JP2011213921A - Composition for forming silicon-containing film, silicon-containing film, and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a silicon-containing film excellent in storage stability, capable of forming a silicon-containing film excellent in adhesion to a resist film, and capable of stably forming a resist pattern excellent in a bottom shape without tailing or the like It is to provide a forming composition.
A composition for forming a silicon-containing film comprising (A1) polysiloxane, (B) a compound having a specific structure, and (C) an organic solvent is provided.
[Selection figure] None

Description

  The present invention relates to a silicon-containing film forming composition, a silicon-containing film, and a pattern forming method. More specifically, the present invention relates to a silicon-containing film forming composition, a silicon-containing film, and a pattern forming method for forming a lower layer film as a base when a resist pattern is formed 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 rectangular resist pattern without tailing, etc., excellent adhesion to the resist, excellent etching selectivity in the resist film / resist lower layer film, It is required to have excellent storage stability.

  Generally, as a catalyst used for the synthesis of polysiloxane contained in a silicon-containing film forming composition, an acid catalyst or a base catalyst is used, and among them, an acid catalyst that requires a small number of steps is preferably used. As the acid catalyst, hydrochloric acid, oxalic acid, maleic acid and the like are common (see Patent Documents 1 to 4).

JP 2000-356854 A JP 2002-40668 A JP 2009-30006 A JP 2007-226170 A

  However, when oxalic acid or maleic acid is used, there is a problem that curing at the time of forming the silicon-containing film is delayed, the bottom shape of the resist pattern is deteriorated or pattern collapse occurs, and when hydrochloric acid is used, There is a problem that storage stability deteriorates.

  An object of the present invention is to provide a silicon-containing film that has excellent storage stability and excellent adhesion to a resist film, and can stably form a resist pattern that has an excellent bottom shape without skirting or the like. An object is to provide a composition for forming a silicon-containing film.

The present invention is as follows.
[1] (A1) polysiloxane (hereinafter also referred to as “polysiloxane (A1)”),
(B) containing a compound represented by the following general formula (1) (hereinafter also referred to as “compound (B)”) and (C) an organic solvent (hereinafter also referred to as “solvent (C)”). A silicon-containing film-forming composition (hereinafter also referred to as “composition I”).

[In General Formula (1), R ¹ represents a fluorine-substituted alkyl group having 1 to 6 carbon atoms, and R represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. ]

[2] (A2) Hydrolyzing and condensing a silane compound in the presence of the compound represented by the general formula (1) (wherein R is a hydrogen atom and this compound is also referred to as “compound (1)”) A silicon-containing film-forming composition (hereinafter referred to as “Composition II”), which comprises polysiloxane (hereinafter also referred to as “polysiloxane (A1)”) obtained by the above-described process, and a solvent (C). Say).
[3] The composition for forming a silicon-containing film according to [1] or [2], wherein the polysiloxane has a polystyrene-equivalent weight average molecular weight by gel permeation column chromatography of 500 to 15000.
[4] The polysiloxane is selected from tetraalkoxysilane (hereinafter also referred to as “compound (a1)”) and a compound represented by the following general formula (2) (hereinafter also referred to as “compound (a2)”). The composition for forming a silicon-containing film according to [1] to [3], which has a structure obtained by hydrolytic condensation of a silane compound containing at least one kind.

[In General Formula (2), R ² represents a fluorine atom, an alkylcarbonyloxy group, or an optionally substituted monovalent hydrocarbon group, X represents a chlorine atom, a bromine atom or OR (where R is 1) A valent organic group). ]

[5] (1) A step of forming a silicon-containing film by applying the silicon-containing film forming composition according to any one of [1] to [4] 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 of the present invention is excellent in storage stability and can form a silicon-containing film having excellent adhesion to a resist film. Furthermore, it is possible to stably form a rectangular resist pattern without skirting. 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 The silicon-containing film-forming composition I of the present invention contains polysiloxane (A1), a mixture with the compound (B), and a solvent (C).
The composition II for forming a silicon-containing film of the present invention contains a polysiloxane (A2) obtained by hydrolytic condensation of a silane compound in the presence of the compound (1), and a solvent (C). And
Polysiloxane (A1) is usually the same compound as polysiloxane (A2). Accordingly, in this specification, the polysiloxane (A1) and the polysiloxane (A2) may be collectively referred to as “polysiloxane (A)”.

