JPWO2021060182A5

JPWO2021060182A5 -

Info

Publication number: JPWO2021060182A5
Application number: JP2020551436A
Authority: JP
Filing date: 2020-09-18
Publication date: 2023-06-12

Description

上記課題を解決するため、本発明の不純物拡散組成物は以下の構成を有する。すなわち、本発明は、（Ａ）ポリビニルアルコール、（Ｂ）不純物拡散成分、および（Ｃ）シロキサンを含み、（Ａ）ポリビニルアルコールのケン化度が２０モル％以上５０モル％未満であり、（Ｂ）不純物拡散成分がホウ酸であり、（Ｃ）シロキサンが下記一般式（１）、（２）のいずれかで示される部分構造と、下記一般式（３）、（４）のいずれかで示される部分構造とをそれぞれ少なくとも１種以上含み、（Ａ）ポリビニルアルコールと（Ｃ）シロキサンの質量比率（Ａ）：（Ｃ）が３０：７０～７５：２５である不純物拡散組成物である。 In order to solve the above problems, the impurity diffusion composition of the present invention has the following constitution. That is, the present invention includes (A) polyvinyl alcohol, (B) an impurity diffusion component, and (C) siloxane, (A) the saponification degree of polyvinyl alcohol is 20 mol% or more and less than 50 mol%, and (B ) the impurity diffusion component is boric acid; (A) polyvinyl alcohol and (C) siloxane in a mass ratio (A):(C) of 30:70 to 75:25.

参考例１
（１）ポリシロキサン溶液Ａの合成
１０００ｍＬの三口フラスコにＫＢＭ－１３（メチルトリメトキシシラン）を１８３．２５ｇ、ＫＢＭ－１０３（フェニルトリメトキシシラン）を２６６．７５ｇ、ＧＢＬを４０３．３６ｇ仕込み、４０℃で攪拌しながら水１４５．２９ｇにギ酸０．４５ｇを溶かしたギ酸水溶液を３０分かけて添加した。滴下終了後、４０℃で１時間撹拌した後、７０℃に昇温し、３０分撹拌した。その後、オイルバスを１１５℃まで昇温した。昇温開始１時間後に溶液の内温が１００℃に到達し、そこから１時間加熱攪拌した（内温は１００～１１０℃）。得られた溶液を氷浴にて冷却し、ポリシロキサン溶液Ａ（ＰｈＴＭＳ（５０）／ＭｅＴＭＳ（５０））を得た。ポリシロキサン溶液Ａの固形分濃度は３９．０質量％であり、重量平均分子量（Ｍｗ）は２５００であった。 Reference example 1
(1) Synthesis of polysiloxane solution A A 1000 mL three-necked flask was charged with 183.25 g of KBM-13 (methyltrimethoxysilane), 266.75 g of KBM-103 (phenyltrimethoxysilane), and 403.36 g of GBL. An aqueous formic acid solution prepared by dissolving 0.45 g of formic acid in 145.29 g of water was added over 30 minutes while stirring at 145.29 g of water. After completion of the dropwise addition, the mixture was stirred at 40°C for 1 hour, then heated to 70°C and stirred for 30 minutes. After that, the temperature of the oil bath was raised to 115°C. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and the solution was heated and stirred for 1 hour (the internal temperature was 100 to 110° C.). The resulting solution was cooled in an ice bath to obtain polysiloxane solution A (PhTMS(50)/MeTMS(50)). Polysiloxane solution A had a solid content concentration of 39.0% by mass and a weight average molecular weight (Mw) of 2,500.

参考例２
ポリビニルアルコールのケン化度を７０モル％としたこと以外は、参考例１と同様にして不純物拡散組成物２を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Reference example 2
An impurity diffusion composition 2 was obtained in the same manner as in Reference Example 1, except that the degree of saponification of polyvinyl alcohol was 70 mol %. As shown in Table 2, the evaluation results of the obtained solutions were all good.

