JP5540509B2 - Composition for forming silicon-containing film for multilayer resist process, silicon-containing film, and pattern forming method - Google Patents

Description

  The present invention relates to a silicon-containing film forming composition for a multilayer resist process, a silicon-containing film, and a pattern forming method for forming a lower layer film as a base when forming a resist pattern on a substrate in a 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, It is required that the amount of penetration of the material into the resist underlayer film is small, the etching selectivity in the resist film / resist underlayer film is excellent, and the storage stability as a solution is excellent.

  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

With the recent miniaturization of resist patterns, it has become more important than ever to suppress the amount of resist material soaked into the resulting underlayer film for processing.
However, in the resin composition for forming a processing underlayer film that has been proposed so far, the suppression of the amount of the resist material soaked into the obtained processing underlayer film is not yet sufficient. There is a need for improvement. Furthermore, there is a need for a resin composition that can provide a processing lower layer film that can stably form a resist pattern without skirting.

  An object of the present invention is to provide a resist pattern that is excellent in storage stability, can form a silicon-containing film having a large Si content and a small amount of permeation of a resist material, and has an excellent bottom shape without skirting or the like. An object of the present invention is to provide a silicon-containing film forming composition for a multilayer resist process, a silicon-containing film, and a pattern forming method, which can be stably formed.

〔一般式（ｂ１）において、Ｒ^１は２価の有機基を表す。Ｒ^２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^３を表し、Ｒ^３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。〕
［３］前記（Ａ）ポリシロキサンが、テトラアルコキシシラン由来の構造単位（ａ１）を含有する前記［１］又は［２］のいずれか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（Ａ）ポリシロキサンが、更に、下記一般式（１）で表されるオルガノシラン由来の構造単位（ａ２）を含有する前記［３］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。

〔一般式（１）において、Ｒ^４は１価の有機基を表す。Ｒ^５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^６を表し、Ｒ^６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の整数である。〕
［５］前記（Ａ）ポリシロキサンが、更に、下記一般式（２）で表されるオルガノシラン由来の構造単位（ａ３）を含有する前記［３］又は［４］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。

〔一般式（２）において、Ｒ^７は１価の有機基を表す。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表す。ｎは１〜４の整数である。〕
［６］更に、酸発生剤を含有する前記［１］乃至［５］のいずれか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］前記［１］乃至［６］のいずれか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を用いて得られることを特徴とするシリコン含有膜。
［８］（１）前記［１］乃至［６］のいずれか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を被加工基板上に塗布してシリコン含有膜を形成する工程と、
（２）得られた前記シリコン含有膜上に、レジスト組成物を塗布してレジスト被膜を形成する工程と、
（３）得られた前記レジスト被膜に、フォトマスクを透過させることにより選択的に放射線を照射して前記レジスト被膜を露光する工程と、
（４）露光した前記レジスト被膜を現像して、レジストパターンを形成する工程と、
（５）前記レジストパターンをマスクとして、前記シリコン含有膜及び前記被加工基板をドライエッチングしてパターンを形成する工程と、を備えることを特徴とするパターン形成方法。 The present invention is as follows.
[1] In a multilayer resist process, when forming a resist pattern on a substrate, a composition for forming a silicon-containing film for a multilayer resist process for forming a lower layer film serving as a base thereof,
(A) a polysiloxane having a silanol group;
(B) an oxetanyl group-containing compound having two or more oxetanyl groups;
(C) an organic solvent,
A composition for forming a silicon-containing film for a multilayer resist process, wherein the oxetanyl group-containing compound is a bisoxetane compound.
[2] The composition for forming a silicon-containing film for a multilayer resist process according to [1], wherein the (B) oxetanyl group-containing compound is a compound represented by the following formula (b1).

[In General Formula (b1), R ¹ represents a divalent organic group. R ² represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or —OR ³ , and R ³ represents a linear or branched alkyl group having 1 to 5 carbon atoms. Represents a group. ]
[3] The composition for forming a silicon-containing film for a multilayer resist process according to any one of [1] or [2], wherein the (A) polysiloxane contains a structural unit (a1) derived from tetraalkoxysilane.
[4] Formation of silicon-containing film for multilayer resist process according to [3], wherein (A) the polysiloxane further contains an organosilane-derived structural unit (a2) represented by the following general formula (1) Composition.

[In General Formula (1), R ⁴ represents a monovalent organic group. R ⁵ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or —OR ⁶ , and R ⁶ represents a linear or branched alkyl group having 1 to 5 carbon atoms. Represents a group. n is an integer of 0-2. ]
[5] The multilayer resist process according to [3] or [4], wherein the (A) polysiloxane further contains an organosilane-derived structural unit (a3) represented by the following general formula (2): A composition for forming a silicon-containing film.

[In General Formula (2), R ⁷ represents a monovalent organic group. R ⁸ represents a linear or branched alkyl group having 1 to 4 carbon atoms. n is an integer of 1-4. ]
[6] The composition for forming a silicon-containing film for a multilayer resist process according to any one of [1] to [5], further comprising an acid generator.
[7] A silicon-containing film obtained by using the composition for forming a silicon-containing film for a multilayer resist process according to any one of [1] to [6].
[8] (1) A step of forming a silicon-containing film by applying the silicon-containing film-forming composition for a multilayer resist process according to any one of [1] to [6] on a substrate to be processed;
(2) A step of applying a resist composition on the obtained silicon-containing film to form a resist film;
(3) The step of exposing the resist film by selectively irradiating radiation by allowing the obtained resist film to pass through a photomask;
(4) developing the exposed resist film to form a resist pattern;
(5) A pattern forming method comprising: forming a pattern by dry etching the silicon-containing film and the substrate to be processed using the resist pattern as a mask.

