JP2010107932A - Composition for forming silicon-containing film for multilayer resist process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming a silicon-containing film for a multilayer resist process, which is excellent in storage stability while preventing an increase of foreign substances generated in the composition due to deterioration with age, and which forms a silicon-containing film excellent in adhesion to a resist film and in reproducibility of a resist pattern and having adequate resistance to a developer and to oxygen ashing in resist removal. <P>SOLUTION: The composition for forming a silicon-containing film for a multilayer resist process includes a polysiloxane (A) and an organic solvent (B), wherein the organic solvent (B) includes 1-50 mass% of an alcoholic organic solvent (B1) and 1-30 mass% of an organic solvent (B2) represented by formula (2) (wherein m denotes an integer of 1-3), provided that the total amount of the organic solvent (B) is considered to be 100 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for forming a silicon-containing film for a multilayer resist process. More specifically, the present invention relates to a composition for forming a silicon-containing film for a multilayer resist process for forming a lower layer film as a base when a resist pattern is formed on a substrate in the multilayer resist process.

In pattern formation when manufacturing semiconductor elements and the like, fine processing of a substrate made of an organic material or an inorganic material is performed by a pattern transfer method using a lithography technique, a resist development process, and an etching technique.
However, as the integration of semiconductor elements and the like on a circuit board increases, it becomes difficult to accurately transfer the pattern of the optical mask to the resist film in the exposure process. For example, it is formed in the resist film in a microfabrication process for the substrate. Due to the influence of the standing wave of the generated light, an error (inconsistency) may occur in the dimension of the formed pattern. In order to reduce the influence of such standing waves, an antireflection film is formed between the resist film and the substrate surface.

  Further, when processing a substrate on which a silicon oxide film, an inorganic interlayer insulating film, or the like is processed, a resist pattern is used as a mask. However, as the pattern becomes finer, it is necessary to make the resist film and the antireflection film thinner. As the resist film becomes thinner in this way, the mask performance of the resist film decreases, and it tends to be difficult to perform desired fine processing without damaging the substrate.

Therefore, a processing lower layer film (silicon-containing film) is formed on the oxide film or interlayer insulating film of the substrate to be processed, a resist pattern is transferred to this, and the processing lower layer film is used as a mask to form an oxide film. In addition, a process of dry etching the interlayer insulating film is performed.
Since the reflectance of such a processing lower layer film varies depending on the film thickness, it is necessary to adjust the composition or the like so that the reflectance is minimized according to the film thickness used. Further, the processing lower layer film can form a resist pattern without tailing, has excellent adhesion to the resist, has sufficient masking properties when processing an oxide film or an interlayer insulating film, There is a demand for a small amount of material to penetrate into the resist underlayer film and excellent etching selectivity in the resist film / resist underlayer film. Furthermore, there is a demand for obtaining a composition that is excellent in storage stability as a solution without increasing the number of foreign matters (foreign matter with time) generated by changes over time in the composition.

  And as an underlayer film for processing proposed so far, for example, a processing underlayer film composed of a hydrolyzate of a specific silane compound and / or a composition containing the condensate thereof (Patent Documents 1 to 3, etc.) Reference).

JP-A-3-45510 JP 2000-356854 A JP 2002-40668 A

However, the resin compositions for forming the processing underlayer film proposed so far are still insufficient in storage stability, and further improvements are required.
Therefore, it is possible to form a silicon-containing film that is excellent in adhesion with the resist film and the reproducibility of the resist pattern, and that has sufficient resistance to a developer used for development and oxygen ashing during resist removal, And the composition provided with the outstanding storage stability is calculated | required.

  The problem of the present invention is that the foreign matter in the composition does not increase with time and is excellent in storage stability, and has excellent adhesion to the resist film and reproducibility of the resist pattern, and development used for development and the like. It is an object of the present invention to provide a composition for forming a silicon-containing film for a multilayer resist process capable of forming a silicon-containing film having sufficient resistance to oxygen ashing during removal of the liquid and the resist.

〔式（２）において、ｍは１〜３の整数を示す。〕
［２］前記アルコール系有機溶媒（Ｂ１）が、プロピレングリコール系アルコールである前記［１］に記載の多層レジストプロセス用シリコン含有膜形成用組成物。
［３］前記ポリシロキサン（Ａ）が、アルコキシシランを出発原料として、有機溶媒中において、水及び触媒の存在下で加水分解及び／又は縮合させて得られたものである前記［１］又は［２］に記載の多層レジストプロセス用シリコン含有膜形成用組成物。
［４］前記ポリシロキサン（Ａ）が、下記式（３）で表される構成単位を含有する前記［１］乃至［３］のいずれか１項に記載の多層レジストプロセス用シリコン含有膜形成用組成物。

〔式（３）において、Ｒ^３は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を示す。ｂは１〜４の整数を示す。〕
［５］前記ポリシロキサン（Ａ）が、下記式（４）で表される構成単位を含有する前記［１］乃至［４］のいずれか１項に記載の多層レジストプロセス用シリコン含有膜形成用組成物。

〔式（４）において、Ｒ^４は、水素原子、ヒドロキシル基、炭素数１〜５の直鎖状若しくは分岐状のアルキル基、又は−ＯＲ^５を示し、Ｒ^５は炭素数１〜５の直鎖状若しくは分岐状のアルキル基を示す。〕
［６］前記ポリシロキサン（Ａ）が、下記式（５）で表される構成単位を含有する前記［１］乃至［５］のいずれか１項に記載の多層レジストプロセス用シリコン含有膜形成用組成物。

［７］紫外光の照射及び／又は加熱により酸を発生する酸発生化合物を更に含有する前記［１］乃至［６］のいずれか１項に記載の多層レジストプロセス用シリコン含有膜形成用組成物。 The present invention is as follows.
[1] A polysiloxane (A) composed of a hydrolyzate and / or a condensate of a compound represented by the following formula (1), and an organic solvent (B),
As said organic solvent (B), 1-50 mass% of alcohol type organic solvents (B1) and 1-30 mass% of organic solvents (B2) represented by following formula (2) [however, organic solvent (B The composition for forming a silicon-containing film for a multilayer resist process is characterized by comprising:
R ¹ _a Si (OR ² ) _4-a (1)
[In Formula (1), R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 15 carbon atoms, or 1 to 10 carbon atoms. Or a group having an acrylic or methacrylic skeleton having 3 to 20 carbon atoms. R ² represents a monovalent organic group. a represents an integer of 0 to 3. ]

[In Formula (2), m shows the integer of 1-3. ]
[2] The composition for forming a silicon-containing film for a multilayer resist process according to [1], wherein the alcohol-based organic solvent (B1) is a propylene glycol-based alcohol.
[3] The above [1] or [3], wherein the polysiloxane (A) is obtained by hydrolysis and / or condensation in an organic solvent in the presence of water and a catalyst using alkoxysilane as a starting material. 2] The composition for forming a silicon-containing film for a multilayer resist process according to [2].
[4] For forming a silicon-containing film for a multilayer resist process according to any one of [1] to [3], wherein the polysiloxane (A) contains a structural unit represented by the following formula (3): Composition.

In [Equation (3), R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms. b shows the integer of 1-4. ]
[5] For forming a silicon-containing film for a multilayer resist process according to any one of [1] to [4], wherein the polysiloxane (A) contains a structural unit represented by the following formula (4): Composition.

[In Formula (4), R ⁴ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to ⁵ carbon atoms, or —OR ⁵ , and R ⁵ is a straight chain having 1 to ⁵ carbon atoms. A chain or branched alkyl group is shown. ]
[6] For forming a silicon-containing film for a multilayer resist process according to any one of [1] to [5], wherein the polysiloxane (A) contains a structural unit represented by the following formula (5): Composition.

[7] The composition for forming a silicon-containing film for a multilayer resist process according to any one of [1] to [6], further comprising an acid generating compound that generates an acid upon irradiation with ultraviolet light and / or heating. .

  The composition for forming a silicon-containing film for a multilayer resist process of the present invention is excellent in storage stability without increasing foreign matters in the composition, and has good adhesion to the resist film and reproducibility of the resist pattern. In addition, it is possible to form a silicon-containing film that is excellent in resistance and sufficiently resistant to a developer used for development and oxygen ashing during resist removal.