(1) Polysiloxane (A)
The polysiloxane (A) in the composition for forming a silicon-containing film of the present invention is usually obtained by hydrolytic condensation of a hydrolyzable silane compound in the presence of the compound (1). The hydrolyzable silane compound preferably contains at least one selected from the compound (a1) and the compound (a2).

Examples of the compound (a1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. , Tetraphenoxysilane, tetrachlorosilane and the like.
Of these, tetramethoxysilane and tetraethoxysilane are preferred.
In addition, a compound (a1) may be used independently and may be used in combination of 2 or more type.

In the general formula (2) representing the compound (a2), R ² is a fluorine atom, an alkylcarbonyloxy group, or an optionally substituted monovalent hydrocarbon group.
Examples of the alkylcarbonyloxy group in R ² include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butylcarbonyloxy group, a vinylcarbonyloxy group, and an allylcarbonyloxy group.
The monovalent hydrocarbon group which may be substituted in R ² is preferably an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and isopropyl. Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group or other linear or branched hydrocarbon group; phenyl group, naphthyl group, biphenyl group, methylphenyl group , Hydrocarbon groups having an aromatic ring such as ethylphenyl group; alicyclic hydrocarbons such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, tricyclodecyl group, tetracyclododecyl group, adamantyl group, etc. Groups and the like. In addition, one or two or more hydrogen atoms in these hydrocarbon groups may be substituted, and examples of the substituent include a halogen atom, an alkoxy group, an epoxy group, a glycidoxy group, a trimethylsilyl group, and a tris (trimethylsilyl) silyl group. Is mentioned.

X in General formula (2) is a chlorine atom, a bromine atom, or OR (however, R shows a monovalent organic group).
Examples of the monovalent organic group for R when X is OR include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group. Among these, an alkyl group and an aryl group are preferable.
The alkyl group is preferably a linear and / or branched alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec. -Butyl group, tert-butyl group, n-pentyl group and the like. In addition, one or two or more hydrogen atoms in these alkyl groups may be substituted with a fluorine atom or the like.
Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. Of these, a phenyl group is preferred.
Examples of the alkenyl group include a vinyl group, a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group.

  Specific examples of the compound (a2) represented by the general formula (2) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxy. Silane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri- n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, n-propyltri Toxisilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, n-propyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec- Butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, isopropyltrichlorosilane, n-butyltrimethoxysilane, n-butyltriethoxysilane N-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltri Phenoxysilane, n-butyltrichlorosilane,

  sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, sec-butyltrichlorosilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butylto-n-propoxysilane, tert-butyltriiso Propoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert-butoxysilane, tert-butyltrif Nokishishiran, tert- butyl trichlorosilane, and the like.

Phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltrimethoxysilane, 4- (n-propyl) phenyltrimethoxysilane, 4- (iso-propyl) phenyltrimethoxysilane, 4- (n- Butyl) phenyltrimethoxysilane, 4- (2-methylpropyl) phenyltrimethoxysilane, 4- (1-methylpropyl) phenyltrimethoxysilane, 4- (tert-butyl) phenyltrimethoxysilane, 4-methoxyphenyltri Methoxysilane, 4-phenoxyphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-dimethylaminophenyltrimethoxysilane, 4-acetylaminophenyltrimethoxysilane, 3 Methylphenyltrimethoxysilane, 3-ethylphenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane, 3-phenoxyphenyltrimethoxysilane, 3-hydroxyphenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, 3-dimethylamino Phenyltrimethoxysilane, 3-acetylaminophenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-ethylphenyltrimethoxysilane, 2-methoxyphenyltrimethoxysilane, 2-phenoxyphenyltrimethoxysilane, 2-hydroxyphenyl Trimethoxysilane, 2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane, 2-acetylaminophenyltrimethoxysilane, 2,4, -Trimethylphenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane, 4-ethylbenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane, 4-phenoxybenzyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 4-amino Examples include benzyltrimethoxysilane, 4-dimethylaminobenzyltrimethoxysilane, and 4-acetylaminobenzyltrimethoxysilane.

Among these, from the viewpoint of reactivity and ease of handling, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane,
Phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltrimethoxysilane, 4- (n-propyl) phenyltrimethoxysilane, 4- (iso-propyl) phenyltrimethoxysilane, 4- (n- Butyl) phenyltrimethoxysilane, 4- (2-methylpropyl) phenyltrimethoxysilane, 4- (1-methylpropyl) phenyltrimethoxysilane, 4- (tert-butyl) phenyltrimethoxysilane, 4-methoxyphenyltri Methoxysilane, 4-methylbenzyltrimethoxysilane and the like are preferable.