The composition for forming a silicon-containing film for a multilayer resist process of the present invention is excellent in storage stability and has good adhesion to a resist film, reproducibility of a resist pattern, resistance to a developer, and oxygen ashing during resist removal. It is possible to form a silicon-containing film that is excellent in masking property (etching resistance). Furthermore, it is possible to form a silicon-containing film having a large Si content and a small amount of permeation of the resist material, and to stably form a resist pattern excellent in a bottom shape without skirting or the like. Therefore, it is particularly preferably used in pattern formation using a multilayer resist process in an area finer than 90 nm (ArF, ArF, F ₂ , EUV, nanoimprint in immersion exposure) among multilayer resist processes. it can.

Hereinafter, embodiments of the present invention will be described in detail.
[1] Silicon-containing film-forming composition for multilayer resist process The silicon-containing film-forming composition for multilayer resist process of the present invention (hereinafter also simply referred to as “silicon-containing film-forming composition”) is a multilayer resist process. In order to form a lower layer film as a base when a resist pattern is formed on a substrate, (A) polysiloxane [hereinafter referred to as “polysiloxane (A)”. And (B) an oxetanyl group-containing compound having two or more oxetanyl groups (hereinafter also referred to simply as “oxetanyl group-containing compound (B)”). ], (C) Organic solvent [hereinafter referred to as “organic solvent (C)”. And containing.

(1) Polysiloxane (A)
The polysiloxane (A) in the present invention preferably contains a structural unit (a1) derived from tetraalkoxysilane.
In the tetraalkoxysilane that gives the structural unit (a1), the four alkoxyl groups bonded to the Si atom may all be the same, or all or a part thereof may be different. The alkoxyl group preferably has 1 to 8 carbon atoms.
Specific tetraalkoxysilanes 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, tetrakis (methoxypro ) 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, and tetra-sec-butoxysilane are preferable.
These tetraalkoxysilanes may be used alone or in combination of two or more.

  In addition, the said polysiloxane (A) may contain only 1 type of the said structural unit (a1), and may contain 2 or more types.

  In addition to the structural unit (a1), the polysiloxane (A) is a structural unit derived from an organosilane represented by the following general formula (1) as other structural unit [hereinafter referred to as “structural unit ( a2) ". ] May be contained.

〔一般式（１）において、Ｒ^４は１価の有機基を表す。Ｒ^５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^６を表し、Ｒ^６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の整数である。〕

[In General Formula (1), R ⁴ represents a monovalent organic group. R ⁵ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or —OR ⁶ , and R ⁶ represents a linear or branched alkyl group having 1 to 5 carbon atoms. Represents a group. n is an integer of 0-2. ]

Examples of the monovalent organic group in R ⁴ of the general 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 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 all the R ⁴ are same or different for all or part.
Examples of the linear or branched alkyl group having 1 to ⁵ carbon atoms in R ⁵ of the general formula (1) 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 ⁵ is —OR ⁶ , the linear or branched alkyl group having 1 to 5 carbon atoms of R ⁶ includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group. , N-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group and the like.

  Specific examples of the organosilane that gives the structural unit (a2) include 2-methylphenyltrimethoxysilane, 2-methylphenyltriethoxysilane, 2-methylphenyltri-n-propoxysilane, and 2-methylphenyltrimethoxysilane. -Iso-propoxysilane, 2-methylphenyltri-n-butoxysilane, 2-methylphenyltri-sec-butoxysilane, 2-methylphenyltri-tert-butoxysilane, 2-methylphenyltrichlorosilane, 2-methylphenyl Triacetoxysilane, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-methylphenyltri-n-propoxysilane, 4-methylphenyltri-iso-propoxysilane, 4-methylphenyltri-n- Butoxy Lan, 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 polysiloxane (A) may contain only 1 type of the said structural unit (a2), and may contain 2 or more types.

  The polysiloxane (A) is a structural unit derived from an organosilane represented by the following general formula (2) as another structural unit [hereinafter referred to as “structural unit (a3)”. ] May be contained.

〔一般式（２）において、Ｒ^７は１価の有機基を表す。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表す。ｎは１〜４の整数である。〕

[In General Formula (2), R ⁷ represents a monovalent organic group. R ⁸ represents a linear or branched alkyl group having 1 to 4 carbon atoms. n is an integer of 1-4. ]

Examples of the monovalent organic group in R ⁷ of the general formula (2) 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 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 all the R ⁷ are same or different for all or part.
Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ⁸ in the general formula (2) 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, n in General formula (2) is an integer of 1-4, Preferably it is an integer of 1-3.

  Specific organosilanes that give the structural unit (a3) include 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, N-3- (methacryloxy-2-hydroxypropyl) -3. -Aminopropyltriethoxysilane, 3- (trimethoxysilyl) ethyl methacrylate, 3- (triethoxysilyl) ethyl methacrylate, 3- (trimethoxysilyl) methyl methacrylate, methacryloxypropyltris (methoxyethoxy) silane, triethoxysilyl Methyl methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, 3- [tris (dimethylvinylsiloxy)] propyl methacrylate, 3- (trichlorosilyl) propyl methacrylate, - (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 polysiloxane (A) may contain only 1 type of the said structural unit (a3), and may contain 2 or more types.

  The polysiloxane (A) is a structural unit represented by the following general formula (3) [hereinafter referred to as “structural unit (a4)” as another structural unit. ] May be contained.

〔一般式（３）において、Ｒ^９は１価の有機基を表し、Ｒ^１０は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を表す。〕

[In General Formula (3), R ⁹ represents a monovalent organic group, and R ¹⁰ represents a linear or branched alkyl group having 1 to 4 carbon atoms. ]

Examples of the monovalent organic group represented by R ⁹ in the general formula (3) 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 γ-aminopropyl group, γ-glycidoxypropyl group and γ-trifluoropropyl group. Among these, a methyl group and an ethyl group are preferable. Each R ⁹ may be the same or all or a part of them may be different.
Examples of the linear or branched alkyl group having 1 to 4 carbon atoms ^{R 10} in the general formula (3), for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl Group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.