Hereinafter, embodiments of the present invention will be described in detail.
[1] Composition for forming a silicon-containing film for a multilayer resist process The composition for forming a silicon-containing film for a multilayer resist process of the present invention (hereinafter also simply referred to as “a composition for forming a silicon-containing film”) is polysiloxane ( A) and an organic solvent (B) are contained.

(1) Polysiloxane (A)
The polysiloxane (A) in the present invention comprises a hydrolyzate of a compound represented by the following formula (1) and / or a condensate thereof.
R ¹ _a Si (OR ² ) _4-a (1)
[In Formula (1), R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 15 carbon atoms, or 1 to 10 carbon atoms. Or a group having an acrylic or methacrylic skeleton having 3 to 20 carbon atoms. R ² represents a monovalent organic group. a represents an integer of 0 to 3. ]

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R ¹ of the formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples include 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.

Examples of the aryl group having 6 to 20 carbon atoms in R ¹ of the formula (1) include a 2-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 4-ethylphenyl group, 4- Propylphenyl group, 4-butylphenyl group, 4-methoxyphenyl group, phenyl group, 4-methoxybenzyl group, benzyl group, 2- (4-methoxyphenyl) ethyl group, 2-phenylethyl group, 1- (4- A methoxyphenyl) ethyl group, a 1-phenylethyl group, and the like.

Furthermore, examples of the ester group having 2 to 15 carbon atoms in R ¹ of the formula (1) include an acetoxy group, a propionoxy group, a butyroxy group, an isobutyroxy group, a valeroxy group, an isovaleroxy group, a pivaloxy group, a benzoxy group, and a phthaloxy group. , Isophthaloxy group, terephthaloxy group, toloxy group and the like.

As the sulfonamide group having 1 to 10 carbon atoms in R ¹ in the formula (1), for example, benzyl sulfonamide group, benzoyl sulfonamide group, a vinyl sulfonamide group, cyanomethyl sulfonamido group, 3-mercaptopropyl -1-sulfonamide group, C- (2-cyanophenyl) methylsulfonamide group, 3,3-dimethylbutylsulfonamide group, 2-oxo-2-phenylethylsulfonamide group, 2- (2,5-di Oxoimidazolin-4-yl) ethylsulfonamide group, C-benzoxazol-2-ylsulfonamide group, ethylsulfonamide group, n-butylsulfonamide group, iso-butylsulfonamide group, octylsulfonamide group, allylsulfone Amido group, 2-phenylethylsulfonamide group, 3 -Aminopropyl sulfonamide group, 2-cyanoethyl sulfonamide group, 3-nitrophenyl sulfonamide group, 4-nitrophenyl sulfonamide group, etc. are mentioned.

Furthermore, examples of the group having an acrylic or methacrylic skeleton having 3 to 20 carbon atoms in R ¹ of the formula (1) include an acryl group, a methacryl group, an acrylate group, a methacrylate group, an ethyl acrylate group, and an n-propyl acrylate. Group, iso-propyl acrylate group, n-butyl acrylate group, 2-methylpropyl acrylate group, 1-methylpropyl acrylate group, t-butyl acrylate group and the like.

Examples of the monovalent organic group in R ² of the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. And an alkyl group which may have a substituent such as a group, γ-aminopropyl group, γ-glycidoxypropyl group, γ-trifluoropropyl group, and the like. Among these, a methyl group and an ethyl group are preferable. Incidentally, it may be each R ² is all the same, may be different for all or part.

  In particular, the polysiloxane (A) in the present invention is a structural unit represented by the following formula (3) [hereinafter referred to as “structural unit (1)”. ] Is preferable.

〔式（３）において、Ｒ^３は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を示す。ｂは１〜４の整数を示す。〕

In [Equation (3), R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms. b shows the integer of 1-4. ]

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ³ in the formula (3) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples include 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.
Moreover, b in Formula (3) is an integer of 1-4, Preferably it is an integer of 1-3.

Examples of the monomer that gives the structural unit (1) include a silane compound represented by the following formula (i).
R ⁶ Si (OR ⁷ ) ₃ (i)
[In formula (i), R ⁶ represents a group represented by the following formula (a), and R ⁷ represents a monovalent organic group. ]

〔式（ａ）において、Ｒ^８は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を示す。ｎは１〜４の整数を示す。〕

[In Formula (a), R ⁸ represents a linear or branched alkyl group having 1 to 4 carbon atoms. n shows the integer of 1-4. ]

For R ⁸ and n in the formula (a), the description of R ³ and b in the formula (3) can be applied as they are. "
Examples of the monovalent organic group in R ⁷ of the formula (i) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. And an alkyl group which may have a substituent such as a group, γ-aminopropyl group, γ-glycidoxypropyl group, γ-trifluoropropyl group, and the like. Among these, a methyl group and an ethyl group are preferable. Incidentally, it may be all the R ⁷ are same or different for all or part.

  Specific examples of the silane compound that gives the structural unit (1) include 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, and N-3- (methacryloxy-2-hydroxypropyl). -3-aminopropyltriethoxysilane, 3- (trimethoxysilyl) ethyl methacrylate, 3- (triethoxysilyl) ethyl methacrylate, 3- (trimethoxysilyl) methyl methacrylate, methacryloxypropyltris (methoxyethoxy) silane, tri Ethoxysilylmethyl methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, 3- [tris (dimethylvinylsiloxy)] propyl methacrylate, 3- (trichlorosilyl) propyl methacrylate 3- (trimethoxysilyl) acrylate, 3- (triethoxysilyl) acrylate.

Among these, from the viewpoint of ease of monomer synthesis, 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) methyl methacrylate, 2- (tri Methoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) ethyl methacrylate and the like are preferable.
These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition, the said structural unit (1) may be contained only 1 type in the said polysiloxane (A), and may be contained 2 or more types.

  The polysiloxane (A) is a structural unit represented by the following formula (4) [hereinafter referred to as “structural unit (2)”. ] Is preferable.

〔式（４）において、Ｒ^４は、水素原子、ヒドロキシル基、炭素数１〜５の直鎖状若しくは分岐状のアルキル基、又は−ＯＲ^５を示し、Ｒ^５は炭素数１〜５の直鎖状若しくは分岐状のアルキル基を示す。ｎは０〜２の整数を示す。〕

[In Formula (4), R ⁴ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to ⁵ carbon atoms, or —OR ⁵ , and R ⁵ is a straight chain having 1 to ⁵ carbon atoms. A chain or branched alkyl group is shown. n shows the integer of 0-2. ]

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms in R ⁴ of the formula (4) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, 2- A methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group and the like can be mentioned.
In addition, when R ⁴ is —OR ⁵ , the linear or branched alkyl group having 1 to ⁵ carbon atoms of R ⁵ includes a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. , N-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group and the like.

Examples of the monomer that provides the structural unit (2) include a silane compound represented by the following formula (ii).
R ⁹ Si (OR ¹⁰ ) ₃ (ii)
[In Formula (ii), R ⁹ represents a group represented by the following Formula (b), and R ¹⁰ represents a monovalent organic group. ]

〔式（ｂ）において、Ｒ^１１は、水素原子、ヒドロキシル基、炭素数１〜５の直鎖状若しくは分岐状のアルキル基、又は−ＯＲ^１２を表し、Ｒ^１２は炭素数１〜５の直鎖状若しくは分岐状のアルキル基を表す。ｎは０〜２の整数を示す。〕

[In Formula (b), R ¹¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or —OR ¹² , and R ¹² is a straight chain having 1 to 5 carbon atoms. A chain or branched alkyl group is represented. n shows the integer of 0-2. ]

For R ¹¹ and R ¹² in the formula (b), the description of R ⁴ and R ⁵ in the formula (4) can be applied as it is.
Examples of the monovalent organic group in R ¹⁰ of the formula (ii) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. And an alkyl group which may have a substituent such as a group, γ-aminopropyl group, γ-glycidoxypropyl group, γ-trifluoropropyl group, and the like. Among these, a methyl group and an ethyl group are preferable. Incidentally, it may be all each R ¹⁰ is the same, may be different for all or part.