参考例３
ポリビニルアルコールのケン化度を６９モル％としたこと以外は、参考例１と同様にして不純物拡散組成物３を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Reference example 3
An impurity diffusion composition 3 was obtained in the same manner as in Reference Example 1, except that the degree of saponification of polyvinyl alcohol was 69 mol%. As shown in Table 2, the evaluation results of the obtained solutions were all good.

参考例４
ポリビニルアルコールのケン化度を５０モル％としたこと以外は、参考例１と同様にして不純物拡散組成物４を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Reference example 4
An impurity diffusion composition 4 was obtained in the same manner as in Reference Example 1, except that the degree of saponification of polyvinyl alcohol was 50 mol %. As shown in Table 2, the evaluation results of the obtained solutions were all good.

実施例５
ポリビニルアルコールのケン化度を４９モル％としたこと以外は、参考例１と同様にして不純物拡散組成物５を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Example 5
An impurity diffusion composition 5 was obtained in the same manner as in Reference Example 1, except that the degree of saponification of polyvinyl alcohol was 49 mol %. As shown in Table 2, the evaluation results of the obtained solutions were all good.

実施例６
ポリビニルアルコールのケン化度を２０モル％としたこと以外は、参考例１と同様にして不純物拡散組成物６を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Example 6
An impurity diffusion composition 6 was obtained in the same manner as in Reference Example 1, except that the degree of saponification of polyvinyl alcohol was 20 mol %. As shown in Table 2, the evaluation results of the obtained solutions were all good.

参考例７
（Ａ）ポリビニルアルコールと（Ｃ）シロキサンの質量比率（Ａ）：（Ｃ）を２０：８０としたこと以外は、実施例５と同様にして不純物拡散組成物７を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Reference example 7
An impurity diffusion composition 7 was obtained in the same manner as in Example 5 except that the mass ratio (A):(C) of (A) polyvinyl alcohol and (C) siloxane was set to 20:80. As shown in Table 2, the evaluation results of the obtained solutions were all good.

参考例１０
（Ａ）ポリビニルアルコールと（Ｃ）シロキサンの質量比率（Ａ）：（Ｃ）を８０：２０としたこと以外は、実施例５と同様にして不純物拡散組成物１０を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Reference example 10
An impurity diffusion composition 10 was obtained in the same manner as in Example 5 except that the mass ratio (A):(C) of (A) polyvinyl alcohol and (C) siloxane was set to 80:20. As shown in Table 2, the evaluation results of the obtained solutions were all good.

実施例１２
水の量を５．０ｇとしたこと以外は、実施例５と同様にして不純物拡散組成物１２を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Example 12
An impurity diffusion composition 12 was obtained in the same manner as in Example 5 , except that the amount of water was 5.0 g. As shown in Table 2, the evaluation results of the obtained solutions were all good.

実施例１３
水の量を２．５ｇとしたこと以外は、実施例５と同様にして不純物拡散組成物１３を得た。得られた溶液の評価結果は、表２に示すとおり、いずれも良好であった。 Example 13
An impurity diffusion composition 13 was obtained in the same manner as in Example 5 , except that the amount of water was 2.5 g. As shown in Table 2, the evaluation results of the obtained solutions were all good.

参考例２０
ホウ酸の代わりにホウ酸トリメチルを使用したこと以外は、実施例５と同様にして不純物拡散組成物２０を得た。得られた溶液の評価結果は、表２に示す結果となった。 Reference example 20
An impurity diffusion composition 20 was obtained in the same manner as in Example 5 except that trimethyl borate was used instead of boric acid. The evaluation results of the obtained solutions are shown in Table 2.

Claims

(A) polyvinyl alcohol, (B) an impurity diffusion component, and (C) siloxane, (A) the degree of saponification of polyvinyl alcohol is 20 mol% or more and less than 50 mol%, and (B) the impurity diffusion component is boron. is an acid, and (C) siloxane is a partial structure represented by any of the following general formulas (1) and (2), and a partial structure represented by any of the following general formulas (3) and (4): An impurity -diffusing composition containing at least one of (A) polyvinyl alcohol and (C) siloxane in a mass ratio (A):(C) of 30:70 to 75:25.

