon group boronic esters include 2-phenyl-1,3,2-dioxaborolane and diisopropylmethylborane. Among these, from the viewpoint of diffusibility, boric acid, hydrocarbyl boric acid, boric acid ester, and hydrocarbyl borate ester are preferable.

The content of the impurity diffusion component (B) in the impurity diffusion composition of the present invention can be arbitrarily determined according to the resistance value obtained in the semiconductor substrate, and is preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.1% by mass. % or more and 20% by mass or less. When the content of the impurity-diffusing component (B) is within the above range, sufficient diffusibility of the impurity-diffusing component (B) in the semiconductor substrate can be obtained.

Further, when a boron compound is used as the impurity diffusion component (B), the impurity diffusion component (B) preferably contains a binder resin. The impurity-diffusing component (B) is particularly preferably one or more selected from the group consisting of boric acid, hydrocarbylboronic acid, boric acid ester, and hydrocarbyl borate, and further contains water and a water-soluble binder. Here, the water-soluble binder means a solubility of 10% by weight or more with respect to water at 25 ° C.

Specifically, the following examples of the binder resin such as the water-soluble binder can be exemplified. For example, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polypropylene decylamine resin, polyvinyl pyrrolidone resin, polyethylene oxide resin, acrylamide alkyl sulfonate resin, cellulose Derivatives, gelatin, gelatin derivatives, starch, starch derivatives, sodium alginate compounds, sambag, guar gum, guar derivatives, scleroglucan, scleroglucan Derivatives, tragacanth, tragacanth derivatives, dextrin, dextrin derivatives, water-soluble (meth) acrylate resins, water-soluble polybutadiene resins, water-soluble styrene resins , butyral resin, copolymers of these, and the like. However, the binder resin in the impurity diffusion component (B) is not limited to these. In addition, the term "(meth)acrylic acid" means "acrylic acid or methacrylic acid".

In the impurity diffusion component (B), the binder resin may be used singly or in combination of two or more. In the case where the impurity-diffusing component (B) is a boron compound, the binder resin preferably has 1 from the viewpoint of the formability of the complex compound of the boron compound and the stability of the formed complex. A 2-diol structure or a 1,3-diol structure, particularly preferably a polyvinyl alcohol.

In addition, the degree of polymerization of the binder resin in the impurity-diffusing component (B) is not particularly limited, and a preferable degree of polymerization is 1,000 or less, and particularly preferably 800 or less. Thereby, the excellent solubility of the hydroxyl group-containing polymer such as polyvinyl alcohol in an organic solvent is exhibited. On the other hand, the lower limit of the degree of polymerization is not particularly limited, and from the viewpoint of ease of handling of the binder resin, it is preferably 100 or more. Further, in the present invention, the degree of polymerization of the binder resin is determined as a polystyrene-equivalent number average degree of polymerization in a gel permeation chromatography (GPC) analysis.

(Solvent) The impurity diffusion composition of the present invention preferably contains a solvent. The solvent can be used without particular limitation, and can be appropriately selected according to a coating method such as a spin coating method, an inkjet method, a screen printing method, or a roll coating method. Examples of such a solvent include a ketone solvent, an ether solvent, an ester solvent, an ether acetate solvent, an aprotic polar solvent, an alcohol solvent, a glycol monoether solvent, a terpene solvent, and the like. Water, etc. These may be used alone or in combination of two or more.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, and methyl n-pentyl group. Ketone, methyl n-hexyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentane Ketone, acetonylacetone, γ-butyrolactone, γ-valerolactone, and the like.

Examples of the ether solvent include diethyl ether, methyl ethyl ether, methyl n-propyl ether, diisopropyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyl dioxane, and ethylene. Alcohol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl n-butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl n-Hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl n-butyl ether, triethylene glycol di-n-butyl ether, Triethylene glycol methyl n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetra-diethylene glycol methyl ethyl ether, tetraethylene glycol methyl n-butyl ether, diethyl Diethylene glycol n-butyl ether, tetraethylene glycol methyl n-hexyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol dibutyl ether, dipropylene glycol Dimethyl ether, two Propylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl n-butyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl n-hexyl ether, tripropylene glycol dimethyl ether , tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl n-hexyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, Tetra-dipropylene glycol methyl ethyl ether, tetrapropylene glycol methyl n-butyl ether, dipropylene glycol di-n-butyl ether, tetrapropylene glycol methyl n-hexyl ether, tetrapropylene glycol di-n-butyl ether, and the like.

Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, and acetic acid. Dipentyl ester, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 2-(2-butoxyethoxy)ethyl acetate , benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, decyl acetate, methyl acetate, ethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy triethylene glycol acetate, C Ethyl acetate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, and the like.

Examples of the ether acetate-based solvent include ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, and diethylene glycol. Methyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol n-butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether Acetate, dipropylene glycol diethyl ether acetate, and the like.

Examples of the aprotic polar solvent include acetonitrile, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, and N-hexylpyrrolidine. Ketone, N-cyclohexyl pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylfluorene, and the like.

Examples of the alcohol-based solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, and 2-methyl. Butanol, second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, positive Octanol, 2-ethylhexanol, second octanol, n-nonanol, n-nonanol, second-undecanol, trimethylnonanol, second-tetradecanol, second-heptadecanol, Phenol, cyclohexanol, methylcyclohexanol, benzyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and the like.

Examples of the glycol monoether solvent include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol single. n-Butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triethylene glycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol single Methyl ether and the like.

Examples of the terpene-based solvent include α-terpinene, α-terpineol, myrcene, allo-ocimene, limonene, dipentene, and α. - Pinene, β-pinene, terpineol, carvone, basilene, phellandrene, and the like.