  Specific examples of the silane compound that gives the structural unit (2) include 2-methylphenyltrimethoxysilane, 2-methylphenyltriethoxysilane, 2-methylphenyltri-n-propoxysilane, and 2-methyl. Phenyltri-iso-propoxysilane, 2-methylphenyltri-n-butoxysilane, 2-methylphenyltri-sec-butoxysilane, 2-methylphenyltri-tert-butoxysilane, 2-methylphenyltrichlorosilane, 2- Methylphenyltriacetoxysilane, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-methylphenyltri-n-propoxysilane, 4-methylphenyltri-iso-propoxysilane, 4-methylphenyltri- n-Butoki Silane, 4-methylphenyltri-sec-butoxysilane, 4-methylphenyltri-tert-butoxysilane, 4-methylphenyltrichlorosilane, 4-methylphenyltriacetoxysilane, 2-ethylphenyltrimethoxysilane, 2-ethyl Phenyltriethoxysilane, 2-ethylphenyltri-n-propoxysilane, 2-ethylphenyltri-iso-propoxysilane, 2-ethylphenyltri-n-butoxysilane, 2-ethylphenyltri-sec-butoxysilane, 2 -Ethylphenyltri-tert-butoxysilane, 2-ethylphenyltrichlorosilane, 2-ethylphenyltriacetoxysilane,

  4-ethylphenyltrimethoxysilane, 4-ethylphenyltriethoxysilane, 4-ethylphenyltri-n-propoxysilane, 4-ethylphenyltri-iso-propoxysilane, 4-ethylphenyltri-n-butoxysilane, 4 -Ethylphenyltri-sec-butoxysilane, 4-ethylphenyltri-tert-butoxysilane, 4-ethylphenyltrichlorosilane, 4-ethylphenyltriacetoxysilane, 4-propylphenyltrimethoxysilane, 4-propylphenyltriethoxy Silane, 4-propylphenyltri-n-propoxysilane, 4-propylphenyltri-iso-propoxysilane, 4-propylphenyltri-n-butoxysilane, 4-propylphenyltri-sec-butoxysilane, -Propylphenyltri-tert-butoxysilane, 4-propylphenyltrichlorosilane, 4-propylphenyltriacetoxysilane, 4-butylphenyltrimethoxysilane, 4-butylphenyltriethoxysilane, 4-butylphenyltri-n-propoxy Silane, 4-butylphenyltri-iso-propoxysilane, 4-butylphenyltri-n-butoxysilane, 4-butylphenyltri-sec-butoxysilane, 4-butylphenyltri-tert-butoxysilane, 4-butylphenyl Trichlorosilane, 4-butylphenyltriacetoxysilane, 4-methoxyphenyltrimethoxysilane, 4-methoxyphenyltriethoxysilane, 4-methoxyphenyltri-n-propoxysilane, 4-methoxyphenyl Lutri-iso-propoxysilane, 4-methoxyphenyltri-n-butoxysilane, 4-methoxyphenyltri-sec-butoxysilane, 4-methoxyphenyltri-tert-butoxysilane, 4-methoxyphenyltrichlorosilane, 4-methoxy Phenyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri- tert-butoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, 4-methoxybenzyltrimethoxysilane, 4-methoxybenzyltriethoxysilane, 4-methoxybenzyltri -N-propoxysilane, 4-methoxybenzyltri-iso-propoxysilane, 4-methoxybenzyltri-n-butoxysilane, 4-methoxybenzyltri-sec-butoxysilane, 4-methoxybenzyltri-tert-butoxysilane, 4-methoxybenzyltrichlorosilane, 4-methoxybenzyltriacetoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltri-n-propoxysilane, benzyltri-iso-propoxysilane, benzyltri-n-butoxysilane, benzyltri-sec- Butoxysilane, benzyltri-tert-butoxysilane, benzyltrichlorosilane, benzyltriacetoxysilane,

  2- (4-methoxyphenyl) ethyltrimethoxysilane, 2- (4-methoxyphenyl) ethyltriethoxysilane, 2- (4-methoxyphenyl) ethyltri-n-propoxysilane, 2- (4-methoxyphenyl) ethyltri -Iso-propoxysilane, 2- (4-methoxyphenyl) ethyltri-n-butoxysilane, 2- (4-methoxyphenyl) ethyltri-sec-butoxysilane, 2- (4-methoxyphenyl) ethyltri-tert-butoxysilane 2- (4-methoxyphenyl) ethyltrichlorosilane, 2- (4-methoxyphenyl) ethyltriacetoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 2-phenylethyltri-n- Propoxysilane, 2-pheny Ethyltri-iso-propoxysilane, 2-phenylethyltri-n-butoxysilane, 2-phenylethyltri-sec-butoxysilane, 2-phenylethyltri-tert-butoxysilane, 2-phenylethyltrichlorosilane, 2-phenyl Ethyltriacetoxysilane, 1- (4-methoxyphenyl) ethyltrimethoxysilane, 1- (4-methoxyphenyl) ethyltriethoxysilane, 1- (4-methoxyphenyl) ethyltri-n-propoxysilane, 1- (4 -Methoxyphenyl) ethyltri-iso-propoxysilane, 1- (4-methoxyphenyl) ethyltri-n-butoxysilane, 1- (4-methoxyphenyl) ethyltri-sec-butoxysilane, 1- (4-methoxyphenyl) ethyltri -Tert Butoxysilane, 1- (4-methoxyphenyl) ethyltrichlorosilane, 1- (4-methoxyphenyl) ethyltriacetoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 1-phenylethyltri- n-propoxysilane, 1-phenylethyltri-iso-propoxysilane, 1-phenylethyltri-n-butoxysilane, 1-phenylethyltri-sec-butoxysilane, 1-phenylethyltri-tert-butoxysilane, 1 -Phenylethyltrichlorosilane, 1-phenylethyltriacetoxysilane and the like.

Among these compounds, from the viewpoint of ease of monomer synthesis, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-methylphenyltri-n-propoxysilane, 4-methylphenyltri -Iso-propoxysilane, 4-methylphenyltri-n-butoxysilane, 4-methylphenyltri-sec-butoxysilane, 4-methoxyphenyltrimethoxysilane, 4-methoxyphenyltriethoxysilane, 4-methoxyphenyltri- n-propoxysilane, 4-methoxyphenyltri-iso-propoxysilane, 4-methoxyphenyltri-n-butoxysilane, 4-methoxyphenyltri-sec-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri − -Propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltri-n-propoxysilane, benzyltri-iso-propoxy Silane, benzyltri-n-butoxysilane, benzyltri-sec-butoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 2-phenylethyltri-n-propoxysilane, 2-phenylethyltri-iso -Propoxysilane, 2-phenylethyltri-n-butoxysilane, 2-phenylethyltri-sec-butoxysilane and the like are preferable.
These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition, the said structural unit (2) may be contained only 1 type in the said polysiloxane (A), and may be contained 2 or more types.

  The polysiloxane (A) is a structural unit represented by the following formula (5) [hereinafter referred to as “structural unit (3)”. ] Is preferable.

Examples of the monomer that gives the structural unit (3) include a silane compound represented by the following formula (iii).
Si (OR ¹³ ) ₄ (iii)
[In Formula (iii), R ¹³ represents a monovalent organic group. ]

Examples of the monovalent organic group in R ¹³ of the formula (iii) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include an alkyl group which may have a substituent such as γ-aminopropyl group, γ-glycidoxypropyl group and γ-trifluoropropyl group. Among these, a methyl group and an ethyl group are preferable. Incidentally, it may be each R ¹³ is all the same, may be different for all or part.