  Specific examples of the compound that gives the structural unit (a4) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, 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, ethyl Lutri-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-propyl Limethoxysilane, 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- Methylpropyl Triethoxysilane, 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-butyltri Toxisilane, 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.
These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition, the said polysiloxane (A) may contain only 1 type of the said structural unit (a4), and may contain 2 or more types.

In addition to the structural units (a2) to (a4), the polysiloxane (A) may further contain the following “other structural units” as other structural units.
Examples of the other structural units include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diphenyldimethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, di-tert-butyldichlorosilane, and diethoxydi. Vinylsilane, di (3-methacryloxypropyl) dimethoxysilane, dimethyldiethoxysilane, dimesityldimethoxysilane, dimesityldichlorosilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dimethyldiacetoxysilane, diethyldiethoxysilane, di Cyclopentyldimethoxysilane, di-n-butyldichlorosilane, di-t-butyldichlorosilane, di-cyclohexyldichlorosilane, acetoxypropyldichlorosila (3-acryloxypropyl) methyldichlorosilane, allylhexyldichlorosilane, allylmethyldichlorosilane, allylphenyldimethoxysilane, aminopropylmethyldiethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, dimethacryloxydimethoxysilane, t-butylmethyldichlorosilane, t-butylphenyldichlorosilane, 2- (carbomethoxy) ethylmethyldichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldimethoxysilane, 3- Cyanopropylphenyldichlorosilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldichlorosilane, merca Tomethylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, isobutylmethyldimethoxysilane, phenylmethyldichlorosilane, ethylmethyldichlorosilane, 3-methacryloxypropylmethyldiethoxysilane, p-tolylmethyldichlorosilane, phenethylmethyldi Structures derived from monomers such as chlorosilane, di (p-tolyl) dichlorosilane, di (3-glycidoxy) propyldimethoxysilane, di (3-glycidoxy) propyldiethoxysilane, (3-cyclohexenyl) propyldimethoxysilane Units are listed.
In addition, the said polysiloxane (A) may contain only 1 type of these other structural units, and may contain 2 or more types.

Moreover, in the said polysiloxane (A), when the sum total of the structural unit which comprises this polysiloxane (A) is 100 mol%, the content rate of a structural unit (a1) is 10-95 mol%. More preferably, it is 10-90 mol%, More preferably, it is 15-85 mol%. When the content ratio of the structural unit (a1) is within the above range, it is preferable because the polymerization reactivity can be easily controlled and the molecular weight can be controlled.
Moreover, it is preferable that the content rate of a structural unit (a2) is 30 mol% or less, More preferably, it is 1-20 mol%, More preferably, it is 2-15 mol%. When the content rate of this structural unit (a2) exists in the said range, since the antireflection function in a wavelength of 193 nm is favorable, it is preferable.
Furthermore, the content ratio of the structural unit (a3) is preferably 60 mol% or less, more preferably 2 to 50 mol%, still more preferably 3 to 30 mol%. When the content ratio of the structural unit (a3) is within the above range, it is preferable because the resist pattern is excellent in shape and sufficient adhesion can be obtained.
Moreover, it is preferable that the content rate of a structural unit (a4) is 90 mol% or less, More preferably, it is 1-50 mol%, More preferably, it is 2-40 mol%. When the content ratio of the structural unit (a4) is within the above range, it is preferable because the polymerization reactivity can be easily controlled and the molecular weight can be controlled.
In addition, such a content rate of each structural unit can be estimated from the analysis result of a ²⁹ Si-NMR spectrum, and the below-mentioned weight average molecular weight, for example.

  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. Is 1000-50000, more preferably 1000-10000. When this Mw is 500 to 100,000, it is preferable because the coating property is good and the storage stability is good.

Although the manufacturing method of the said polysiloxane (A) in this invention is not specifically limited, It can obtain by carrying out a hydrolysis condensation reaction using the compound which gives each said structural unit as a starting material. Specifically, for example, it can be prepared by dissolving the starting material in an organic solvent, adding water intermittently or continuously to the solution, and causing a hydrolysis condensation reaction. At this time, the catalyst may be dissolved or dispersed in advance in an organic solvent, or may be dissolved or dispersed in the added water. Moreover, the temperature for performing a hydrolysis-condensation reaction is 0-100 degreeC normally.
In preparing the polysiloxane (A), (1) a mixture of each compound as a starting material may be subjected to a hydrolytic condensation reaction, or (2) the hydrolyzate of each compound and the condensate thereof. Hydrolysis condensation reaction or condensation reaction may be performed using at least one of at least one of them, a hydrolyzate of a mixture of selected compounds, and a condensate thereof.

  Although it does not specifically limit as water for performing the said hydrolysis-condensation reaction, 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 compound used as a raw material. 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, 1-pentanol, 1-methyl-1-butanol, 2-methyl-1-butanol, 3-methyl- 1-butanol, cyclopentanol, 1-hexanol, 4-methyl-2-pentanol, cyclohexanol, 1-heptanol, cycloheptanol, 1-octanol, n-nonyl alcohol, n-decyl alcohol, diethylene glycol, dipropylene Glycol, triethylene glycol, Propylene 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, 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- so-butoxyethanol, 2-hexyloxyethanol, 2- (2-ethyl) hexyloxyethanol, 2-allyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 1-methoxy-2-propanol, 1-ethoxy- Examples include 2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol and the like.

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 triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n. -Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di -N-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetyl) Acetonato) titanium, di-t-butoxy Bis (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n -Butoxy tris (acetylacetonato) titanium, mono-sec-butoxy tris (acetylacetonato) titanium, mono-t-butoxy tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium,

  Triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) Titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl aceto) Acetate) titanium, di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t- Butoxy bis (ethylacetate Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris Titanium chelate compounds such as (ethyl acetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

  Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonate) zirconium,

  Triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) Zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl aceto) Acetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl) Cetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy Tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, Tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum, etc. 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.

Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and titanium chelate compounds and organic acids are particularly preferable.
These catalysts may be used alone or in combination of two or more.

  Moreover, it is preferable that the usage-amount of a catalyst is 0.001-10 mass parts with respect to a total of 100 mass parts of a raw material compound, More preferably, it is 0.01-10 mass parts.

Moreover, after performing a hydrolysis condensation reaction, it is preferable to perform the removal process of reaction by-products, such as lower alcohols, such as methanol and ethanol, for example. Thereby, since the purity of the organic solvent is increased, it is possible to obtain a composition having excellent coating properties and excellent storage stability.
The method for removing the reaction by-product is not particularly limited as long as the reaction of the hydrolyzate or its condensate does not proceed. For example, the reaction by-product has a boiling point lower than that of the organic solvent. , It can be distilled off under reduced pressure.

  Moreover, 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.

(2) Oxetanyl group-containing compound (B)
The composition for forming a silicon-containing film of the present invention contains the oxetanyl group-containing compound (B) having two or more oxetanyl groups (oxetanyl ring), so that resist penetration resistance and the bottom shape of the resulting resist pattern can be obtained. Can be improved.

The oxetanyl group-containing compound (B), Ri oxetane compound der containing two oxetanyl groups, in particular, is preferably a compound represented by the following general formula (b1).

〔一般式（ｂ１）において、Ｒ^１は２価の有機基を表す。Ｒ^２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^３を表し、Ｒ^３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。〕

[In General Formula (b1), R ¹ represents a divalent organic group. R ² represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or —OR ³ , and R ³ represents a linear or branched alkyl group having 1 to 5 carbon atoms. Represents a group. ]

Examples of the divalent organic group represented by R ¹ in the general formula (b1) include a methylene group, a substitutable alkylene group, a substitutable phenylene group, and a substitutable alkylene group.
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms of R ² in the general formula (b1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. Group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group and the like.
In addition, when R ² is —OR ³ , the linear or branched alkyl group having 1 to 5 carbon atoms of R ³ 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.
Note that two R ² may be the same or different.

  Specific examples of the oxetanyl group-containing compound (B) include isophthalic acid bis [(3-ethyl-3-oxetanyl) methyl] ester, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3 , 3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3 -Oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis 3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanyl) Methyl) Ether, and the compound represented by PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) above general formula such as ether (b1),

Trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa Kis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipenta Erythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, di Limethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, hereinafter trade names “Aron oxetane OXT-101”, “same 121” Among them, those containing two oxetanyl groups are used, such as “Same 221” (manufactured by Toagosei Co., Ltd.), “OXTP”, “OXBP”, “OXIPA” (manufactured by Ube Industries).

Among these oxetanyl group-containing compounds (B), isophthalic acid bis [(3-ethyl-3-oxetanyl) methyl] ester (“OXIPA” (manufactured by Ube Industries)), 1,4-bis [(3- Ethyl-3-oxetanylmethoxy) methyl] benzene, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether is preferred.
In addition, an oxetanyl group containing compound (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

  It is preferable that content of the said oxetanyl group containing compound (B) is 1-30 mass parts with respect to 100 mass parts of solid content of the said polysiloxane (A), More preferably, it is 1-20 mass parts, Furthermore, Preferably it is 1-10 mass parts. When this content is 1 to 30 parts by mass, the bottom shape of the resist pattern is favorable, which is preferable.

(3) Solvent (C)
Examples of the solvent (C) include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane and i-octane. Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di- Aromatic hydrocarbon solvents such as i-propyl benzene, n-amyl naphthalene, trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n -Pentanol, -Pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3 , N-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -Heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, creso Monoalcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol Polyhydric alcohol solvents such as -2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin;

  Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i- Ketone solvents such as butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, i-propyl ether, n-butyl ether, n- Hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, Tylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether , Propire Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, ether solvents such as 2-methyltetrahydrofuran;

Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec -Pentyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl acetate Ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl acetate Chill ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, N-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid Ester solvents such as diethyl; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetate Nitrogen-containing solvents such as amide, N-methylpropionamide, N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone, etc. be able to.
These solvent (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

(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 heat treatment (hereinafter also referred to as “latent thermal acid generator”) and a compound that generates an acid by an ultraviolet light irradiation treatment (hereinafter “latent”). Also referred to as a “active photoacid generator”.

The latent thermal acid generator is a compound that generates an acid by heating to 50 to 450 ° C, preferably 200 to 350 ° C.
Examples of the latent thermal acid generator include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts.
Specific examples of the sulfonium salt include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl- Alkylsulfonium salts such as 4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate; benzyl -4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl- Benzylsulfonium salts such as 3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzoin tosylate, 2-nitrobenzyl tosylate;

  Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as p-chlorobenzyl-4-hydroxypheny Methylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxy Substituted benzylsulfonium such as phenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate salt;

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3- (p- Benzylbenzothiazolium such as methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate Salt.
Furthermore, 2,4,4,6-tetrabromocyclohexadienone can also be mentioned as a thermal acid generator other than the above.

  Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate Nate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate and the like are preferably used. Examples of these commercially available products include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).