The content of the solvent in the impurity diffusion composition of the present invention can be arbitrarily determined depending on the viscosity of the impurity diffusion composition, and is preferably in the range of 1% by mass or more and 90% by mass or less.

(Surfactant) The impurity diffusion composition of the present invention may also contain a surfactant. When the impurity-diffusing composition contains a surfactant, coating unevenness when the impurity-diffusing composition is applied to the semiconductor substrate is improved, and as a result, a uniform coating film of the impurity-diffusing composition can be obtained. As the surfactant, a fluorine-based surfactant or an anthrone-based surfactant can be preferably used.

Specific examples of the fluorine-based surfactant include a fluorine-based surfactant containing a compound having a fluoroalkyl group or a fluorine-extended alkyl group at at least any 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-tetra. Fluoryl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether , propylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether, perfluorododecyl sulfonate 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-carboxymethyleneammonium betaine, perfluoroalkylsulfonamide propyltrimethylammonium salt, perfluoro Alkyl-N-ethylsulfonylglycine, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl phosphate), monoperfluoroalkylethyl phosphate, and the like.

In addition, as a commercial item, 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 (New Akita) Made by the company), Fluorad FC-430, Fluorad FC-431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, FTX-218, DFX-218 (manufactured by Neos) A fluorine-based surfactant.

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

When the surfactant is added to the impurity diffusion composition, the content of the surfactant in the impurity diffusion composition is preferably 0.0001% by mass or more and 1% by mass or less. By setting the content of the surfactant to be within the above range, excellent coating properties of the impurity diffusion composition with respect to the semiconductor substrate can be obtained.

(Thickener) In order to adjust the viscosity, the impurity diffusion composition of the present invention may also contain a thickener. Examples of the thickener include an organic thickener and an inorganic thickener. Examples of the organic thickener include cellulose, cellulose derivatives, starch, starch derivatives, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polyamine. Carbamate resin, polyurea resin, polyimine resin, polyamide resin, epoxy resin, polystyrene resin, polyester resin, synthetic rubber, natural rubber, polyacrylic acid, various acrylic resins, poly Ethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, eucalyptus oil, sodium alginate, Sanxian gum polysaccharide, lanolin polysaccharide, guar gum polysaccharide, carrageenan polysaccharide , locust bean gum polysaccharide, carboxyvinyl polymer, hydrogenated castor oil, hydrogenated castor oil and fatty acid guanamine wax system mixture, special fatty acid system, oxidized polyethylene system, oxidized polyethylene system and amide amine system A mixture, a fatty acid-based polycarboxylic acid, a phosphate ester surfactant, a salt of a long-chain polyamine amide and a phosphoric acid, and a special modified polyamine. Examples of the inorganic thickener include bentonite, montmorillonite, magnesium montmorillonite, iron montmorillonite, iron-magnesium montmorillonite, beidellite, aluminum beidellite, saponite, and aluminum. Soapstone, laponite, aluminum niobate, aluminum magnesium niobate, organolithium bentonite, fine particle cerium oxide, colloidal alumina, calcium carbonate, and the like. These can be used in combination.

Among these thickeners, examples of the thixotropic agent to which thixotropy is imparted include cellulose, cellulose derivatives, sodium alginate, trisaccharide-based polysaccharides, leucosaccharides, and guar. Gummy polysaccharides, carrageenan polysaccharides, locust bean gum polysaccharides, carboxyvinyl polymers, hydrogenated castor oils, hydrogenated castor oils and fatty acid amide waxes, special fatty acid systems, oxidized polyethylene systems , a mixture of oxidized polyethylene and guanamine, a fatty acid polycarboxylic acid, a phosphate ester surfactant, a salt of a long-chain polyamine amide and phosphoric acid, a special modified polyamine, bentonite, montmorillonite , magnesium montmorillonite, iron montmorillonite, iron magnesium montmorillonite, beide stone, aluminum beide stone, soap stone, aluminosilicate, laponite, aluminum niobate, aluminum magnesium niobate, organolithium swelling Stone, particulate cerium oxide, colloidal alumina, calcium carbonate, and the like.

In addition, as a commercial product of a cellulose thickener, there are 1110, 1120, 1130, 1140, 1150, 1160, 1170, 1180, 1190, 2200, 2260, 2280 manufactured by Daicel Fine Chemical Co., Ltd. , 2450, etc. As a commercial product of a polysaccharide thickener, there are Viscarin PC209, Viscarin PC389, SeaKem XP8012 manufactured by FMC Chemical Co., Ltd., and CAM manufactured by Mitsubishi Corporation. -H, GJ-182, SV-300, LS-20, LS-30, XGT, XGK-D, G-100, LG-10, etc.

As a commercial product of the hydrogenated castor oil-based thickener, there are Disparlon 308, NAMLONT-206 manufactured by Nanben Chemical Co., Ltd., T-20SF, T-75F manufactured by Ito Oil Co., Ltd., and the like. As a commercial product of the oxidized polyethylene thickener, D-10A, D-120, D-120-10, D-1100, DS-525, DS-313 manufactured by Ito Oil Co., Ltd., manufactured by Nanben Chemical Co., Ltd. Disparlon 4200-20, Disparlon PF-911, Disparlon PF-930, Disparlon 4401-25X, Disparlon NS-30, Disparlon NS-5010, Disparlon NS-5025, Disparlon NS-5810, Disparlon NS-5210, Di Disparlon NS-5310, Flownon SA-300, Flownon SA-300H, etc. manufactured by Kyoeisha Chemical Co., Ltd. As a commercially available product of a guanamine-based thickener, there are T-250F, T-550F, T-850F, T-1700, T-1800, and T-2000 manufactured by Ito Oil Co., Ltd., Dispa made by Nanben Chemical Co., Ltd. Disparlon 6500, Disparlon 6300, Disparlon 6650, Disparlon 6700, Disparlon 3900EF, Tower manufactured by Kyoritsu Chemical Co., Ltd. Talen 7200, Talen 7500, Talen 8200, Talen 8300, Talen 8700, Talen 8900, Talen KY-2000, Talen KU-700, Talen M-1020, Talen VA-780, Talen VA-750B, Talen 2450, Flownon SD -700, Flownon SDR-80, etc.