Specific examples of hydrolyzable silane compounds other than the compounds (a1) and (a2) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-glycidoxy-5-trimethoxysilyl. Bicyclo [2,2,1] heptene, 2-glycidoxy-5-triethoxysilylbicyclo [2,2,1] heptene, 2-glycidoxy-6-trimethoxysilylbicyclo [2,2,1] heptene, 2- Glycidoxy-6-triethoxysilylbicyclo [2,2,1] heptene, 2,3-epoxy-5-trimethoxysilylbicyclo [2,2,1] heptene, 2,3-epoxy-5-triethoxysilylbicyclo [2,2,1] heptene, 2,3-epoxy-6-trimethoxysilylbicyclo [2,2,1] heptene, 2, -Epoxy-6-triethoxysilylbicyclo [2,2,1] heptene, 2,3-epoxy-5- (2-trimethoxysilylethyl) bicyclo [2,2,1] heptene, 2,3-epoxy- 5- (2-triethoxysilylethyl) bicyclo [2,2,1] heptene, 2,3-epoxy-6- (2-trimethoxysilylethyl) bicyclo [2,2,1] heptene, 2,3- Epoxy-6- (2-triethoxysilylethyl) bicyclo [2,2,1] heptene, 2,2'-bisglycidoxymethyl-5-trimethoxysilylbicyclo [2,2,1] heptene, 2, 2'-bisglycidoxymethyl-5-triethoxysilylbicyclo [2,2,1] heptene, 2,2'-bisglycidoxymethyl-6-trimethoxysilylbicyclo [2,2,1] he 2,2'-bisglycidoxymethyl-6-triethoxysilylbicyclo [2,2,1] heptene, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane

Tris (trimethylsilyl) silylethyltrimethoxysilane, tris (trimethylsilyl) silylethyltriethoxysilane, 2-tris (trimethylsilyl) -5-trimethoxysilylbicyclo [2,2,1] heptene, 2-tris (trimethylsilyl) -5 -Triethoxysilylbicyclo [2,2,1] heptene, 2-tris (trimethylsilyl) -6-trimethoxysilylbicyclo [2,2,1] heptene, 2-tris (trimethylsilyl) -6-triethoxysilylbicyclo [ 2,2,1] heptene, (2-trimethoxysilyl) ethylpentamethyldisilane, (2-triethoxysilyl) ethylpentamethyldisilane, 1- (2-trimethoxysilyl) ethylheptamethyltrisilane, 1- ( 2-Trimethoxysilyl) ethyl Tamethyltrisilane, 1- (2-triethoxysilyl) ethylheptamethyltrisilane, 1- (2-trimethoxysilyl) ethylnonamethyltetrasilane, 1- (2-triethoxysilyl) ethylnonamethyltetrasilane, Trimethoxysilylundecamethylcyclohexasilane, ethyltrimethoxysilylnonamethylcyclopentasilane, ethyltriethoxysilylnonamethylcyclopentasilane, trimethoxysilylundecamethylcyclohexasilane, triethoxysilylundecamethylcyclohexasilane, Tristrimethylsilyl (2-ethyltrimethoxysilyl) dimethylsilylsilane,
And tristrimethylsilyl (2-ethyltrimethoxysilyl) dimethylsilylsilane.

Among these, from the viewpoint of reactivity and ease of handling, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, tris (trimethylsilyl) silylethyltrimethoxysilane, and tris (trimethylsilyl) silylethyltriethoxysilane are preferred. In preparing the silicon-containing polymer (A), A compound (a1) may be used independently and may be used in combination of 2 or more type.

In preparing the silicon-containing polymer (A), other hydrolyzable silane compounds may be used in combination with the compounds (a1) and (a2).
As another hydrolyzable silane compound, for example, a compound represented by the following general formula (3) (hereinafter also referred to as “compound (a3)”) can be used.

_{^{R 3 x (X) 3-}} x Si- (R 5) z -Si (X) 3-y R 4 y (3)
[In General Formula (3), R ³ represents a monovalent organic group. If R ³ there are a plurality, plural of R ³ may be the same or may be different. R ⁴ represents a monovalent organic group. If R ⁴ there are a plurality to the plurality of R ⁴ may be the same or different. R ⁵ represents an oxygen atom, a phenylene group, or a group represented by — (CH ₂ ) _n — (wherein n is an integer of 1 to 6). X represents a halogen atom or OR (where R represents a monovalent organic group). When there are a plurality of Xs, the plurality of Xs may be the same or different. x shows the number of 0-2. y shows the number of 0-2. z represents 0 or 1. ]

In the general formula (3) representing the compound (a3), R ³ and R ⁴ are each a monovalent organic group, and examples thereof include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group. For these functional groups, the examples of monovalent organic groups represented by X in the general formula (2) representing the compound (a2) and the description thereof can be applied as they are.
Moreover, in General formula (3), X is a chlorine atom, a bromine atom, or OR (however, R shows monovalent organic group). As for X, the illustration of X in the general formula (2) and the description thereof can be applied as they are.