(R ¹ and R ² are each independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. The plurality of R ¹ and R ² may be the same or different, R ³ represents an aryl group having 6 to 15 carbon atoms, and the plurality of R ³ may be the same or different. ⁴ is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. represents either, and the plurality of R ⁴ may be the same or different.)

Furthermore, (D) contains a solvent, (D) the solvent contains a lactam solvent or a cyclic ester solvent, and (D) the content of the lactam solvent or cyclic ester solvent in the solvent is 20% by mass or more. The impurity diffusion composition according to claim 1.

(D) The impurity diffusion composition according to claim 2 , wherein the content of water in the solvent is 0.1 to 10% by mass.

4. The impurity diffusion composition according to any one of claims 1 to 3 , further comprising (E) a thixotropic agent, wherein (E) the thixotropic agent is fine particles of silicon oxide.

5. The impurity diffusion composition according to any one of claims 1 to 4 , further comprising (F) 0.01 to 0.1% by mass of a carboxylic acid.

6. The impurity diffusion composition according to claim 5 , wherein (F) the carboxylic acid is formic acid.

The impurity diffusion composition according to any one of claims 1 to 6 , which has a pH of 4.0 to 6.5.

applying the impurity diffusion composition according to any one of claims 1 to 7 to a semiconductor substrate to form an impurity diffusion composition film; and diffusing impurities from the impurity diffusion composition film to diffuse the impurities into the semiconductor substrate. A method of manufacturing a semiconductor device, including the step of forming layers.

applying an n-type impurity diffusion composition to a semiconductor substrate to form an n-type impurity diffusion composition film; A method of manufacturing a semiconductor device, comprising: forming an impurity diffusion composition film by coating; and heating the semiconductor substrate to simultaneously form an n-type impurity diffusion layer and a p -type impurity diffusion layer.

forming a p-type impurity diffusion composition film by applying the impurity diffusion composition according to any one of claims 1 to 7 , which is a p-type impurity diffusion composition, on one surface of a semiconductor substrate; applying an n-type impurity diffusion composition to the other surface of the semiconductor substrate to form an n-type impurity diffusion composition film; and heating the semiconductor substrate to form a p-type impurity diffusion layer and an n-type impurity diffusion layer. A method of manufacturing a semiconductor device, including a step of forming simultaneously.

A first p-type impurity diffusion composition film is formed by partially coating one surface of a semiconductor substrate with the impurity diffusion composition according to any one of claims 1 to 7 , which is a p-type impurity diffusion composition. a step of applying a second p-type impurity diffusion composition to a portion where the first p-type impurity diffusion composition film is not formed to form a low-concentration p-type impurity diffusion composition film; applying an n-type impurity diffusion composition to the other surface of the semiconductor substrate to form an n-type impurity diffusion composition film; and heating the semiconductor substrate to form a high-concentration p-type impurity diffusion layer; A method of manufacturing a semiconductor device including a step of simultaneously forming a low-concentration p-type impurity diffusion layer and an n-type impurity diffusion layer.

A method for manufacturing a semiconductor device using a plurality of semiconductor substrates, comprising the following steps (a) to (c), wherein the steps (b) and (c) include: 1. A method of manufacturing a semiconductor element in which the surfaces on which the impurity diffusion composition film of the first conductivity type is formed are arranged so as to face each other.
(a) A step of applying the impurity diffusion composition according to any one of claims 1 to 7 to one surface of each semiconductor substrate to form a first conductivity type impurity diffusion composition film.
(b) heating the semiconductor substrate on which the first conductivity type impurity diffusion composition film is formed to diffuse the first conductivity type impurity into the semiconductor substrate to form a first conductivity type impurity diffusion layer; process of forming.
(c) heating the semiconductor substrate in an atmosphere containing a gas containing second-conductivity-type impurities to diffuse the second-conductivity-type impurities into the other surface of the semiconductor substrate; forming a diffusion layer;

A method for manufacturing a solar cell, comprising the method for manufacturing a semiconductor device according to any one of claims 8 to 12.