As a commercial product of a bentonite thickener, there are Bengel, Bengel HV, Bengel HVP, and Bengel F manufactured by Hojun Co., Ltd. , Bengel FW, Bengel Bright 11, Bengel A, Bengel W-100, Bengel W-100U, Bengue Bengel W-300U, Bengel SH, MultiBen, S-Ben, S-Ben C, S-Ben E, S-Ben W, S-Ben P, S- Ben WX, Organite, Organite D, etc. As a commercial product of the particulate cerium oxide thickener, there are AEROSIL R972, AEROSIL R974, and AEROSIL manufactured by AEROSIL, Japan. NY50, AEROSIL RY200S, AEROSIL RY200, AEROSIL RX50, AEROSIL NAX50, AEROSIL RX200, Irothy AEROSIL RX300, AEROSIL VPNKC130, AEROSIL R805, AEROSIL R104, AEROSIL R711, AEROSIL OX50 , AEROSIL 50, AEROSIL 90G, AEROSIL 130, AEROSIL 200, AEROSIL 300, Aerosil (AEROSIL) 380, WACKER HDK S13, WACKER HDK V15, WACKER HDK N20, WACKER HDK N20P, WACKER HDK T30, watts manufactured by Asahi Kasei Corporation WACKER HDK T40, WACKER HDK H15, WACKER HDK H18, WACKER CKER) HDK H20, WACKER HDK H30, etc.

The thickener is preferably polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, or various acrylate resins from the viewpoint of decomposability. Among these, polyethylene oxide, polypropylene oxide or acrylate resin is more preferable, and polyethylene oxide is particularly preferable.

Examples of the acrylate-based resin include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, and polyacrylic acid. Polyacrylates such as propyl ester, polybutyl acrylate, polyhydroxyethyl methacrylate, polybenzyl methacrylate, polyglycidyl methacrylate, and copolymers thereof. When the acrylate resin is a copolymer, the acrylate component may be 60 mol% or more in terms of a polymerization ratio, and as another copolymer component, polyacrylic acid, polystyrene or the like may be vinylated. The polymerized components are copolymerized.

Further, as for the polyethylene oxide and the polypropylene oxide, a copolymer of the two kinds is also preferable. The acrylate resin, polyethylene oxide, and polypropylene oxide are preferably those having a weight average molecular weight of 100,000 or more and a high thickening effect. The content of the thickener in the impurity-diffusing composition is preferably in the range of 1% by mass or more and 20% by mass or less.

The viscosity of the impurity-diffusing composition of the present invention is not particularly limited, and can be appropriately changed depending on the coating method or film thickness of the impurity-diffusing composition. For example, when the coating method of the impurity diffusion composition is a spin coating method, the viscosity of the impurity diffusion composition is preferably 100 [mPa·s] or less. Further, in the case where the coating method of the impurity diffusion composition is a screen printing method, the viscosity of the impurity diffusion composition is preferably 5,000 [mPa·s] or more and 100,000 [mPa·s] or less.

Here, when the viscosity is less than 1,000 [mPa·s], it is based on Japanese Industrial Standards (JIS) Z8803 (1991) "Solid Viscosity - Measurement Method", using an E-type digital viscometer at a rotational speed of 20 The value measured by rpm. In addition, when the viscosity is 1,000 [mPa×s] or more, it is a value measured by a B-type digital viscometer at a number of revolutions of 20 rpm based on JIS Z8803 (1991) "Solid viscosity-measurement method".

The solid content concentration of the impurity diffusion composition of the present invention is not particularly limited, but is preferably 1% by mass or more and 90% by mass or less. When the solid content concentration of the impurity diffusion composition is within the above range, the diffusibility and storage stability of the impurity diffusion composition are improved.

(Method of Manufacturing Semiconductor Element) Next, a method of manufacturing a semiconductor element using the impurity diffusion composition of the present invention will be described. A method of producing a semiconductor device according to an embodiment of the present invention is a method of forming an impurity diffusion layer using a diffusion-forming composition containing an impurity of the polyoxyalkylene (A) and the impurity diffusion component (B). A method of manufacturing such a semiconductor device includes: a film forming step of applying the impurity diffusion composition onto a semiconductor substrate to form an impurity diffusion composition film; and a layer forming step of diffusing the impurity diffusion component (B) from the impurity The composition film is diffused into the semiconductor substrate to form an impurity diffusion layer.

Further, as a preferred embodiment of the present invention, a method of manufacturing a semiconductor device includes: the film forming step; and a layer forming step of irradiating a film of the impurity diffusion composition film on the semiconductor substrate with a laser beam to diffuse the impurity component ( B) An impurity diffusion layer is formed by diffusing the impurity diffusion composition film into the semiconductor substrate. In particular, the method for manufacturing a semiconductor device according to the present embodiment includes: the film forming step; and a layer forming step of irradiating a part of the impurity diffusion composition film formed on the semiconductor substrate with laser light to cause the impurity diffusion component (B) to be A part of the impurity diffusion composition film is diffused into the semiconductor substrate to form an impurity diffusion layer; and a removing step of removing the unirradiated portion of the impurity diffusion film that is not irradiated with the laser light by an acid or a base.