  In the general formula (3), examples of the compound when z = 0 include hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, , 1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2- Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-penta Methoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2 − Tramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2, , 2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, , 1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2- Diphenyldisilane,

  1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2,2-trimethyl Disilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1,2,2 -Triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1 1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dipheno 1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1, 2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane and the like.

  Among these, hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1 , 1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetra Methyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane and the like are preferable.

  In the general formula (3), the compound in the case where z = 1 is bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri- iso-propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) Ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane, 1,2-bis (tri-iso-propoxysilyl) ethane, 1,2-bis ( Tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2-bis (tri-tert-butyl) Xylyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-iso-propoxymethylsilyl) -1- (tri-iso-propoxysilyl) methane, 1- (di-n-butoxymethylsilyl) -1 -(Tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- ( Tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethyl) Silyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-iso-propoxymethylsilyl) -2- (Tri-iso-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- (tri -Sec-butoxysilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (tri-tert-butoxysilyl) ethane,

  Bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-iso-propoxymethylsilyl) methane, bis (di-n-butoxymethylsilyl) ) Methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) Ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-iso-propoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane, 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethyl) Silyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri -Iso-propoxysilyl) benzene, 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-tert-butoxysilyl) ) Benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1,3-bis (tri- iso-propoxysilyl) benzene, 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene Zen, 1,3-bis (tri-tert-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n) -Propoxysilyl) benzene, 1,4-bis (tri-iso-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene 1,4-bis (tri-tert-butoxysilyl) benzene and the like.

Among these, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethyl) Silyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- ( Diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis ( Diethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (trie Xylsilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) Benzene and the like are preferred.
In preparing the silicon-containing polymer (A), the compound (a3) may be used alone or in combination of two or more.

The content ratio of the structural unit derived from the compound (a1) in the silicon-containing polymer (A) is preferably when the total of all the structural units contained in the silicon-containing polymer (A) is 100 mol%. Is from 50 to 100 mol%, more preferably from 60 to 97 mol%, still more preferably from 70 to 95 mol%. When this content ratio is 50 to 99 mol%, the balance between the process margin (such as the depth of focus) and the film physical properties (such as the low dielectric constant) of the cured film is good.
Further, the content ratio of the structural unit derived from the compound (a2) is preferably 0 to 50 mol% when the total of all the structural units contained in the silicon-containing polymer (A) is 100 mol%. More preferably, it is 3-40 mol%, More preferably, it is 5-30 mol%. When the content ratio is 0 to 50 mol%, the balance between the process margin during the curing process and the film physical properties of the cured film becomes good.
In the case where the silicon-containing polymer (A) includes a structural unit derived from the compound (a3), the content ratio is 100 mol% of the total of all the structural units included in the silicon-containing polymer (A). In this case, it is preferably 20 mol% or less, more preferably 1 to 15 mol%, and still more preferably 5 to 10 mol%.

  Moreover, the weight average molecular weight (Mw) of polystyrene conversion by the gel permeation chromatography (GPC) of the said silicon-containing polymer (A) is 500-15,000, Preferably it is 700-10000, More preferably, it is 1000- 5000. When this Mw is 500 to 15,000, the resulting composition is preferable because the coating property is good.

Moreover, the content rate of the carbon atom in the said silicon containing polymer (A) is not specifically limited, It can select suitably according to the reaction type of the composition of this invention, and the intended purpose. For example, it is preferable that it is 8-40 atomic%, More preferably, it is 8-20 atomic%. When this content is less than 8 atomic%, when a silica-based film is formed using the radiation-sensitive resin composition for immersion exposure containing the silicon polymer (A), a film having a sufficiently low relative dielectric constant is obtained. Is difficult. On the other hand, when it exceeds 40 atomic%, film shrinkage (pattern shrinkage) after the curing treatment is large, and it becomes difficult to obtain a desired pattern.
Incidentally, the carbon atom content (atomic%) of the silicon-containing polymer (A) is determined so that the hydrolyzable group of the component (hydrolyzable silane compound) used for the synthesis of the silicon-containing polymer (A) is completely hydrolyzed. It is determined from the elemental composition when it is decomposed to form a silanol group, and the generated silanol group is completely condensed to form a siloxane bond.
Carbon atom content (atomic%) = (number of carbon atoms in organic silica sol) / (total number of atoms in organic silica sol) × 100