Specific examples of the silane compound that gives the structural unit (3) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra- sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraisocyanatosilane, tetrakis (butoxyethoxyethoxy) silane, tetrakis (dimethylsiloxy) silane, tetrakis (ethoxyethoxy) silane, Tetrakis (2-ethylhexyloxy) silane, tetrakis (2-methacryloxyethoxy) silane, tetrakis (methoxyethoxyethoxy) silane, tetrakis (methoxyethoxy) silane, Rakisu (methoxypropoxy) silane, tetrakis (methyl ethyl ketone creaking Roh) silane, tetrakis (trichlorosilylethyl) silane, tetrakis (trimethylsiloxy) silane, tetrakis (vinyldimethylsiloxy) silane. Among these, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxy are considered from the viewpoints of reactivity and easy handling of substances. Silane and the like are preferable.
These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The polysiloxane (A) is a structural unit represented by the following formula (6) [hereinafter referred to as “structural unit (4)”. ] Is preferable.

〔式（６）において、Ｒ^１４は、直鎖状又は分岐状の炭素数１〜４のアルキル基を表す。〕

In [Equation ^{(6), R 14} represents a linear or branched alkyl group having 1 to 4 carbon atoms. ]

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ¹⁴ in the formula (4) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples include 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.

Examples of the monomer that gives the structural unit (4) include a silane compound represented by the following formula (iv).
R ¹⁵ Si (OR ¹⁶ ) ₃ (iv)
[In Formula (iv), R ¹⁵ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and R ¹⁶ represents a monovalent organic group. ]

For R ¹⁵ in the formula (iv), the description of R ¹⁴ in the formula (4) can be applied as it is.
Examples of the monovalent organic group for R ¹⁶ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, and γ-aminopropyl. And an alkyl group which may have a substituent such as a group, γ-glycidoxypropyl group and γ-trifluoropropyl group. Among these, a methyl group and an ethyl group are preferable. Incidentally, it may be all the R ¹⁶ is the same, may be different for all or part.

  Specific examples of the silane compound that gives the structural unit (4) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, and methyltri-n-butoxysilane. Methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, methyltriacetoxysilane, methyltrichlorosilane, methyltriisopropenoxysilane, methyltris (dimethylsiloxy) silane, methyltris (methoxyethoxy) silane, Methyltris (methylethylketoxime) silane, methyltris (trimethylsiloxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane Ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, ethylbis (trimethylsiloxy) silane, ethyldichlorosilane, ethyltriacetoxysilane, ethyl Trichlorosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyl Tri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, n-propyltriacetoxysilane, n-propyltrichlorosilane, i-pro Rutrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane I-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, n-butyltrichlorosilane, 2-methylpropyltrimethoxysilane, 2- Methylpro Pyrtriethoxysilane, 2-methylpropyltri-n-propoxysilane, 2-methylpropyltri-iso-propoxysilane, 2-methylpropyltri-n-butoxysilane, 2-methylpropyltri-sec-butoxysilane, 2 -Methylpropyltri-tert-butoxysilane, 2-methylpropyltriphenoxysilane, 1-methylpropyltrimethoxysilane, 1-methylpropyltriethoxysilane, 1-methylpropyltri-n-propoxysilane, 1-methylpropyltri -Iso-propoxysilane, 1-methylpropyltri-n-butoxysilane, 1-methylpropyltri-sec-butoxysilane, 1-methylpropyltri-tert-butoxysilane, 1-methylpropyltriphenoxysilane, t-butyl Limethoxysilane, t-butyltriethoxysilane, t-butyltri-t-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri -Tert-butoxysilane, t-butyltriphenoxysilane, t-butyltrichlorosilane, t-butyldichlorosilane and the like.

Among these, from the viewpoint of reactivity and easy handling of substances, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri- sec-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysila Etc. are preferred.
In addition, these monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, the said structural unit (4) may be contained only 1 type in the said polysiloxane (A), and may be contained 2 or more types.

<Other structural units>
The polysiloxane (A) may further contain other structural units in addition to the structural units (1) to (4).
Examples of the other structural units include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diphenyldimethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, di-tert-butyldichlorosilane, and diethoxydivinylsilane. , Di (3-methacryloxypropyl) dimethoxysilane, dimethyldiethoxysilane, dimesityldimethoxysilane, dimesityldichlorosilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dimethyldiacetoxysilane, diethyldiethoxysilane, dicyclopentyl Dimethoxysilane, di-n-butyldichlorosilane, di-t-butyldichlorosilane, di-cyclohexyldichlorosilane, acetoxypropyldichlorosilane, 3-acryloxypropyl) methyldichlorosilane, allylhexyldichlorosilane, allylmethyldichlorosilane, allylphenyldimethoxysilane, aminopropylmethyldiethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, dimethacryloxydimethoxysilane, t- Butylmethyldichlorosilane, t-butylphenyldichlorosilane, 2- (carbomethoxy) ethylmethyldichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldimethoxysilane, 3-cyanopropyl Phenyldichlorosilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldichlorosilane, mercapto Tylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, isobutylmethyldimethoxysilane, phenylmethyldichlorosilane, ethylmethyldichlorosilane, 3-methacryloxypropylmethyldiethoxysilane, p-tolylmethyldichlorosilane, phenethylmethyldichlorosilane , Di (p-tolyl) dichlorosilane, di (3-glycidoxy) propyldimethoxysilane, di (3-glycidoxy) propyldiethoxysilane, (3-cyclohexenyl) propyldimethoxysilane Is mentioned.

  Furthermore, N-3- (triethoxysilyl) propylmethylsulfonamide, N-3- (triethoxysilyl) propylbenzylsulfonamide, N-3- (triethoxysilyl) propylbenzoylsulfonamide, N-3- ( Triethoxysilyl) propylvinylsulfonamide, N-3- (triethoxysilyl) propylcyanomethylsulfonamide, N-3- (triethoxysilyl) propyl-3-mercaptopropyl-1-sulfonamide, N-3- ( Triethoxysilyl) propylbenzylsulfonamide, N-3- (triethoxysilyl) propyl-C- (2-cyanophenyl) methylsulfonamide, N-3- (triethoxysilyl) propyl-3,3-dimethylbutylsulfone Amido, N-3- (triethoxysilyl) pro Ru-2-oxo-2-phenylethylsulfonamide, N-3- (triethoxysilyl) propyl-2- (2,5-dioxoimidazolin-4-yl) ethylsulfonamide, N-3- (triethoxy Silyl) propyl-C-benzoxazol-2-ylsulfonamide, N-3- (triethoxysilyl) propyl-C-benzoxazol-2-ylsulfonamide, N-2- (triethoxysilyl) ethylbenzylsulfonamide N-2- (triethoxysilyl) ethylbenzoylsulfonamide, N-2- (triethoxysilyl) ethylmethylsulfonamide, N-2- (triethoxysilyl) ethylethylsulfonamide, N-2- (triethoxy Silyl) ethyl-n-butylsulfonamide, N-2- (triethoxysilyl) Ethyl-iso-butylsulfonamide, N-2- (triethoxysilyl) ethyloctylsulfonamide, N-2- (triethoxysilyl) ethylvinylsulfonamide, N-2- (triethoxysilyl) ethylallylsulfonamide, N-2- (triethoxysilyl) ethyl-2-phenylethylsulfonamide, N-2- (triethoxysilyl) ethyl-3-aminopropylsulfonamide, N-2- (triethoxysilyl) ethyl-2-cyanoethyl Sulfonamide, N-2- (triethoxysilyl) ethyl-3-nitrophenylsulfonamide, N-2- (triethoxysilyl) ethyl-4-nitrophenylsulfonamide,