FIG. 1A is a view showing an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. In the present embodiment, a method of manufacturing a semiconductor element for a back junction type solar cell is exemplified. In the semiconductor element for a back junction type 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 of the solar cell.

Specifically, as shown in FIG. 1A, in the method of manufacturing a semiconductor device, first, a first film forming step (step ST101) is performed. In the step ST101, the first conductivity type impurity diffusion composition of the present invention is applied onto a predetermined surface (back surface of the solar cell) of the semiconductor substrate 1. Thereby, the impurity diffusion composition film 2 is formed on a predetermined surface of the semiconductor substrate 1. The impurity diffusion composition film 2 is a first conductivity type impurity diffusion composition film having a predetermined conductivity type (n-type or p-type).

In the present embodiment, the first conductivity type impurity diffusion composition is an impurity diffusion composition containing the polyoxyalkylene oxide (A) and the first conductivity type impurity diffusion component (B-1). The first conductivity type impurity diffusion component (B-1) is an aspect of the impurity diffusion component (B) (for example, a compound containing a group 13 element or a group 15 element), and has a second conductivity type to be described later. Impurity diffusion component (B-2) is a different conductivity type.

Examples of the semiconductor substrate 1 include n-type single crystal germanium having an impurity concentration of 10 ¹⁵ [atoms/cm ³ ] to 10 ¹⁶ [atoms/cm ³ ], polycrystalline germanium, and crystallization of other elements such as germanium, carbon, and the like. Substrate. Alternatively, a p-type crystallization or a semiconductor substrate other than ruthenium may be used. The semiconductor substrate 1 preferably has a thickness of 50 [μm] to 300 [μm] and an outer shape of a substantially quadrangular shape having a side of 100 [μm] to 250 [μm]. Further, in order to remove the slice damage or the natural oxide film on each surface of the semiconductor substrate 1, it is preferable to etch each surface of the semiconductor substrate 1 with a hydrofluoric acid solution or an alkali solution in advance.

Further, a protective film may be formed on the light receiving surface of the semiconductor substrate 1 (the surface opposite to the surface on which the impurity diffusion composition film 2 is formed). The protective film can be formed by a chemical vapor deposition (CVD) method or a spin-on glass (SOG) method. For example, as the protective film, a known protective film such as ruthenium oxide or tantalum nitride can be applied.

Examples of the coating method of the first conductivity type impurity diffusion composition applied to step ST101 include a spin coating method, a screen printing method, an inkjet printing method, a slit coating method, a letterpress printing method, and a gravure printing method. Printing method, etc. In step ST101, it is preferable to form the impurity diffusion composition film 2 by any of the coating methods, and then use a hot plate, an oven, an infrared ray heater, or the like at 50 ° C to 200 The impurity diffusion composition film 2 was dried in the range of ° C for 1 second to 30 minutes. When the diffusibility of the impurity diffusion component (B-1) in the semiconductor substrate 1 is considered, the film thickness of the impurity diffusion composition film 2 after drying is preferably 200 [nm] or more and 5 [μm] or less.

After the end of the step ST101, as shown in FIG. 1A, a first layer forming step (step ST102) is performed. In the step ST102, the impurity diffusion component (B-1) is diffused from the impurity diffusion composition film 2 into the semiconductor substrate 1, whereby the impurity diffusion layer 3 is formed in the semiconductor substrate 1. The impurity diffusion layer 3 is a first conductivity type impurity diffusion layer having the same conductivity type as the impurity diffusion composition film 2.

In the present embodiment, the laser light 10 is irradiated to the impurity diffusion composition film 2, and the impurity diffusion component (B-1) is diffused from the impurity diffusion composition film 2 into the semiconductor substrate 1. Specifically, the target portion (for example, a part of a desired pattern) in the impurity diffusion composition film 2 is irradiated with the laser light 10. By the heating by the irradiation of the laser light 10 (hereinafter referred to as "laser heating"), the impurity diffusion component (B-1) in the impurity diffusion composition film 2 is locally diffused (desired pattern) to the semiconductor. In the substrate 1. As a result, as shown in FIG. 1A, the impurity diffusion layer 3 is formed in a desired pattern on the semiconductor substrate 1. At this time, in the entire impurity-diffused composition film 2, the portion (the dotted line portion in FIG. 1A) in which the impurity diffusion layer 3 is formed by laser heating can be eliminated by ablation or remaining without being lost.

Further, the laser light 10 used in the laser heating is not particularly limited, and a known one can be used. For example, as the laser light 10, a base harmonic (1064 [nm]) or a second harmonic of a Nd: Yttrium Aluminum Garnet (YAG) laser or a Nd: Yttrium vanadate (YVO ₄ ) laser can be used. (532 [nm]) or third-order harmonic (355 [nm]), or XeCl excimer laser (308 [nm]), KrF excimer laser (248 [nm]), ArF excimer laser (198 [nm]) Laser light.

The energy density of the laser light 10 is preferably 0.25 [J/cm ² ] or more and 25 [J/cm ² ] or less. The diffusion time of the impurity-diffusing component (the impurity-diffusion component (B-1) in the step ST102) heated by the laser can be appropriately set so as to obtain the diffusion characteristics required for the concentration and diffusion depth of the impurity component to be diffused. For example, the concentration of the impurity diffusion component in the surface of the semiconductor substrate is preferably such that an impurity diffusion layer of 10 ¹⁹ [atoms/cm ³ ] to 10 ²¹ [atoms/cm ³ ] can be formed. The diffusion environment of the diffusion component of the impurity heated by the laser is not particularly limited, and may be an environment similar to that of the atmosphere, or an environment in which an inert gas such as nitrogen or argon is used to appropriately control the amount of oxygen in the environment.