The latent photoacid generator is a compound that generates an acid upon irradiation with ultraviolet light of usually 1 to 100 mJ, preferably 10 to 50 mJ.
Examples of the photoacid generator include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium nonafluoro n-butanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, Bis (4-t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium naphthalenesulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) ) Iodonium nonafluoro n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Sulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium nonafluoro n-butanesulfonate, (hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxo (Cyclohexyl) sulfonium trifluoromethanesulfonate,

  Dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethyl Sulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1- Naphthyl-diethylsulfonium trifluoro Methanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydro Thiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoro Lomethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trif Oromethanesulfonate, 4- (1-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy- 1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,

  4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxyvinyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-1- Naphtyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethane Sulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (naphthylacetomethyl) tetrahydrothio Onium salt photoacid generators such as phenium trifluoromethanesulfonate; phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s -Halogen-containing compound photoacid generators such as triazine;

1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,3,4-naphthoquinonediazide-4-sulfonic acid ester of 2,3,4,4′-tetrabenzophenone or 1 , 2-naphthoquinonediazide-5-sulfonic acid esters and other diazo ketone compound photoacid generators; 4-trisphenacylsulfone, mesitylphenacylsulfone, sulfonic acid compound photoacid generators such as bis (phenylsulfonyl) methane Agents: benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3- Dicarbodiimide, N-hydro Examples thereof include sulfonic acid compound-based photoacid generators such as xylsuccinimide trifluoromethanesulfonate and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.
In addition, these acid generators may be used independently and may be used in combination of 2 or more type.

  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.

(4-2) 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 β-diketones may be used singly 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 solvent (C) is 100 parts by mass. is there.

(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.
The colloidal silica is a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent. Usually, the average particle size is 5 to 30 mμ, preferably 10 to 20 mμ, and the solid content concentration is 10 to 40% by mass. It is about. Examples of such colloidal silica include Nissan Chemical Industries, Ltd., methanol silica sol, isopropanol silica sol; Catalyst Chemical Industry Co., Ltd., Oscar. These colloidal silicas may be used alone or in combination of two or more.
Examples of the colloidal alumina include alumina sol 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; alumina clear sol, alumina sol 10, and 132 manufactured by Kawaken Fine Chemical Co., Ltd. These colloidal aluminas may be used alone or in combination of two or more.

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 organic polymers may be used individually by 1 type, and may be used in combination of 2 or more type.
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 surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

[2] Manufacturing method of silicon-containing film forming composition for multilayer resist process The manufacturing method of the silicon-containing film forming composition of the present invention is not particularly limited. For example, (1) the polysiloxane (A) and the above It can be obtained by mixing the oxetanyl group-containing compound (B), the solvent (C), and, if necessary, the other additive.
Moreover, in the composition for forming a silicon-containing film of the present invention, the solid content concentration of the resin is not particularly limited, but is preferably 1 to 20% by mass, more preferably 1 to 15% by mass.

[3] Silicon-containing film The silicon-containing film of the present invention has high adhesion to a resist film and other resist underlayer films, and has resistance to oxygen ashing for removing the resist developer and the resist. A resist pattern with high reproducibility can be obtained with a high content and a low penetration of the resist material. Therefore, it can be suitably used in a multilayer resist process. Further, among multilayer resist processes, it is particularly preferably used in pattern formation using a multilayer resist process in a region finer than 90 nm (ArF, ArF, F ₂ , EUV, nanoimprint in immersion exposure). it can.
This silicon-containing film can be obtained by using the above-described composition for forming a silicon-containing film of the present invention. Specifically, for example, a coating film of a composition for forming a silicon-containing film is formed by coating on the surface of a resist film or other lower layer film (antireflection film), and the coating film is heat-treated. Alternatively, when a latent photoacid generator is contained, it can be cured by ultraviolet irradiation and heat treatment to form a silicon-containing film (resist underlayer film).
As a method for applying the silicon-containing film forming composition, 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.

[4] Pattern Forming Method The pattern forming method of the present invention includes (1) a step of forming a silicon-containing film by applying a composition for forming a silicon-containing film on a substrate to be processed [hereinafter simply referred to as “step (1)”. That's it. And (2) a step of applying a resist composition on the obtained silicon-containing film to form a resist film [hereinafter referred to simply as “step (2)”]. And (3) a step of exposing the resist film by selectively irradiating the resist film by transmitting a radiation through the photomask through the photomask [hereinafter referred to simply as “step (3)”]. And (4) a step of developing the exposed resist film to form a resist pattern [hereinafter simply referred to as “step (4)”. And (5) a step of dry-etching the silicon-containing film and the substrate to be processed using the resist pattern as a mask (etching mask) [hereinafter referred to simply as “step (5)”]. ].
According to the pattern forming method of the present invention, a resist pattern can be faithfully transferred to a substrate to be processed with high reproducibility in a dry etching process.

(4-1) Step (1)
In the step (1), a silicon-containing film is formed on a substrate to be processed using the above-described composition for forming a silicon-containing film. Thereby, the substrate with a silicon-containing film in which the silicon-containing film is formed on the substrate to be processed can be obtained.

  As the substrate to be processed, for example, an insulating film such as silicon oxide, silicon nitride, silicon oxynitride, polysiloxane, etc., hereinafter all trade names are black diamond (manufactured by AMAT), silk (manufactured by Dow Chemical), LKD5109. An interlayer insulating film such as a wafer coated with a low dielectric insulating film such as [manufactured by JSR] can be used. As the substrate to be processed, a patterned substrate such as a wiring course (trench) or a plug groove (via) may be used.

In addition, a resist underlayer film (another resist underlayer film different from the silicon-containing film obtained by using the silicon-containing film forming composition for multilayer resist process of the present invention) is formed in advance on the substrate to be processed. Also good.
This resist underlayer film has a predetermined function (for example, reflection) required for further supplementing the function of the silicon-containing film and / or the resist film in the formation of the resist pattern or for obtaining the function that these do not have. It is a film provided with a prevention function, coating film flatness, and high etching resistance against a fluorine-based gas such as CF ₄ .

  The resist underlayer film can be formed using a material that is commercially available under a trade name such as “NFC HM8005” (manufactured by JSR), “NFC CT08” (manufactured by JSR), or the like.