The silicon-containing polymer (A) is a hydrolyzable silane compound, that is, the compounds (a1) to (a3) as a starting material, the starting material is dissolved in an organic solvent, and water is intermittently added to the solution. Alternatively, it can be produced by continuously adding it to cause a hydrolytic condensation reaction. At this time, a catalyst may be used. This catalyst may be previously dissolved or dispersed in an organic solvent, or may be dissolved or dispersed in added water. Moreover, the temperature for performing a hydrolysis-condensation reaction is 0 degreeC-100 degreeC normally.
In the case of producing the silicon-containing polymer (A), the mixture of the compounds (a1), (a2) and (a3) may be subjected to a hydrolytic condensation reaction, or the hydrolyzate of each compound and the condensate thereof. A hydrolytic condensation reaction or a condensation reaction may be carried out 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 0.25 to 3 mol, preferably 0.3 to 1 mol per mol of an alkoxyl group of the hydrolyzable silane compound used (for example, X in the general formulas (1) and (2)). Used in an amount of 2.5 moles. 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, and examples thereof include propylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether.

As the catalyst, the compound (1) represented by the general formula (1) is used.
Specific examples of the compound (1) include trifluoroacetic acid and pentafluoropropionic acid, and trifluoroacetic acid is particularly preferable.
In addition, you may use another catalyst together with a compound (1), As this other catalyst, a metal chelate compound, an organic acid, an inorganic acid, an organic base, an inorganic base etc. are mentioned, for example.

Examples of the metal chelate compound include a titanium chelate compound, a zirconium chelate compound, and an aluminum chelate compound. Specifically, compounds described in JP 2000-356854 A 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 inorganic acids are preferred. The said catalyst may be used independently and may be used in combination of 2 or more type.
The usage-amount of a compound (1) is 0.001-50 mass parts normally with respect to 100 mass parts of said hydrolysable silane compounds, Preferably it is 0.01-40 mass parts.

Further, after the hydrolysis condensation reaction, it is preferable to perform a removal treatment of reaction by-products such as lower alcohols such as methanol and ethanol. Thereby, the composition which has the outstanding applicability | paintability with respect to a board | substrate, and also has favorable storage stability can be obtained.
The method for removing the reaction by-product is not particularly limited as long as the reaction of the hydrolyzate and / or its condensate does not proceed. For example, the boiling point of the reaction by-product is the boiling point of the organic solvent. If it is lower, it can be distilled off under reduced pressure.

(2) Compound (B)
The compound (B) is usually obtained by hydrolytic condensation of a hydrolyzable silane compound in the presence of the compound (1), and is a component derived from the compound (1).
R ¹ in the general formula (1) represents a fluorine-substituted alkyl group having 1 to 6 carbon atoms, and examples thereof include a monofluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group. Among these, a C1-C4 perfluoroalkyl group is preferable, and a trifluoromethyl group is particularly preferable.
R in the general formula represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. As the substituent for these alkyl groups, a halogen atom, an alkoxyl group and the like can be mentioned, and an alkoxyl group is particularly preferred.
Specific examples of the compound (B) include trifluoroacetic acid, pentafluoropropionic acid, and alkyl esters thereof, and trifluoroacetic acid alkyl esters such as trifluoroacetic acid and trifluoroacetic acid methyl ester are particularly preferable.

(3) Solvent (C)
Examples of the solvent (C) in the silicon-containing film-forming composition of the present invention include n-pentane, iso-pentane, n-hexane, i-hexane, n-heptane, iso-heptane, 2, 2, 4 -Aliphatic hydrocarbon solvents such as trimethylpentane, n-octane, iso-octane, cyclohexane, methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, iso-propyl benzene, diethylbenzene , Aromatic hydrocarbon solvents such as iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene, trimethylbenzene; methanol, ethanol, n-propanol, iso-propanol, n-butanol, so-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpen Tanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, 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-trimethylcyclohexane Monoalcohol solvents such as sanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, cresol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl- 2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, etc. A monohydric alcohol solvent;

  Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso- Ketone solvents such as butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, iso-propyl ether, n-butyl ether, n- Hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2 Ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2- (2-ethylbutoxy) ethanol, 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, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl 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, iso-propyl acetate, n-butyl acetate, iso-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 acetate Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, propionic acid Ethyl, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, Ester solvents such as diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Nitrogen-containing solvents such as methylacetamide, N-methylpropionamide, N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone, etc. Can be mentioned.
Among these solvents (C), ether solvents and ester solvents are preferable. Furthermore, among ether solvents and ester solvents, glycol solvents are particularly preferred because of their excellent film formability. Specific examples of the glycol solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like. It is done.
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- Alkyl sulfonium 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-tert-butylphenyl) iodonium trifluoromethanesulfonate, Bis (4-tert-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium naphthalenesulfonate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, bis (4-tert-butylphenyl) ) Iodonium nonafluoro n-butanesulfonate, triphenylsulfonium trifluoro Tansulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium nonafluoro n-butanesulfonate, (hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, Dicyclohexyl (2-oxocyclohexyl) 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-iso-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxyvinyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-tert-butoxycarbonyloxy-1- Naphtyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethane Sulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (naphthylacetomethyl) tetra Onium salt photoacid generators such as drothiophenium trifluoromethanesulfonate; phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) Halogen-containing compound photoacid generators such as -s-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 nm, preferably 10 to 20 nm, 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] 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, the polysiloxane component (A), the solvent (C), If necessary, it can be obtained by mixing the other additives.
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 a high adhesiveness with a resist film and other resist underlayer films, and a resist pattern having an excellent bottom shape without skirting or the like can be obtained. 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.

Moreover, a resist underlayer film (another resist underlayer film different from the silicon-containing film obtained by using the silicon-containing film-forming composition of the present invention) may be formed in advance on the substrate to be processed.
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, and ion beams.
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 ₃ 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.
In addition, determination of the content rate of solid content in a present Example and the measurement of a weight average molecular weight (Mw) and NMR were performed with the following method.
<Determination of solid content>
By baking 0.5 g of the siloxane resin solution at 250 ° C. for 30 minutes, the weight of the solid content relative to 0.5 g of the resin solution was measured, and the solid content of the siloxane resin solution was determined.
<Measurement of weight average molecular weight (Mw)>
Tosoh GPC columns (trade name “G2000HXL”, 2 trade names “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. < ¹⁹ F-NMR analysis>
Measurement was performed using a model “JNM-Delta400” manufactured by JEOL Ltd.

[1] Synthesis of Polymer [Polysiloxane (A)] In each of the synthesis examples described below, a polymer was synthesized using monomers of the following compounds (M-1) to (M-6). . The structure of each monomer is shown in the following formula.
Compound (M-1); Tetramethoxysilane compound (M-2); Methyltrimethoxysilane compound (M-3); Phenyltrimethoxysilane compound (M-4); 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane compound (M-5); 3-glycidoxypropyltrimethoxysilane compound (M-6); Tris (trimethylsilyl) silylethyltrimethoxysilane

Synthesis Example 1 [Polysiloxane (A-1)]
An aqueous trifluoroacetic acid solution was prepared by dissolving 4.85 g of trifluoroacetic acid in 6.12 g of water. Then, tetramethoxysilane [formula (M-1)] 12.24 g, methyltrimethoxysilane [formula (M-2)] 3.91 g, phenyltrimethoxysilane [formula (M-3)] 1. A cooling tube and a dropping funnel containing the prepared aqueous trifluoroacetic acid solution were set in a flask containing 14 g and 71.74 g of propylene glycol-1-ethyl ether. Subsequently, after heating at 60 degreeC with an oil bath, the aqueous trifluoroacetic acid 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 and then set in an evaporator, and methanol produced by the reaction was removed to obtain 45.4 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 18.0% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of solid content was 1900. Moreover, when the measurement sample which added deuterated chloroform (0.4 ml) to the obtained resin solution (0.6 ml) was prepared and ¹⁹ F-NMR was measured, the peak was observed at -76.5 ppm. From this result, it was confirmed that the polysiloxane (A-1) contains a compound derived from trifluoroacetic acid.