  N-3- (trimethoxysilyl) propylbenzylsulfonamide, N-3- (trimethoxysilyl) propylbenzoylsulfonamide, N-3- (trimethoxysilyl) propylvinylsulfonamide, N-3- (trimethoxysilyl) ) Propyl cyanomethylsulfonamide, N-3- (trimethoxysilyl) propyl-3-mercaptopropyl-1-sulfonamide, N-3- (trimethoxysilyl) propylbenzylsulfonamide, N-3- (trimethoxysilyl) ) Propyl-C- (2-cyanophenyl) methylsulfonamide, N-3- (trimethoxysilyl) propyl-3,3-dimethylbutylsulfonamide, N-3- (trimethoxysilyl) propyl-2-oxo- 2-phenylethylsulfonamide, N-3- (trimethyl Xylyl) propyl-2- (2,5-dioxoimidazolin-4-yl) ethylsulfonamide, N-3- (trimethoxysilyl) propyl-C-benzoxazol-2-ylsulfonamide, N-3- ( Trimethoxysilyl) propyl-C-benzoxazol-2-ylsulfonamide, N-2- (trimethoxysilyl) ethylbenzylsulfonamide, N-2- (trimethoxysilyl) ethylbenzoylsulfonamide, N-2- ( Triethoxysilyl) ethylmethylsulfonamide, N-2- (trimethoxysilyl) ethylethylsulfonamide, N-2- (trimethoxysilyl) ethyl-n-butylsulfonamide, N-2- (trimethoxysilyl) ethyl -Iso-butylsulfonamide, N-2- (trimethoxysilyl) Ethyloctylsulfonamide, N-2- (trimethoxysilyl) ethylvinylsulfonamide, N-2- (trimethoxysilyl) ethylallylsulfonamide, N-2- (trimethoxysilyl) ethyl-2-phenylethylsulfonamide N-2- (trimethoxysilyl) ethyl-3-aminopropylsulfonamide, N-2- (trimethoxysilyl) ethyl-2-cyanoethylsulfonamide, N-2- (trimethoxysilyl) ethyl-3-nitro Examples thereof include structural units derived from a monomer having a sulfonamide group such as phenylsulfonamide and N-2- (trimethoxysilyl) ethyl-4-nitrophenylsulfonamide.

Among the monomers having the sulfonamide group, N-3- (triethoxysilyl) propylmethylsulfonamide and N-3- (triethoxysilyl) propylbenzylsulfone are preferable from the viewpoint of ease of monomer synthesis. Amide, N-2- (triethoxysilyl) ethylbenzylsulfonamide, N-2- (triethoxysilyl) ethylmethylsulfonamide, N-2- (triethoxysilyl) ethylethylsulfonamide, N-2- (tri Ethoxysilyl) ethyl-n-butylsulfonamide, N-2- (triethoxysilyl) ethyl-2-phenylethylsulfonamide and the like are preferable.
In addition, these “other structural units” may be included alone or in combination of two or more.

  Although the content rate of the said structural unit (1) in the said polysiloxane (A) is not specifically limited, When the sum total of all the structural units contained in a polysiloxane (A) is 100 mol%, 1 mol% It is preferable that it is above, More preferably, it is 2-50 mol%, More preferably, it is 3-30 mol%. When the content is 1 mol% or more, it is preferable because the resist pattern is excellent in shape and sufficient adhesion is obtained.

  The content ratio of the structural unit (2) is not particularly limited, but when the total of all the structural units contained in the polysiloxane (A) is 100 mol%, it is preferably 30 mol% or less, Preferably it is 1-20 mol%, More preferably, it is 2-15 mol%. A content of 30 mol% or less is preferable because the antireflection function at a wavelength of 193 nm is good.

  The content ratio of the structural unit (3) is not particularly limited, but is preferably 95 mol% or less when the total of all the structural units contained in the polysiloxane (A) is 100 mol%. Preferably it is 10-90 mol%, More preferably, it is 15-80 mol%. When the content is 95 mol% or less, it is preferable because the polymerization reactivity can be easily controlled and the molecular weight can be controlled.

  The content ratio of the structural unit (4) is not particularly limited, but is preferably 90 mol% or less when the total of all the structural units contained in the polysiloxane (A) is 100 mol%, Preferably it is 1-50 mol%, More preferably, it is 2-40 mol%. When the content is 90 mol% or less, it is preferable because the polymerization reactivity can be easily controlled and the molecular weight can be controlled.

  The content of the other structural units is not particularly limited, but is preferably 30 mol% or less, more preferably 100 mol% when the total of all the structural units contained in the polysiloxane (A) is 100 mol%. Is 1 to 20 mol%, more preferably 2 to 10 mol%. When this content is 30 mol% or less, good coating properties can be secured, which is preferable.

  The polystyrene equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of the polysiloxane (A) measured by gel permeation chromatography (GPC) is preferably 500 to 100,000, more preferably 1,000 to 50,000. More preferably, it is 1000-10000.

(2) Production method of polysiloxane (A) The production method of the polysiloxane (A) is not particularly limited. For example, hydrolysis and hydrolysis in the presence of water and a catalyst in an organic solvent using alkoxysilane as a starting material. It can be obtained by condensation. More specifically, the starting material is dissolved in an organic solvent, and water is intermittently or continuously added to the solution. At this time, the catalyst may be dissolved or dispersed in advance in an organic solvent, or may be dissolved or dispersed in water to be added. Moreover, the temperature for performing a hydrolysis reaction and / or a condensation reaction is 0-100 degreeC normally.
Examples of the alkoxysilane that is the starting material include monomers that give the respective structural units [the structural units (1) to (4) and other structural units, etc.] in the polysiloxane (A). .

  Although it does not specifically limit as water for performing the said hydrolysis and / or condensation, It is preferable to use ion-exchange water. The water is used in an amount of 0.25 to 3 mol, preferably 0.3 to 2.5 mol, per mol of alkoxyl group of the alkoxysilane used. By using water in an amount in the above range, there is no possibility that the uniformity of the formed coating film will be lowered, and there is little possibility that the storage stability of the composition will be lowered.

The organic solvent is not particularly limited as long as it is an organic solvent used for this kind of application. For example, ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, glycerin, 1-butanol, 2- Butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1,4-butanediol, pentanol, 1-methyl-1-butanol, 2-methyl-1-butanol, 3-methyl-1- Butanol, cyclopentanol, hexanol, 4-methyl-2-pentanol, cyclohexanol, heptanol, cycloheptanol, octanol, nonyl alcohol, decyl alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, Ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, diethylene glycol mono-iso-butyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ethanol, diethylene glycol monobenzyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, 4-methoxy-1-butanol, 2-methoxyethanol, 2-iso-propoxyethanol, 2-butoxyethanol, 2-iso- Butoxyethan 2-hexyloxyethanol, 2- (2-ethyl) hexyloxyethanol, 2-allyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, Examples include 1-propoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, and the like.
Among these, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 4-methyl-2-pentanol, heptanol, cycloheptanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol is preferable, and 4-methyl-2-pentanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-propoxy-2-propanol are more preferable.
These organic solvents may be used alone or in combination of two or more.

Examples of the catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, inorganic bases, and the like.
Examples of the metal chelate compound include a titanium chelate compound, a zirconium chelate compound, and an aluminum chelate compound. Specifically, compounds described in Patent Document 1 (Japanese Patent Laid-Open No. 2000-356854) and the like can be used.
Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, Gallic acid, butyric acid, merit acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene Examples include sulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diaza Bicyclononane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Of these catalysts, metal chelate compounds, organic acids and organic bases are preferred. The said catalyst may be used independently and may be used in combination of 2 or more type.
The catalyst is usually used in a range of 0.001 to 10 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the solid content of the polysiloxane (A).

  Further, in the production of the polysiloxane (A), after the hydrolysis and / or condensation of the alkoxysilane, for example, the removal of reaction byproducts such as lower alcohols such as methanol and ethanol is performed. Is preferred. The method for removing the reaction by-product is not particularly limited as long as the reaction of the hydrolyzate of alkoxysilane and / or the condensate thereof does not proceed. For example, the boiling point of the reaction by-product is When it is lower than the boiling point of the organic solvent, it can be distilled off under reduced pressure.

  In addition, the said polysiloxane (A) may be contained only 1 type in the composition for silicon-containing film formation of this invention, and may be contained 2 or more types.

(3) Organic solvent (B)
In the composition for forming a silicon-containing film of the present invention, as the organic solvent (B), an alcohol-based organic solvent (B1) [hereinafter also simply referred to as “solvent (B1)”. And an organic solvent (B2) represented by the following formula (2) [hereinafter also simply referred to as “solvent (B2)”. ] Is included.