After the end of the step ST102, as shown in FIG. 1A, a first removal step (step ST103) is performed. In step ST103, the impurity diffusion composition film 2 remaining on the semiconductor substrate 1 is removed using the cleaning liquid. In the present embodiment, the laser non-irradiated portion of the impurity diffusion composition film 2 that is not irradiated with the laser light 10 remains on the semiconductor substrate 1. In step ST103, such a laser non-irradiated portion is removed by the cleaning liquid. As the cleaning liquid, for example, a known acid or alkali cleaning solution such as hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid, tetramethylammonium hydroxide (TMAH) or KOH can be used. Among them, from the viewpoint of suppressing damage to the protective film formed on the semiconductor substrate 1, it is preferred to use a cleaning liquid of an alkali such as TMAH or KOH.

After the end of the step ST103, as shown in FIG. 1A, a second film forming step (step ST104) is performed. In the step ST104, the second conductivity type impurity diffusion composition of the present invention is applied onto a predetermined surface of the semiconductor substrate 1. Thereby, the impurity diffusion composition film 4 is formed on a predetermined surface of the semiconductor substrate 1. The coating method of the second conductivity type impurity diffusion composition is not particularly limited, and a known coating method similar to the method of applying the first conductivity type impurity diffusion composition in the above step ST101 can be used. .

In the present embodiment, the impurity diffusion composition film 4 is a conductivity type second conductivity type impurity diffusion composition film having a conductivity type (first conductivity type) different from that of the impurity diffusion composition film 2. The second conductivity type impurity diffusion composition is an impurity diffusion composition containing the polyaluminoxane (A) and the second conductivity type impurity diffusion component (B-2). The second conductivity type impurity diffusion component (B-2) is an aspect of the impurity diffusion component (B) (for example, a compound containing a group 13 element or a group 15 element), and has a first conductivity type Impurity diffusion component (B-1) is a different conductivity type.

Further, in step ST104, similarly to step ST101, it is preferable to form the impurity diffusion composition film 4, and then the impurity is diffused from the composition film 4 and dried. The film thickness of the impurity-diffused composition film 4 after drying is set, for example, in consideration of the diffusibility of the impurity diffusion component (B-2) in the semiconductor substrate 1.

After the end of the step ST104, as shown in FIG. 1A, a second layer forming step (step ST105) is performed. In the step ST105, the impurity diffusion component (B-2) is diffused from the impurity diffusion composition film 4 into the semiconductor substrate 1, whereby the impurity diffusion layer 5 is formed in the semiconductor substrate 1. The impurity diffusion layer 5 is a second conductivity type impurity diffusion layer having the same conductivity type as the impurity diffusion composition film 4. That is, the conductivity type (second conductivity type) of the impurity diffusion layer 5 is different from the conductivity type (first conductivity type) of the formed impurity diffusion layer 3.

In the present embodiment, the laser light 10 is irradiated to the impurity diffusion composition film 4, and the impurity diffusion component (B-2) is diffused from the impurity diffusion composition film 4 into the semiconductor substrate 1. Specifically, the target portion (for example, a portion other than the impurity diffusion layer 3 and a part of forming a desired pattern) in the impurity diffusion composition film 4 is irradiated with the laser light 10, and the target portion is subjected to laser irradiation. heating. By the laser heating, the impurity diffusion component (B-2) in the impurity diffusion composition film 4 is partially diffused into the semiconductor substrate 1 (desired pattern shape). As a result, as shown in FIG. 1A, the impurity diffusion layer 5 is formed in a desired pattern on the semiconductor substrate 1. At this time, in the entire impurity-diffused composition film 4, the portion (the dotted line portion in FIG. 1A) in which the impurity diffusion layer 5 is formed by laser heating can be eliminated by ablation or left without being lost.

Further, the laser light 10 used in the laser heating is not particularly limited, and laser heating of the impurity-diffusion composition of the first conductivity type (the impurity diffusion composition film 2) in the step ST102 may be used. The same method is known to the public. The diffusion time of the impurity-diffusing component (the impurity-diffusion component (B-2) in the step ST105) heated by the laser can be appropriately set so as to obtain the diffusion characteristics required for the concentration and diffusion depth of the impurity component to be diffused. For example, the concentration of the impurity diffusion component in the surface of the semiconductor substrate is preferably such that an impurity diffusion layer of 10 ¹⁹ [atoms/cm ³ ] to 10 ²¹ [atoms/cm ³ ] can be formed. The diffusion environment of the diffusion component of the impurity heated by the laser is not particularly limited, and may be an environment similar to that of the atmosphere, or an environment in which an inert gas such as nitrogen or argon is used to appropriately control the amount of oxygen in the environment.

After the end of the step ST105, as shown in FIG. 1A, a second removing step (step ST106) is performed. In step ST106, the impurity diffusion composition film 4 remaining on the semiconductor substrate 1 is removed using the cleaning liquid. In the present embodiment, the laser non-irradiated portion of the impurity diffusion composition film 4 remains on the semiconductor substrate 1. In step ST106, such a laser non-irradiated portion is removed by the cleaning liquid. As the cleaning liquid, for example, a known acid or alkali cleaning solution such as hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid, TMAH or KOH can be used. Among them, from the viewpoint of suppressing damage to the protective film formed on the semiconductor substrate 1, it is preferred to use a cleaning liquid of an alkali such as TMAH or KOH.

The semiconductor element 15 of the present embodiment can be manufactured by sequentially performing the above steps ST101 to ST106. This semiconductor element 15 is suitably used as a semiconductor element for a back junction type solar cell.

Next, a method of manufacturing a solar cell using the semiconductor element of the embodiment of the present invention will be described. FIG. 1B is a view showing an example of a method of manufacturing a solar cell using a semiconductor element according to an embodiment of the present invention. Fig. 1B shows a step after the manufacture of the semiconductor element 15 (see Fig. 1A) used in the manufacture of the solar cell of the present embodiment.