The method for forming the resist underlayer film is not particularly limited.For example, a coating film formed by applying the above-described material for forming the resist underlayer film on a substrate to be processed by a known method such as a spin coat method, It can be formed by curing by exposure and / or heating.
Examples of the radiation used for this exposure include visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, γ-rays, molecular beams, ion beams, and the like.
Moreover, the temperature at the time of heating a coating film is although it does not specifically limit, It is preferable that it is 90-550 degreeC, More preferably, it is 90-450 degreeC, More preferably, it is 90-300 degreeC.

  The film thickness of the resist underlayer film is not particularly limited, but is preferably 100 to 20000 nm.

  Further, the above-described explanation (the explanation in “[3] Silicon-containing film”) can be applied as it is for the formation method and film thickness of the silicon-containing film in the step (1).

(4-2) Step (2)
In the step (2), a resist film is formed on the silicon-containing film obtained in the step (1) using the resist composition.
Examples of the resist composition used in this step (2) include a positive or negative chemically amplified resist composition containing a photoacid generator, and a positive type comprising an alkali-soluble resin and a quinonediazide-based photosensitizer. Suitable examples include resist compositions, negative resist compositions comprising an alkali-soluble resin and a crosslinking agent.

Moreover, the solid content concentration of the resist composition is not particularly limited, but is preferably 5 to 50% by mass, for example.
Moreover, as a resist composition, what was filtered using the filter with a hole diameter of about 0.2 micrometer can be used conveniently. In the pattern forming method of the present invention, a commercially available resist composition can be used as it is as such a resist composition.

  The method for applying the resist composition is not particularly limited, and for example, it can be applied by a conventional method such as spin coating. In addition, when apply | coating a resist composition, the quantity of the resist composition to apply | coat is adjusted so that the resist film obtained may become a predetermined film thickness.

The resist film may be formed by volatilizing a solvent (that is, a solvent contained in the resist composition) in the coating film by pre-baking the coating film formed by applying the resist composition. it can.
Although the temperature at the time of prebaking is suitably adjusted according to the kind etc. of resist composition to be used, it is preferable that it is 30-200 degreeC, More preferably, it is 50-150 degreeC.

(4-3) Step (3)
In the step (3), the resist film obtained in the step (2) is selectively irradiated with radiation through a photomask to expose the resist film.

The radiation used in this step (3) includes visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, molecular beams, ions, depending on the type of acid generator used in the resist composition. Although it is appropriately selected from a beam or the like, it is preferable to use far ultraviolet rays, and in particular, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (wavelength 157 nm), Kr ₂ excimer laser (wavelength 147 nm) ), ArKr excimer laser (wavelength 134 nm), extreme ultraviolet light (wavelength 13 nm, etc.) and the like can be mentioned as preferred examples.
The exposure method is not particularly limited, and can be performed in accordance with a conventionally known method for pattern formation.

(4-4) Step (4)
In the step (4), the resist film exposed in the step (3) is developed to form a resist pattern.

  The developer used for development can be appropriately selected according to the type of resist composition used. In the case of a positive type chemically amplified resist composition or a positive type resist composition containing an alkali-soluble resin, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n -Propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5 4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, and other alkaline aqueous solutions can be used. These alkaline aqueous solutions may be those obtained by adding an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, and a surfactant.

  Further, in the case of a negative chemically amplified resist composition and a negative resist composition containing an alkali-soluble resin, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc. Inorganic alkalis, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triethanolamine Alcohol amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and other quaternary ammonium salts, and alkaline aqueous solutions such as pyrrole and piperidine cyclic amines can be used.

  In step (4), after developing with the developer, washing and drying can form a predetermined resist pattern corresponding to the photomask.

  In this step (4), in order to improve resolution, pattern profile, developability, etc., it is preferable to perform post-bake before development (that is, after exposure in step (3)). The post-baking temperature is appropriately adjusted according to the type of resist composition used, but is preferably 50 to 200 ° C, more preferably 80 to 150 ° C.

(4-5) Step (5)
In the step (5), the silicon-containing film and the substrate to be processed are dry-etched using the resist pattern formed in the step (4) as a mask (etching mask) to form a pattern. When the substrate to be processed on which the resist underlayer film is formed is used, the resist underlayer film is also dry etched together with the silicon-containing film and the substrate to be processed.

The dry etching can be performed using a known dry etching apparatus.
The source gas during dry etching depends on the elemental composition of the film to be etched, but includes oxygen atoms such as O ₂ , CO, and CO ₂ , inert gases such as He, N ₂ , and Ar, Cl ₂ , chlorine gas such as BCl ₄ , H ₂ , NH ₄ gas, or the like can be used. These gases can be used in combination.

  In the pattern forming method of the present invention, a predetermined pattern for substrate processing can be formed by appropriately performing the steps (1) to (5) described so far.

  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] Synthesis of Polymer [Polysiloxane (A)] In each of the synthesis examples described later, a polymer was synthesized using a monomer having the following structure.
Compound (M-1); Phenyltrimethoxysilane compound (M-2); Methyltrimethoxysilane compound (M-3); Tetramethoxysilane compound (M-4); 4-Tolyltrimethoxysilane compound (M-5) ); Benzyltriethoxysilane compound (M-6); 3- (trimethoxysilyl) propyl methacrylate compound (M-7); phenethyltrimethoxysilane

尚、式中の「Ｍｅ」はメチル基を示し、「Ｅｔ」はエチル基を示し、「Ｐｈ」はフェニル基を示す。

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

Synthesis Example 1 [Polysiloxane (A-1)]
An aqueous oxalic acid solution was prepared by dissolving 0.45 g of oxalic acid in 21.6 g of water by heating. Thereafter, 0.99 g of phenyltrimethoxysilane [formula (M-1)], 3.40 g of methyltrimethoxysilane [formula (M-2)], tetramethoxysilane [formula (M-3)] 10. A cooling tube and a dropping funnel containing the prepared oxalic acid aqueous solution were set in a flask containing 7 g and 53.5 g of propylene glycol-1-ethyl ether. 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 set in an evaporator, and methanol produced by the reaction was removed to obtain 48 g of a resin solution. Let the solid content in this resin solution be polysiloxane (A-1).
The content ratio of the solid content in the obtained resin solution was 16.3% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of solid content was 1200.