〔式（２）において、ｍは１〜３の整数を示す。〕

[In Formula (2), m shows the integer of 1-3. ]

Examples of the solvent (B1) include propylene glycol, glycerin, dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, 1- Propylene glycol alcohols such as methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, ethylene glycol, diethylene glycol, tri Ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl Ether, triethylene glycol monobutyl ether, diethylene glycol mono-iso-butyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ethanol, diethylene glycol monobenzyl ether, 2-methoxyethanol, 2-iso-propoxyethanol, 2-butoxyethanol, Ethylene glycol alcohols such as 2-iso-butoxyethanol, 2-hexyloxyethanol, 2- (2-ethyl) hexyloxyethanol, 2-allyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, ethanol, 1- Propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2 Propanol, 1,4-butanediol, pentanol, 1-methyl-1-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, cyclopentanol, hexanol, 4-methyl-2-pentanol And other alcohols such as cyclohexanol, heptanol, cycloheptanol, octanol, nonyl alcohol and decyl alcohol.
Among these, propylene glycol alcohol is preferable. In particular, propylene glycol alcohols such as 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, and 1-phenoxy-2-propanol are preferable.
In addition, only 1 type may be contained for these solvents (B1), and 2 or more types may be contained.

Examples of the solvent (B2) include β-propiolactone, γ-butyrolactone, and δ-valerolactone.
Among these, γ-butyrolactone is preferable.
In addition, these solvent (B2) may be contained only 1 type and may be contained 2 or more types.

In addition to the solvent (B1) and the solvent (B2), the organic solvent (B) in the present invention is also referred to as another organic solvent (B3) [hereinafter simply referred to as “solvent (B3)”. ] Is included.
The solvent (B3) is not particularly limited as long as it can dissolve the polysiloxane (A). For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene Propylene glycol monoalkyl ether acetates such as glycol mono-n-butyl ether acetate, lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, iso-propyl lactate, n-amyl formate, iso-amyl formate, ethyl acetate N-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, n-amyl acetate, iso-amyl acetate, iso-propyl propionate, n-butyl propionate, propiate Fatty acid esters such as iso-butyl acid, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, Other esters such as 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether etc Ethers. Among these, propylene glycol monomethyl ether acetate and ethyl lactate are preferable.
These solvents (B3) may be included alone or in combination of two or more.

The content of the solvent (B1) is 1 to 50% by mass, preferably 100% by mass when the entire organic solvent (B) [total of the solvents (B1), (B2) and (B3)] is 100% by mass, Is 5 to 40% by mass, more preferably 10 to 35% by mass.
The content of the solvent (B2) is 1 to 30% by mass, preferably 100% by mass when the entire organic solvent (B) [total of the solvents (B1), (B2) and (B3)] is 100% by mass, Is 3 to 20% by mass, more preferably 5 to 15% by mass.
The content ratio of the solvent (B3) is 20 to 98% by mass, preferably 100% by mass when the entire organic solvent (B) [total of the solvents (B1), (B2) and (B3)] is 100% by mass. Is 40 to 92 mass%, more preferably 50 to 85 mass%.
When each of these solvents is in the above range, it is preferable because excellent storage stability is obtained.

(4) Other components (i)
(4-1) Acid-generating compound In addition to the polysiloxane and the solvent, the silicon-containing film-forming composition of the present invention includes an acid-generating compound that generates an acid upon irradiation with ultraviolet light and / or heating (hereinafter, simply “ Also referred to as “acid generator”.
When such an acid generator is contained, an acid is generated in the silicon-containing film by exposing the resist or heating after exposure, and an acid is generated at the interface between the silicon-containing film and the resist film. Is supplied. As a result, a resist pattern excellent in resolution and reproducibility can be formed in the alkali development treatment of the resist film.
Examples of the acid generator include a compound that generates an acid by performing ultraviolet light irradiation treatment (hereinafter also referred to as “latent photoacid generator”) and a compound that generates an acid by performing a heat treatment (hereinafter “latent”). Also referred to as a “refining thermal acid generator”.
Examples of the latent photoacid generator include onium salt photoacid generators, halogen-containing compound photoacid generators, diazoketone compound photoacid generators, sulfonic acid compound photoacid generators, Examples thereof include sulfonate compound-based photoacid generators. These may be used alone or in combination of two or more.
Examples of the latent thermal acid generator include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. Among these, sulfonium salts and benzothiazolium salts include preferable. More specific compounds include compounds described in Patent Document 1 and the like. These may be used alone or in combination of two or more.

  It is preferable that content of the said acid generator is 0.1-10 mass parts with respect to 100 mass parts of solid content of polysiloxane (A), More preferably, it is 0.1-5 mass parts.

(3-2) β-diketone Further, the composition for forming a silicon-containing film of the present invention may contain β-diketone in order to improve the uniformity of the formed coating film and the storage stability. Good.
Examples of the β-diketone include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- Nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexa Examples include fluoro-2,4-heptanedione. These may be used alone or in combination of two or more.

  The content of the β-diketone is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass when the total of the β-diketone and the organic solvent (B) is 100 parts by mass. It is.

(5) Other components (ii)
Further, the composition for forming a silicon-containing film of the present invention may further contain components such as colloidal silica, colloidal alumina, an organic polymer, and a surfactant.
Examples of the organic polymer include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, an acrylate compound, a methacrylate compound, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, and a polyamide. , Polyquinoxaline, polyoxadiazole, fluorine-based polymer, and the like. These may be used alone or in combination of two or more.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. Surfactant etc. are mentioned. These may be used alone or in combination of two or more.

[2] Method for Producing Silicon-Containing Film-Forming Composition The method for producing the silicon-containing film-forming composition of the present invention is not particularly limited. For example, (1) the polysiloxane (A) and the solvent (B) [Solvent (B1), (B2), (B3)] and, if necessary, the above-mentioned other additives are mixed, or (2) one or more of the solvents (B) are mixed with polysiloxane ( It can be obtained by mixing the resin solution in which A) is dissolved, the solvent (B), and, if necessary, the other additive.
Moreover, it is preferable that the solid content density | concentration of the composition for silicon-containing film formation of this invention is 1-20 mass%, especially 1-15 mass%.

[3] Method for Forming Silicon-Containing Film The composition for forming a silicon-containing film of the present invention forms a coating film of this composition by, for example, applying it to the surface of an antireflection film, and heat-treating this coating film When the latent photoacid generator is contained, a silicon-containing film (resist underlayer film) can be formed by performing ultraviolet light irradiation and heat treatment.
As a method of applying the composition for forming a silicon-containing film of the present invention, a spin coating method, a roll coating method, a dip method, or the like can be used. Moreover, the heating temperature of the coating film formed is 50-450 degreeC normally, and the film thickness after heat processing is 10-200 nm normally.
The silicon-containing film formed as described above has high adhesion to other resist underlayer films and resist films, has resistance to oxygen ashing for removing the resist developer and resist, and is reproducible. High resist pattern can be obtained.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, “part” and “%” are based on mass unless otherwise specified.

[1] Production of polysiloxane As shown in the following synthesis examples (synthesis examples 1 to 4), polysiloxanes [resins (A-1) to (A-4)] were prepared. In addition, the measurement of the weight average molecular weight (Mw) of resin obtained by each synthesis example was performed by the following method.

<Measurement of weight average molecular weight (Mw)>
Tosoh GPC columns (trade name "G2000HXL", trade name "G3000HXL", trade name "G4000HXL" 1), flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature : Measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C.

<Synthesis Example 1 (A-1)>
An aqueous oxalic acid solution was prepared by dissolving 0.45 parts of oxalic acid in 21.6 parts of water by heating. Then, 0.50 parts of 3- (trimethoxysilyl) propyl methacrylate [following formula (M-1)], 0.99 parts of phenyltrimethoxysilane [following formula (M-2)], methyltrimethoxysilane [following formula (M-3)] 3.13 parts, tetramethoxysilane [following formula (M-4)] 10.7 parts, and a flask containing 53.5 parts of propylene glycol-1-ethyl ether, A dropping funnel containing the oxalic acid aqueous solution prepared as described above was set. Subsequently, after heating to 60 degreeC with an oil bath, the oxalic acid aqueous solution was dripped slowly, and it was made to react at 60 degreeC for 4 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool, and then methanol produced by distillation under reduced pressure was removed to obtain a propylene glycol-1-ethyl ether resin solution. Let solid content (polysiloxane) in this resin solution be resin (A-1).
The solid content concentration of the obtained resin solution was 16.3% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of resin (A-1) was 1200. In addition, the structural monomer ratio (M-1: M-2: M-3: M-4) of resin (A-1) is 2: 5: 23: 70 (mol%).