The method of manufacturing a solar cell of the present embodiment includes a method of manufacturing the semiconductor device 15 shown in FIG. 1A. In other words, after the semiconductor element 15 is manufactured as described above, the solar cell (back junction type solar cell) of the present embodiment can be manufactured by a known method.

For example, in the method of manufacturing a solar cell of the present embodiment, following the manufacturing process of the semiconductor element 15 shown in FIG. 1A, as shown in FIG. 1B, a protective film forming step (step ST201) is performed. In step ST201, the protective film 6 is formed on the back surface of the semiconductor substrate 1. The back surface of the semiconductor substrate 1 is a surface opposite to the light receiving surface of the semiconductor element 15 (the surface on the lower side of the paper surface in FIG. 1B), and the impurity diffusion layer 3 and the impurity diffusion layer 5 having different conductivity types are formed. The side of one side. In the present embodiment, the protective film 6 is formed on the entire back surface of such a semiconductor substrate 1. Examples of the protective film 6 include a thermal oxide layer, an aluminum oxide layer, a SiNx layer, and an amorphous germanium layer. In addition, examples of the method for forming the protective film 6 include a vapor deposition method such as a plasma CVD method or an atomic layer deposition (ALD) method, or a coating method.

After the end of step ST201, as shown in FIG. 1B, a pattern processing step is performed (step ST202). In step ST202, the protective film 6 on the back surface of the semiconductor substrate 1 is processed (patterned) in a desired pattern by an etching method or the like. Thereby, a plurality of openings 6a are formed in the protective film 6. Each of the plurality of openings 6a exposes the impurity diffusion layer 3 and the impurity diffusion layer 5 formed in the state of the semiconductor substrate 1 discontinuously.

After the end of the step ST202, as shown in FIG. 1B, an electrode forming step (step ST203) is performed. In step ST203, the electrode paste is applied in a pattern to each region of the opening portion 6a including the protective film 6 in the back surface of the semiconductor substrate 1 by a method such as a stripe coating method or a screen printing method. The coated electrode paste is calcined. Thereby, the contact electrode 7 and the contact electrode 8 are formed in each of the regions of the semiconductor substrate 1. Among these, one contact electrode 7 is a first conductivity type contact electrode that is connected to the first conductivity type impurity diffusion layer 3. The other contact electrode 8 is a second conductivity type contact electrode connected to the second conductivity type impurity diffusion layer 5. The back junction type solar cell 9 of the present embodiment can be manufactured by the above steps.

In each of the semiconductor element 15 and the solar cell 9, the "first conductivity type" and the "second conductivity type" are different conductivity types, one of which is p-type and the other of which is n-type. For example, if the first conductivity type is p-type, the second conductivity type is n-type.

Further, another example of the method for producing a semiconductor device using the impurity diffusion composition of the present invention can be applied to a solar cell of a double-sided power generation type, a passive emitter and a rear contact (PERC) type sun. The formation of a selective emitter layer of various solar cells, such as a battery, a passivated emitter, and a solar cell with a Passive Emitter and Rear Totally Diffused (PERT) type.

The impurity diffusion composition of the present invention and the method for producing the semiconductor element using the same are not limited to the above embodiment, and various modifications such as design changes may be applied based on the knowledge of those skilled in the art, and the embodiment in which the deformation is applied is also applied. It is included in the scope of the present invention.

Further, the impurity diffusion composition of the present invention may be developed to a photovoltaic element such as a solar cell or a semiconductor element in which an impurity diffusion layer is patterned on a semiconductor substrate surface, for example, a transistor array or a diode array, and a photodiode. Body arrays, converters, etc. [Examples]

Hereinafter, the present invention will be further specifically described by way of examples. Furthermore, the present invention is not limited to the following examples.

(Evaluation of Sheet Resistance Value) The sheet resistance value was evaluated by evaluating the sheet resistance value (also referred to as surface resistivity) of the impurity diffusion layer in the semiconductor substrate. In the sheet resistance evaluation, the semiconductor substrate for evaluation was an n-type germanium wafer (manufactured by Ferrotec Silicon Co., Ltd., surface resistivity 410 [Ω/□]) which was cut into 3 cm × 3 cm. The tantalum wafer was immersed in a 1% aqueous solution of hydrofluoric acid for 5 minutes, washed with water, and then heat-treated at 100 ° C for 5 minutes by blasting.

Then, the impurity-diffusion composition to be measured is applied to the ruthenium wafer for evaluation by a known spin coating method so that the pre-bake film thickness is about 400 nm, and the measurement is performed on the ruthenium wafer surface. The object of the impurity diffuses the coating film of the composition (i.e., the impurity diffusion composition film). Next, the tantalum wafer was prebaked at 140 ° C for 3 minutes. Thereafter, the pre-baked film thickness of the film of the diffusion material on the surface of the germanium wafer by the surface shape measuring device (Surfcom 1400 Tokyo Precision Co., Ltd.) (pre-baked film) Thick) was measured.

Then, for each of the tantalum wafers on which the impurity diffusion composition film is formed by the above method, predetermined laser light is irradiated in a range of 1 cm × 1 cm, and the impurities are diffused into the impurity diffusion component in the composition film (B). Thermal diffusion into the individual wafers. At this time, the laser light is set to Nd:YVO ₄ laser. In the laser light, the wavelength was set to 355 [nm], the pulse width was set to 25 [ns], and the frequency was set to 20 [kHz]. In addition, the laser output is set to 1 [W]. The spot shape is set to a rectangle of 40 [μm]. The scanning speed is set to 3000 [mm/s].