In addition, the measurement of the weight average molecular weight (Mw) in a present Example was performed with 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 2 [Polysiloxane (A-2)]
An aqueous tetraammonium hydroxide solution was prepared by dissolving 3.65 g of tetramethylammonium hydroxide in 10.94 g of water by heating. Then, in a flask containing 14.59 g of the prepared tetraammonium hydroxide aqueous solution, 4.53 g of water, and 40 g of methanol, a cooling tube, 0.99 g of phenyltrimethoxysilane [formula (M-1)], methyltrimethyl A dropping funnel containing 3.40 g of methoxysilane [formula (M-2)], 10.7 g of tetramethoxysilane [formula (M-3)] and 50 g 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.
Then, 5.10 g of maleic anhydride was dissolved in 18.72 g of water and 18.72 g of methanol, and the reaction solution cooled as described above was added dropwise to 42.54 g of a maleic acid methanol solution separately prepared. Stir for 30 minutes. After adding 50 g of 4-methyl-2-pentenone, it was set in an evaporator, and the reaction solvent and methanol produced by the reaction were removed to obtain a 4-methyl-2-pentenone resin solution. After the obtained resin solution was transferred to a separatory funnel, 40 g of water was added to perform first washing with water, and 20 g of water was added to perform second washing with water. Thereafter, 50 g of propylene glycol-1-ethyl ether was added to the 4-methyl-2-pentenone resin solution transferred from the separatory funnel to the flask, and then set in an evaporator to remove 4-methyl-2-pentenone. 54 g of resin solution was obtained. Let the solid content in this resin solution be polysiloxane (A-2).

Synthesis Examples 3 to 13 [Polysiloxane (A-3) to (A-13)]
<Polysiloxane (A-3), (A-5), (A-6), (A-8), (A-10), (A-12) and (A-13)>
Polysiloxanes (A-3) and (A-5) were prepared in the same manner as in Synthesis Example 1 except that the monomers shown in Tables 1 and 2 were used in the amounts shown in Tables 1 and 2. ), (A-6), (A-8), (A-10), (A-12) and (A-13) were synthesized.
<Polysiloxane (A-4), (A-7), (A-9) and (A-11)>
Polysiloxanes (A-4) and (A-7) were prepared in the same manner as in Synthesis Example 2 except that the monomers shown in Tables 1 and 2 were used in the amounts shown in Tables 1 and 2. ), (A-9) and (A-11) were synthesized.

  In addition, the usage-amount of the monomer in the resin solution obtained in the above-mentioned synthesis examples 2-13, solid content concentration, and the weight average molecular weight (Mw) of solid content were measured similarly to the synthesis example 1, and those The results are summarized in Tables 1 and 2. Tables 1 and 2 also show the resin composition (theoretical value, unit: mol%) determined by the amount of each monomer used.

[2] Production of composition for forming silicon-containing film for multilayer resist process Polysiloxane (A) [Polymers (A-1) to (A-13)] obtained in each of the above synthesis examples, oxetanyl group-containing compound (B) [Oxetanyl group-containing compound (B-1)], solvent (C) [solvents (C-1) to (C-2)], and acid generator (D) [acid generator (D-1) )] Was used to prepare silicon-containing film-forming compositions of Examples 1 to 14 and Comparative Examples 1 and 2 as described below.

<Example 1>
As shown in Table 3, 7 parts of polysiloxane (A-1) obtained in Synthesis Example 1, 0.1 part of oxetanyl group-containing compound (B-1), 44 parts of solvent (C-1), and solvent (C-2) After dissolving in 9 parts, this solution was filtered with a filter having a pore size of 0.2 μm to obtain a composition for forming a silicon-containing layer film for multilayer resist process of Example 1.
The details of the oxetanyl group-containing compound (B) and the solvent (C) in Table 3 are as follows.
(B-1): Isophthalic acid bis [(3-ethyl-3-oxetanyl) methyl] ester (see below for structure)

(C-1): Propylene glycol-1-propyl ether (C-2): Propylene glycol-1-ethyl ether

<Examples 2-14 and Comparative Examples 1-2>
Except having used each component in the ratio shown in Table 3, the composition for silicon-containing layer film formation for multilayer resist processes of Examples 2-14 and Comparative Examples 1-2 was obtained in the same manner as Example 1.
The details of the acid generator (D) in Table 3 are as follows.
(D-1): Diphenyliodonium trifluoromethanesulfonate

[3] Evaluation of silicon-containing film-forming compositions (Examples 1 to 14 and Comparative Examples 1 and 2) Each of the silicon-containing film formations of Examples 1 to 14 and Comparative Examples 1 and 2 obtained as described above The composition was subjected to the following various evaluations. The results are shown in Table 4.

(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 = T ₀ ).
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.
Then, the difference (T−T ₀ ) between the initial film thickness T ₀ and the post-storage film thickness T is obtained, and the ratio [(T−T ₀ ) / T ₀ ] of the difference with respect to the average film thickness T ₀ is obtained. The film thickness change rate was calculated, and a case where the value was 5% or less was evaluated as “◯”, and a 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 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 “S306C” (manufactured by Nikon Corporation), the substrate was irradiated at 32 mJ / cm ² and then heated at 115 ° C. for 60 seconds. Subsequently, the resist film was developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds to form an 80 nm line and space resist pattern.
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) Reproducibility of resist pattern A resist pattern formed by the same method as in (2) above is observed with an SEM, and no resist film remains in the area irradiated with the laser. The case where the AND space pattern was faithfully reproduced was evaluated as “◯”, and the case where it was not faithfully reproduced was evaluated as “X”.