尚、式中の「Ｍｅ」はメチル基を示し、「Ｐｈ」はフェニル基を示す。

In the formula, “Me” represents a methyl group, and “Ph” represents a phenyl group.

<Synthesis Example 2 (A-2)>
An aqueous tetraammonium hydroxide solution was prepared by dissolving 1.82 parts of tetramethylammonium hydroxide in 5.47 parts of water. Thereafter, in a flask containing 7.29 parts of the prepared tetraammonium hydroxide aqueous solution, 2.27 parts of water, and 20 parts of methanol, a condenser tube and 3- (trimethoxysilyl) propyl methacrylate [formula (M-1 ] 1.50 parts, phenyltrimethoxysilane [formula (M-2)] 0.50 parts, methyltrimethoxysilane [formula (M-3)] 2.04 parts, tetramethoxysilane [formula ( M-4)] A dropping funnel containing 4.19 parts and 25 parts of methanol was set. Subsequently, after heating at 60 degreeC with an oil bath, the monomer methanol solution was dripped slowly and it was made to react at 60 degreeC for 2 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool.
Thereafter, 2.50 parts of maleic anhydride was dissolved in 9.18 parts of water and 9.18 parts of methanol, and 21 parts of maleic acid methanol solution prepared separately was added dropwise to the reaction solution which had been allowed to cool as described above. And stirred for 30 minutes. Next, 25 parts of 4-methyl-2-pentenone was added, and then methanol produced by distillation under reduced pressure was removed to obtain a 4-methyl-2-pentenone resin solution. After the obtained resin solution was transferred to a separatory funnel, 40 parts of water was added to perform first washing with water, and 20 parts of water was further added to perform second washing with water. Thereafter, 25 parts of propylene glycol-1-ethyl ether was added to the 4-methyl-2-pentenone resin solution transferred to the flask from the separatory funnel, and then 4-methyl-2-pentenone was removed by distillation under reduced pressure. A propylene glycol-1-ethyl ether resin solution was obtained. Let solid content (polysiloxane) in this resin solution be resin (A-2).
The solid concentration of the obtained resin solution was 13.6% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of resin (A-2) was 4600. The constituent monomer ratio (M-1: M-2: M-3: M-4) of the resin (A-2) is 10: 5: 30: 55 (mol%).

<Synthesis Example 3 (A-3)>
An aqueous tetraammonium hydroxide solution was prepared by dissolving 1.82 parts of tetramethylammonium hydroxide in 5.47 parts of water. Then, in a flask containing 7.29 parts of the prepared tetraammonium hydroxide aqueous solution, 2.27 parts of water, and 20 parts of methanol, a cooling tube, phenyltrimethoxysilane [formula (M-2)] 0.99 Then, a dropping funnel containing 3.41 parts of methyltrimethoxysilane [formula (M-3)], 10.7 parts of tetramethoxysilane [formula (M-4)] and 25 parts of methanol was set. Subsequently, after heating at 60 degreeC with an oil bath, the monomer methanol solution was dripped slowly and it was made to react at 60 degreeC for 2 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool.
Thereafter, 2.50 parts of maleic anhydride was dissolved in 9.18 parts of water and 9.18 parts of methanol, and 21 parts of maleic acid methanol solution prepared separately was added dropwise to the reaction solution which had been allowed to cool as described above. And stirred for 30 minutes. Next, 25 parts of 4-methyl-2-pentenone was added, and then methanol produced by distillation under reduced pressure was removed to obtain a 4-methyl-2-pentenone resin solution. After the obtained resin solution was transferred to a separatory funnel, 40 parts of water was added to perform first washing with water, and 20 parts of water was further added to perform second washing with water. Thereafter, 25 parts of propylene glycol-1-ethyl ether was added to the 4-methyl-2-pentenone resin solution transferred to the flask from the separatory funnel, and then 4-methyl-2-pentenone was removed by distillation under reduced pressure. A propylene glycol-1-ethyl ether resin solution was obtained. Let solid content (polysiloxane) in this resin solution be resin (A-3).
As a result of measuring the solid content concentration of the obtained resin solution by the firing method, it was 14.0%. Moreover, the weight average molecular weight (Mw) of resin (A-3) was 5000. The constituent monomer ratio (M-2: M-3: M-4) of the resin (A-3) is 5:25:70 (mol%).

<Synthesis Example 4 (A-4)>
An aqueous tetraammonium hydroxide solution was prepared by dissolving 1.82 parts of tetramethylammonium hydroxide in 5.47 parts of water. Thereafter, in a flask containing 7.29 parts of the prepared tetraammonium hydroxide aqueous solution, 2.27 parts of water, and 20 parts of methanol, a condenser tube and methyltrimethoxysilane [formula (M-3)] 4.9 were added. A dropping funnel containing 10.7 parts of tetramethoxysilane [formula (M-4)] and 25 parts of methanol was set. Subsequently, after heating at 60 degreeC with an oil bath, the monomer methanol solution was dripped slowly and it was made to react at 60 degreeC for 2 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool.
Thereafter, 2.50 parts of maleic anhydride was dissolved in 9.18 parts of water and 9.18 parts of methanol, and 21 parts of maleic acid methanol solution prepared separately was added dropwise to the reaction solution which had been allowed to cool as described above. And stirred for 30 minutes. Next, 25 parts of 4-methyl-2-pentenone was added, and then methanol produced by distillation under reduced pressure was removed to obtain a 4-methyl-2-pentenone resin solution. After the obtained resin solution was transferred to a separatory funnel, 40 parts of water was added to perform first washing with water, and 20 parts of water was further added to perform second washing with water. Thereafter, 25 parts of propylene glycol-1-ethyl ether was added to the 4-methyl-2-pentenone resin solution transferred to the flask from the separatory funnel, and then 4-methyl-2-pentenone was removed by distillation under reduced pressure. A propylene glycol-1-ethyl ether resin solution was obtained. Let solid content (polysiloxane) in this resin solution be resin (A-4).
As a result of measuring the solid content concentration of the obtained resin solution by the firing method, it was 15.5%. Moreover, the weight average molecular weight (Mw) of resin (A-4) was 5200. In addition, the structural monomer ratio (M-3: M-4) of resin (A-4) is 34:69 (mol%).

  Table 1 summarizes the monomer charge amount, the solid content concentration of the obtained resin solution, and the weight average molecular weight (Mw) of the solid content in the obtained resin solution in each of the above synthesis examples.

[2] Preparation of composition for forming silicon-containing film for multilayer resist process Propylene glycol-1-ethyl ether resin solution obtained in Synthesis Examples 1 to 4 above [resins (A-1) to (A-4) Containing resin solution], various solvents (B), and optionally using an acid generator (C), for forming silicon-containing films for multilayer resist processes of Examples 1 to 5 and Comparative Example 1 as described below. A composition was prepared.

<Example 1>
14.89 parts of the propylene glycol-1-ethyl ether resin solution (solid content concentration: 16.3%) obtained in Synthesis Example 1 was replaced with 27.67 parts of propylene glycol monomethyl ether acetate [solvent (B1)], propylene After dissolving in 13.83 parts of glycol-1-ethyl ether [solvent (B2)] and 4.61 parts of γ-butyrolactone [solvent (B3)], the solution was filtered with a filter having a pore size of 0.2 μm. The composition for forming a silicon-containing film for a multilayer resist process of Example 1 was obtained. The content of each component is shown in Table 2.

<Examples 2 to 5 and Comparative Example 1>
A propylene glycol-1-ethyl ether resin solution containing the polysiloxane [resin (A)] obtained in each of the above synthesis examples, various solvents (B) and an acid generator (C), each component shown in Table 2 The compositions for forming a silicon-containing film for multilayer resist processes of Examples 2 to 5 and Comparative Example 1 were obtained in the same manner as in Example 1.