After thermal diffusion of the impurity diffusion component (B), each of the ruthenium wafers was immersed in a 1 mass% TMAH aqueous solution at 23 ° C for 10 minutes. Thereby, the impurity diffusion composition film (diffusion agent) hardened by the irradiation of the laser light is peeled off. The p/n determination was performed using a p/n judger for each of the tantalum wafers after the film was peeled off, and a four-probe surface resistance measuring device (RT-70V Napson) was used. The surface resistance of the diffused portion of the impurity diffusion component (B) in the wafer was measured, and the obtained measured value was taken as the sheet resistance value. The sheet resistance value is an index of the diffusibility of the impurity diffusion component (B) in the semiconductor substrate. The small sheet resistance value means that the diffusion amount of the impurity diffusion component (B) is large.

(Evaluation of the cleansing property of the dry film) The evaluation of the cleansing property of the dry film is a film of the impurity-diffusion composition which remains on the surface of the semiconductor substrate in a dry state after thermal diffusion of the impurity-diffusion component (B) irradiated with the laser light (dry) The cleanability of the film) was evaluated. In the evaluation of the cleanability of the dried film, the semiconductor substrate for evaluation was an n-type germanium wafer cut into 3 cm × 3 cm (manufactured by Ferrotec Silicon Co., Ltd., surface resistivity 410 [Ω/□] ). The tantalum wafer was immersed in a 1% aqueous solution of hydrofluoric acid for 5 minutes, washed with water, and then heat-treated at 100 ° C for 5 minutes by blasting.

Then, the impurity-diffusion composition to be measured is applied to the ruthenium wafer for evaluation by a known spin coating method so that the pre-bake film thickness is about 400 nm, and the measurement is performed on the ruthenium wafer surface. The impurity of the object diffuses into the composition film. Next, the tantalum wafer was prebaked at 140 ° C for 3 minutes. Thereby, the impurity diffusion composition film to be measured is used as a dried film (prebaked film). Thereafter, the ruthenium wafer was immersed in a cleaning liquid, and the time until the prebaking film on the ruthenium wafer surface was dissolved was measured. In the cleaning evaluation, it was judged that the prebaked film was dissolved within 1 minute, and the prebaked film was dissolved within 3 minutes, and the prebaked film was judged to be good. The case where the dissolution took 5 minutes or more was judged as a bad.

(Example 1) In Example 1, polyfluorene oxide (A) was synthesized in the following manner, and sheet resistance value evaluation and dry film were performed on the impurity diffusion composition containing the obtained polyaluminoxane (A). Cleanability evaluation.

In the synthesis of the polyoxyalkylene (A) of Example 1, 15.73 g (0.06 mol) of 3-trimethoxydecylpropyl succinic acid and 155.29 g (1.14 mol) of A were placed in a 500 mL three-necked flask. A tris-methoxydecane and 192.29 g of propylene glycol monomethyl ether were added to an aqueous phosphoric acid solution in which 0.5 g of formic acid was dissolved in 64.0 g of water while stirring at 40 ° C for 30 minutes. 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 rise, the internal temperature of the solution reached 100 ° C, and the solution was heated and stirred for 1 hour from this time (the internal temperature was 100 ° C to 110 ° C). The solution obtained by the above method was cooled using an ice bath to obtain a polyoxyalkylene solution. The solid concentration of the obtained polyoxyalkylene solution was 42.0% by mass. The polyoxyalkylene (A) of Example 1 can be obtained from the polyoxynitane solution.

The impurity diffusion composition of Example 1 was adjusted using the polysiloxane (A) synthesized as described above, the composition ratio of each composition described in Table 1 below, the molar ratio, and the content. The sheet resistance value evaluation of Example 1 and the evaluation of the cleanability of the dried film were carried out on the impurity diffusion composition of Example 1. As a result, as shown in Table 2 below, a good value (that is, a good diffusibility of the impurity diffusion component (B) (hereinafter referred to as "impurity diffusibility")) was obtained in the evaluation of the sheet resistance value, and the cleaning property evaluation was performed. Excellent (excellent).

(Examples 2 to 8) In Examples 2 to 8, the polydecane (A) was synthesized in the same manner as in Example 1 at the ratio of the organodecane compound described in Table 1, and Table 1 The composition ratio of each composition described above, the molar ratio, and the content of each of the impurity diffusion compositions of Examples 2 to 8 were adjusted. In the examples 2 to 8, the sheet resistance value evaluation and the cleanability evaluation of the dried film were performed on the impurity diffusion composition obtained in each of the examples. As a result, as shown in Table 2, in any of Examples 2 to 8, the sheet resistance value (impurity diffusibility) and the cleaning property evaluation were both good. In particular, in Examples 2 to 5 and Example 8, the impurity diffusibility was good, and the cleanability was evaluated as excellent. In Examples 2 to 5 and Example 8, the polysiloxane was used. The content ratio (mol ratio) of at least one organic decane having a carboxyl group and a dicarboxylic anhydride structure in A), Si in terms of the molar number of Si atoms of the polyoxosiloxane (A) derived from organic decane The atomic molar ratio is 5 mol% or more and 30 mol% or less.

(Example 9) In Example 9, "X-22-3701E" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a polysiloxane (A) having a carboxyl group. The polyoxyalkylene (A) (8 g), phosphoric acid (6 g), BYK333 (0.03 g), and propylene glycol monomethyl ether (85.97 g) were mixed to adjust the impurity diffusion composition of Example 9. In Example 9, the impurity resistance composition obtained as described above was evaluated for sheet resistance and the cleaning property of the dried film. As a result, as shown in Table 2, in the evaluation of the sheet resistance value, a good value (good impurity diffusibility) was obtained, and the cleanability was evaluated as good.