Synthesis Example 2 [Polysiloxane (A-2)]
An aqueous trifluoroacetic acid solution was prepared by dissolving 3.43 g of trifluoroacetic acid in 4.33 g of water. Thereafter, 8.66 g of tetramethoxysilane [formula (M-1)], 0.81 g of phenyltrimethoxysilane [formula (M-3)], 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 5 Into a flask containing 0.000 [formula (M-4)] g and propylene glycol-1-ethyl ether 77.78 g, a cooling tube and a dropping funnel containing the prepared aqueous trifluoroacetic acid solution were set. Subsequently, after heating at 60 degreeC with an oil bath, the aqueous trifluoroacetic acid 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 and then set in an evaporator, and methanol produced by the reaction was removed to obtain 46.4 g of a resin solution. Let the solid content in this resin solution be polysiloxane (A-2).
The content ratio of the solid content in the obtained resin solution was 17.6% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of solid content was 2000. Moreover, when the measurement sample which added deuterated chloroform (0.4 ml) to the obtained resin solution (0.6 ml) was prepared and ¹⁹ F-NMR was measured, the peak was observed at -76.5 ppm. From this result, it was confirmed that the polysiloxane (A-3) contains a compound derived from trifluoroacetic acid.

Synthesis Example 3 [Polysiloxane (A-3)]
An aqueous trifluoroacetic acid solution was prepared by dissolving 3.50 g of trifluoroacetic acid in 4.43 g of water. Then, tetramethoxysilane [formula (M-1)] 8.85 g, phenyltrimethoxysilane [formula (M-3)] 0.82 g, 3-glycidoxypropyltrimethoxysilane [formula (M- 5)] A cooling tube and a dropping funnel containing the prepared aqueous trifluoroacetic acid solution were set in a flask containing 4.91 g and propylene glycol-1-ethyl ether 77.49 g. Subsequently, after heating at 60 degreeC with an oil bath, the aqueous trifluoroacetic acid 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 and then set in an evaporator, and methanol produced by the reaction was removed to obtain 50.2 g of a resin solution. Let the solid content in this resin solution be polysiloxane (A-3).
The content ratio of the solid content in the obtained resin solution was 16.0% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of solid content was 1800. Moreover, when the measurement sample which added deuterated chloroform (0.4 ml) to the obtained resin solution (0.6 ml) was prepared and ¹⁹ F-NMR was measured, the peak was observed at -76.5 ppm. From this result, it was confirmed that the polysiloxane (A-3) contains a compound derived from trifluoroacetic acid.

Synthesis Example 4 [Polysiloxane (A-4)]
An aqueous trifluoroacetic acid solution was prepared by dissolving 2.43 g of trifluoroacetic acid in 3.07 g of water. Thereafter, 6.13 g of tetramethoxysilane [formula (M-1)], 0.57 g of phenyltrimethoxysilane [formula (M-3)], tris (trimethylsilyl) silylethyltrimethoxysilane [formula (M- 6)] A cooling tube and a dropping funnel containing the prepared aqueous trifluoroacetic acid solution were set in a flask containing 5.70 g and 82.11 g of propylene glycol-1-ethyl ether. Subsequently, after heating at 60 degreeC with an oil bath, the aqueous trifluoroacetic acid 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 and then set in an evaporator, and methanol generated by the reaction was removed to obtain 48.5 g of a resin solution. Let the solid content in this resin solution be polysiloxane (A-4).
The content ratio of the solid content in the obtained resin solution was 17.0% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of solid content was 1700. Moreover, when the measurement sample which added deuterated chloroform (0.4 ml) to the obtained resin solution (0.6 ml) was prepared and ¹⁹ F-NMR was measured, the peak was observed at -76.5 ppm. From this result, it was confirmed that the polysiloxane (A-4) contains a compound derived from trifluoroacetic acid.

Synthesis Example 5 [Polysiloxane (A-5)]
An aqueous oxalic acid solution was prepared by dissolving 0.55 g of oxalic acid in 7.66 g of water. Then, tetramethoxysilane [formula (M-1)] 12.24 g, methyltrimethoxysilane [formula (M-2)] 3.91 g, phenyltrimethoxysilane [formula (M-3)] 1. A cooling tube and a dropping funnel containing the prepared aqueous trifluoroacetic acid solution were set in a flask containing 14 g and propylene glycol-1-ethyl ether (74.51 g). Subsequently, after heating to 60 degreeC with an oil bath, the acid aqueous 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 and then set in an evaporator, and methanol produced by the reaction was removed to obtain 49.2 g of a resin solution. Let the solid content in this resin solution be polysiloxane (A-5).
The content ratio of the solid content in the obtained resin solution was 18.0% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of solid content was 1600.