(4) Infiltration resistance Each silicon-containing layer film-forming composition was applied on a silicon wafer by a spin coat method, and baked at 200 ° C. for 60 seconds to form a silicon-containing layer film having a film thickness of 45 nm. Then, a resist (manufactured by JSR, “AIM5056JN”) is applied on the silicon-containing film (resist underlayer film), dried at 100 ° C. for 1 minute, and the thickness of the resulting resist is measured by a film thickness meter (Dainippon Screen Co., Ltd.). , And trade name “VM2010”). Next, ArF irradiation was performed through a non-patterned quartz mask. Then, after baking for 90 second at 115 degreeC, it developed for 1 minute with 2.38% tetramethylammonium hydroxide aqueous solution. The film thickness of the resist after development was measured with the film thickness meter.
Then, the difference between the resist film thickness before exposure and the resist film thickness after exposure / development is calculated as the permeation resistance, and when the value is 10 mm or less, “◯”, when it exceeds 10 mm, “× ".

(5) Bottom shape of resist pattern An antireflection film (manufactured by JSR, “NFC CT08”) was applied on a silicon wafer and dried on a hot plate at 190 ° C. for 1 minute to form an antireflection film having a thickness of 300 nm. . Next, each silicon-containing layer film-forming composition was applied by spin coating, baked at 200 ° C. for 60 seconds, and further baked at 300 ° C. for 60 seconds to form a silicon-containing layer film having a thickness of 45 nm. . Thereafter, a resist (manufactured by JSR, “AIM5056JN”) was applied on the silicon-containing film (resist underlayer film) and dried at 100 ° C. for 1 minute. Next, ArF irradiation was performed through a quartz mask. Then, after baking for 90 seconds at 115 ° C., development was performed with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute to obtain a 75 nm line-and-space resist pattern.
Then, the bottom shape of the resist pattern was visually evaluated using a SEM (manufactured by Hitachi High-Tech Fielding, trade name “S-4800”) at a magnification of 150,000 times. The evaluation criteria are as follows.
○: When skirting is not observed and has a rectangular resist pattern ×: When skirting is observed and does not have a rectangular resist pattern

(6) Resistance to developer The composition for forming a silicon-containing film is 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.
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”.

(7) Mask properties (oxygen ashing resistance)
A silicon-containing film is formed by applying a silicon-containing film-forming composition on the surface of a silicon wafer using a spin coater under the conditions of a rotation speed of 2000 rpm and 20 seconds, and then drying on a hot plate at 250 ° C. for 60 seconds. 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 film thickness of the silicon-containing film before the treatment and the film thickness of the silicon-containing film after the treatment 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”.

  As is clear from Table 4, it was found that the silicon-containing film forming compositions of Examples 1 to 14 were excellent in storage stability. In addition, these compositions are excellent in adhesion to a resist film, reproducibility of a resist pattern, resistance to a developing solution, and masking property (etching resistance) against oxygen ashing during resist removal, and have a high Si content. It was found that a silicon-containing film having a small amount of material penetration can be formed, and a resist pattern excellent in a bottom shape without skirting or the like can be stably formed.

Claims (8)

In a multilayer resist process, when forming a resist pattern on a substrate, a composition for forming a silicon-containing film for a multilayer resist process for forming a lower layer film serving as a base thereof,
(A) a polysiloxane having a silanol group;
(B) an oxetanyl group-containing compound having two or more oxetanyl groups;
(C) an organic solvent,
A composition for forming a silicon-containing film for a multilayer resist process, wherein the oxetanyl group-containing compound is a bisoxetane compound. 2. The composition for forming a silicon-containing film for a multilayer resist process according to claim 1, wherein the (B) oxetanyl group-containing compound is a compound represented by the following formula (b1).

[In General Formula (b1), R ¹ represents a divalent organic group. R ² represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or —OR ³ , and R ³ represents a linear or branched alkyl group having 1 to 5 carbon atoms. Represents a group. ]   The composition for forming a silicon-containing film for a multilayer resist process according to claim 1 or 2, wherein the (A) polysiloxane contains a structural unit (a1) derived from tetraalkoxysilane. The composition for forming a silicon-containing film for a multilayer resist process according to claim 3, wherein the (A) polysiloxane further contains an organosilane-derived structural unit (a2) represented by the following general formula (1).

[In General Formula (1), R ⁴ represents a monovalent organic group. R ⁵ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, or —OR ⁶ , and R ⁶ represents a linear or branched alkyl group having 1 to 5 carbon atoms. Represents a group. n is an integer of 0-2. ] The composition for forming a silicon-containing film for a multilayer resist process according to claim 3 or 4, wherein the (A) polysiloxane further contains an organosilane-derived structural unit (a3) represented by the following general formula (2). object.

[In General Formula (2), R ⁷ represents a monovalent organic group. R ⁸ represents a linear or branched alkyl group having 1 to 4 carbon atoms. n is an integer of 1-4. ]   Furthermore, the composition for silicon-containing film formation for multilayer resist processes of any one of Claim 1 thru | or 5 containing an acid generator.   A silicon-containing film obtained by using the composition for forming a silicon-containing film for a multilayer resist process according to claim 1. (1) forming a silicon-containing film by applying the silicon-containing film forming composition for a multilayer resist process according to any one of claims 1 to 6 on a substrate to be processed;
(2) A step of applying a resist composition on the obtained silicon-containing film to form a resist film;
(3) The step of exposing the resist film by selectively irradiating radiation by allowing the obtained resist film to pass through a photomask;
(4) developing the exposed resist film to form a resist pattern;
(5) A pattern forming method comprising: forming a pattern by dry etching the silicon-containing film and the substrate to be processed using the resist pattern as a mask.