Further, although not shown in Table 1, the content ratio of the component derived from the organodecane having a carboxyl group in the polyoxane "X-22-3701E" of Example 9 is relative to the organic decane derived from The polyatomane has a Si atom atomic molar Si atom molar ratio of less than 5 mol%.

(Comparative Example 1) In Comparative Example 1, a polydecane was synthesized at a ratio of the organodecane compound described in Table 1 in the same manner as in Example 1, and the composition ratio of each composition described in Table 1 was observed. The impurity diffusion composition of Comparative Example 1 was adjusted in comparison with the content. The sheet resistance value of Comparative Example 1 and the cleanability evaluation of the dried film were performed on the impurity diffusion composition of Comparative Example 1 obtained in the above manner. As a result, as shown in Table 2, the sheet resistance value (impurity diffusibility) was good, but the cleanability was evaluated as a bad.

[Table 1] (Table 1)

[Table 2] (Table 2) [Industrial availability]

As described above, the impurity diffusion composition of the present invention and the method for producing a semiconductor device using the same are suitable for the cleaning property of the impurity diffusion composition film remaining on the semiconductor substrate after diffusing impurities and impurities of the semiconductor substrate. Both of them improve the situation.

1‧‧‧Semiconductor substrate

2, 4‧‧‧ impurity diffusion composition film

3, 5‧‧‧ impurity diffusion layer

6‧‧‧Protective film

6a‧‧‧ openings

7, 8‧‧‧ contact electrode

9‧‧‧Solar battery

10‧‧‧Laser light

15‧‧‧Semiconductor components

FIG. 1A is a view showing an example of a method of manufacturing a semiconductor device according to an embodiment of the present invention. FIG. 1B is a view showing an example of a method of manufacturing a solar cell using a semiconductor element according to an embodiment of the present invention.

Claims (10)

An impurity diffusion composition comprising: a polyoxyalkylene oxide (A) and an impurity diffusion component (B), and the polyoxyalkylene oxide (A) contains at least one of a carboxyl group and a dicarboxylic anhydride structure. The impurity diffusion composition according to claim 1, wherein the polyoxyalkylene (A) is a polyoxyalkylene represented by the following formula (1). In the formula (1), R ¹ represents a substituent containing at least one of a carboxyl group and a dicarboxylic anhydride structure, and a plurality of R ^{1 's} may be the same or different, and R ² , R ³ and R ⁴ represent a hydroxyl group and a carbon number. Any one of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; R ² , R ³ and R ⁴ may be the same or different, and n and m represent the composition ratio (%) of the components in each parenthesis, n + m = 100, and n: m = 5: 95 to 30: 70. The impurity diffusion composition according to the second aspect of the invention, wherein R ¹ in the formula (1) includes a group represented by any one of the following formulas (2) to (6), In the general formulae (2) to (6), R ⁵ , R ⁷ , R ⁸ and R ⁹ represent a divalent organic group having 1 to 20 carbon atoms; and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹⁰ , R ¹¹ and R ¹² represent a single bond or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a carbonyl group; And an ether group, an ester group, a decylamino group, an aromatic group having 6 to 16 carbon atoms, or a divalent group having any of these; the hydrogen atom of the group may be an alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, a hydroxyl group, an amine group, a carboxyl group or a thiol group; h, j, k and l represent An integer from 0 to 3. The impurity diffusion composition according to any one of claims 1 to 3, wherein the content of the impurity diffusion component (B) is 0.1% by mass or more and 20% by mass or less. The impurity diffusion composition according to any one of claims 1 to 3, wherein the impurity diffusion component (B) contains a compound selected from the group consisting of phosphoric acid, phosphorus pentoxide, polyphosphoric acid, phosphoric acid ester, and boron oxide. And one or more of boric acid, boric acid ester, hydrocarbyl boric acid, and hydrocarbyl borate. The impurity diffusion composition according to any one of claims 1 to 3, wherein the impurity diffusion component (B) contains a compound selected from the group consisting of boric acid, hydrocarbylboronic acid, boric acid ester, and hydrocarbyl borate. One or more, further containing water and a water-soluble binder. The impurity diffusion composition according to claim 6, wherein the water-soluble binder is polyvinyl alcohol. A method of producing a semiconductor device, comprising: a film forming step of applying an impurity diffusion composition containing a polysiloxane (A) and an impurity diffusion component (B) onto a semiconductor substrate to form an impurity diffusion composition film And a layer forming step of diffusing the impurity diffusion component from the impurity diffusion composition film into the semiconductor substrate to form an impurity diffusion layer, and the polyaluminoxane (A) contains a carboxyl group and a dicarboxylic anhydride structure at least one. A method of producing a semiconductor device, comprising: a film forming step of applying an impurity diffusion composition containing a polysiloxane (A) and an impurity diffusion component (B) onto a semiconductor substrate to form an impurity diffusion composition film And a layer forming step of irradiating the impurity diffusion composition film with laser light, diffusing the impurity diffusion component from the impurity diffusion composition film into the semiconductor substrate to form an impurity diffusion layer, and forming the impurity buffer layer (A) at least one of a carboxyl group and a dicarboxylic anhydride structure. A method of producing a semiconductor device, comprising: a film forming step of applying an impurity diffusion composition containing a polysiloxane (A) and an impurity diffusion component (B) onto a semiconductor substrate to form an impurity diffusion composition film a layer forming step of irradiating a portion of the impurity diffusion composition film with laser light, diffusing a part of the impurity diffusion component from the impurity diffusion composition film into the semiconductor substrate to form an impurity diffusion layer; and removing the step Removing, by the acid or the base, the unirradiated portion of the impurity diffusion composition film that is not irradiated with the laser light, and the polyoxyalkylene (A) contains at least a carboxyl group and a dicarboxylic anhydride structure One.