The details of the (B) solvent and (C) acid generator in Table 2 are as follows.
<(B) Solvent>
B1-1: Propylene glycol-1-ethyl ether [corresponding to the aforementioned solvent (B1)]
B2-1: γ-butyrolactone [corresponding to the aforementioned solvent (B2)]
B3-1: Propylene glycol monomethyl ether acetate [corresponding to the above-mentioned solvent (B3)]
<(C) Acid generator>
C-1: Diphenyliodonium trifluoromethanesulfonate

[3] Evaluation of silicon-containing film-forming compositions (Examples 1 to 5 and Comparative Example 1) The following various evaluations were performed on the silicon-containing film-forming compositions obtained in the Examples and Comparative Examples. The results are shown in Table 3.

(1) Storage stability of solution A silicon-containing film-forming composition was applied to the surface of a silicon wafer using a spin coater under the conditions of a rotation speed of 2000 rpm for 20 seconds, and then on a hot plate at 250 ° C. for 60 seconds. A silicon-containing film was formed by drying. About the obtained silicon-containing film, the film thickness was measured at 50 points using an optical film thickness meter (manufactured by KLA-Tencor, “UV-1280SE”), and the average film thickness (initial film thickness = T0). )
Furthermore, using the composition for forming a silicon-containing film after being stored at a temperature of 23 ° C. for 3 months, a silicon-containing film was formed in the same manner as described above, and the film thickness was measured. Thickness = T) was determined.
And the difference (T-T0) between the initial film thickness T0 and the post-storage film thickness T is obtained, and the ratio [(T-T0) / T0] of the difference with respect to the average film thickness T0 is taken as the film thickness change rate. The case where the value was 5% or less was evaluated as “◯”, and the case where the value exceeded 5% was evaluated as “X”.

(2) Adhesion By applying a composition for forming a lower layer film (trade name “NFC HM8005”, manufactured by JSR Corporation) on a silicon wafer with a spin coater and drying it on a hot plate at 250 ° C. for 60 seconds. A lower layer film having a thickness of 300 nm was formed.
Thereafter, a silicon-containing film-forming composition for a multilayer resist process was applied onto this lower layer film by a spin coater and baked on a hot plate at 250 ° C. for 60 seconds to form a silicon-containing film.
Next, a resist material “AIM5056JN” (manufactured by JSR Corporation) was applied onto the silicon-containing film and dried at 90 ° C. for 60 seconds. The resist film thickness at this time was controlled to 120 nm. Thereafter, using an ArF excimer laser irradiation apparatus (manufactured by Nikon Corporation), the substrate was irradiated with 32 mJ of ArF excimer laser (wavelength: 193 nm) through a quartz mask having a 0.08 μm line and space pattern. The substrate was heated at 115 ° C. for 60 seconds. Subsequently, the resist pattern was formed by developing with a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds.
When the resist pattern formed on the substrate as described above is observed with a scanning electron microscope (SEM), the case where the resist pattern is not developed and peeled is indicated as “◯”, and the case where the developed film is peeled off. Evaluated as “x”.

(3) Resist pattern reproducibility A resist pattern formed by the same method as in (2) above was observed with an SEM. Resist film residue did not occur in the area irradiated with the laser, and the optical mask was 0.08 μm. The case where the line and space pattern was faithfully reproduced was evaluated as “◯”, and the case where the line and space pattern was not faithfully reproduced was evaluated as “x”.

(4) Resistance to developer The composition for forming a silicon-containing film for a multilayer resist process is applied to the surface of a silicon wafer using a spin coater under the conditions of a rotational speed of 2000 rpm and 20 seconds, and then a hot plate at 250 ° C. A silicon-containing film was formed by drying for 60 seconds.
Next, the silicon-containing film was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds.
And the film thickness of the silicon-containing film before being immersed in a developing solution was compared with the film thickness of the silicon-containing film after being immersed, and the difference was calculated. When the difference between the two was 1 nm or less, it was a good silicon-containing film, and the evaluation was “◯”. On the other hand, the case where this difference exceeded 1 nm was designated as “x”.

(5) Mask properties (oxygen ashing resistance)
A silicon-containing film forming composition for a multilayer resist process is applied to the surface of a silicon wafer using a spin coater under the conditions of a rotational speed of 2000 rpm and 20 seconds, and then dried on a hot plate at 250 ° C. for 60 seconds. Thus, a silicon-containing film was formed.
The silicon-containing film is subjected to an oxygen ashing process at 300 W for 15 seconds using an etching apparatus “EXAM” (manufactured by Shinko Seiki Co., Ltd.). The difference was calculated. When the difference between the two was 5 nm or less, it was a good silicon-containing film, and the evaluation was “◯”. On the other hand, the case where this difference exceeded 5 nm was defined as “x”.

(6) Temporal change in the number of foreign matter in solution Using the composition for forming a silicon-containing film after storage for 3 months at a temperature of 23 ° C., a device for measuring the number of foreign matters in liquid “KS-41” (manufactured by Rion Co., Ltd.) The number of foreign particles in the liquid of 0.15 μm or more is measured, the difference between the initial number of foreign particles P0 and the number of foreign particles in the liquid after storage (P−P0) is obtained, and the magnitude of the difference with respect to the initial number of foreign particles P0 The ratio [(P−P0) / P0] was calculated as the rate of change in the number of foreign matter in the liquid, and the case where the value was 5% or less was designated “◯”. On the other hand, the case where this value exceeded 5% was evaluated as “x”.

  As is apparent from Table 3, the silicon-containing film-forming compositions for the multilayer resist processes of Examples 1 to 5 have excellent storage stability without increasing foreign matter over time in the compositions, and resists It was found that a silicon-containing film having excellent adhesion to the film and reproducibility of the resist pattern and having sufficient resistance to oxygen ashing during the developer and resist removal can be formed.

Claims (7)

Containing a hydrolyzate of a compound represented by the following formula (1) and a condensate thereof, or a polysiloxane (A) composed of either one, and an organic solvent (B),
As said organic solvent (B), 1-50 mass% of alcohol type organic solvents (B1) and 1-30 mass% of organic solvents (B2) represented by following formula (2) [however, organic solvent (B The composition for forming a silicon-containing film for a multilayer resist process is characterized by comprising:
R ¹ _a Si (OR ² ) _4-a (1)
[In Formula (1), R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, an ester group having 2 to 15 carbon atoms, or 1 to 10 carbon atoms. Or a group having an acrylic or methacrylic skeleton having 3 to 20 carbon atoms. R ² represents a monovalent organic group. a represents an integer of 0 to 3. ]

[In Formula (2), m shows the integer of 1-3. ]   The composition for forming a silicon-containing film for a multilayer resist process according to claim 1, wherein the alcohol-based organic solvent (B1) is a propylene glycol-based alcohol.   The multilayer according to claim 1 or 2, wherein the polysiloxane (A) is obtained by hydrolysis and / or condensation in an organic solvent in the presence of water and a catalyst using alkoxysilane as a starting material. Composition for forming silicon-containing film for resist process. The composition for forming a silicon-containing film for a multilayer resist process according to any one of claims 1 to 3, wherein the polysiloxane (A) contains a structural unit represented by the following formula (3).

In [Equation (3), R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms. b shows the integer of 1-4. ] The composition for forming a silicon-containing film for a multilayer resist process according to any one of claims 1 to 4, wherein the polysiloxane (A) contains a structural unit represented by the following formula (4).

[In Formula (4), R ⁴ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to ⁵ carbon atoms, or —OR ⁵ , and R ⁵ is a straight chain having 1 to ⁵ carbon atoms. A chain or branched alkyl group is shown. n shows the integer of 0-2. ] The composition for forming a silicon-containing film for a multilayer resist process according to any one of claims 1 to 5, wherein the polysiloxane (A) contains a structural unit represented by the following formula (5).

  The composition for forming a silicon-containing film for a multilayer resist process according to any one of claims 1 to 6, further comprising an acid generating compound that generates an acid upon irradiation with ultraviolet light and / or heating.