Synthesis Example 6 [Polysiloxane (A-6)]
An aqueous oxalic acid solution was prepared by dissolving 4.12 g of oxalic acid in 57.73 g of water. Then, tetramethoxysilane [formula (M-1)] 16.08 g, tetramethoxysilane [formula (M-1)] 16.08 g, methyltrimethoxysilane [formula (M-2)] 0.80 g , Phenyltrimethoxysilane [formula (M-3)] 1.16 g and propylene glycol-1-ethyl ether 20.11 g in a flask containing a condenser and the prepared trifluoroacetic acid aqueous solution Set. Subsequently, after heating to 35 degreeC with an oil bath, acid aqueous solution was dripped slowly, and it heated up at 60 degreeC after that, and was made to react for 2 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 12.2 g of a resin solution. Let the solid content in this resin solution be polysiloxane (A-6).
The content ratio of the solid content in the obtained resin solution was 14.0% as a result of measurement by a firing method. Moreover, the weight average molecular weight (Mw) of solid content was 2100.

[2] Production of composition for forming silicon-containing film Polysiloxane (A) [polysiloxane (A-1) to (A-5)] obtained in each of the above synthesis examples, and organic solvent (C) [organic Using the solvents (B-1) to (B-3)], compositions for forming silicon-containing films of Examples 1 to 9 and Comparative Examples 1 to 4 were prepared as follows.
<Example 1>
As shown in Table 2, after dissolving 11 parts of polysiloxane (A-1) obtained in Synthesis Example 1 in 74 parts of organic solvent (B-1) and 15 parts of organic solvent (B-2) The solution was filtered through a filter having a pore size of 0.2 μm to obtain the silicon-containing film forming composition of Example 1.
Details of the organic solvent (C) in Table 2 are as follows.
B-1: Propylene glycol monomethyl ether acetate B-2: Propylene glycol-1-ethyl ether <Examples 2-4 and Comparative Examples 1-2>
Except having used each component in the ratio shown in Table 2, the composition for silicon-containing film formation of Examples 2-4 and Comparative Example 1 was prepared in the same manner as Example 1.

[3] Evaluation of silicon-containing film-forming compositions (Examples 1 to 4 and Comparative Examples 1 and 2) Each of the silicon-containing film formations of Examples 1 to 4 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 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 = T ₀ ).
Further, using the composition for forming a silicon-containing film after heating at 80 ° C. for 6 hours, a silicon-containing film was formed in the same manner as described above, and the film thickness was measured. = T).
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 “ARX2014J” (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 100 nm. Further, a liquid immersion upper layer film material “NFC TCX091-7” (manufactured by JSR Corporation) was applied on the formed resist film and dried at 90 ° C. for 60 seconds. At this time, the film thickness of the liquid immersion upper layer film was controlled to 30 nm. Thereafter, using an ArF excimer laser irradiation apparatus “S610C” (manufactured by Nikon Corporation), irradiation was performed under the condition of 16 mJ / cm ² , and then the substrate was heated at 115 ° C. for 60 seconds. Next, the resist film was developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds to form a 50 nm line and space resist pattern.
The resist pattern formed on the substrate as described above is observed with a scanning electron microscope (SEM). When the resist pattern is not developed and peeled off, “◯” is given. “×”.
(3) Resist pattern reproducibility 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. In an & space pattern, the case where the bottom of the resist pattern did not have a bottom was evaluated as “◯”, and the case where there was a bottom was evaluated as “×”.

  As is clear from Table 3, the silicon-containing film forming compositions of Examples 1 to 4 were found to be excellent in storage stability. Further, it was found that these compositions can form a silicon-containing film having excellent adhesion to a resist film, and can stably form a resist pattern having an excellent bottom shape without skirting or the like. .

Claims (5)

(A1) polysiloxane,
(B) A silicon-containing film-forming composition comprising a compound represented by the following general formula (1) and (C) an organic solvent.

[In General Formula (1), R ¹ represents a fluorine-substituted alkyl group having 1 to 6 carbon atoms, and R represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. ] (A2) a polysiloxane obtained by hydrolytic condensation of a silane compound in the presence of the compound represented by the general formula (1) (where R is a hydrogen atom), and (C) an organic solvent. A composition for forming a silicon-containing film, comprising: The composition for forming a silicon-containing film according to claim 1 or 2, wherein the polysiloxane has a polystyrene-reduced weight average molecular weight of 500 to 15000 as determined by gel permeation column chromatography. 4. The silicon according to claim 1, wherein the polysiloxane has a structure obtained by hydrolytic condensation of a silane compound containing at least one selected from tetraalkoxysilane and a compound represented by the following general formula (2). Containing film-forming composition.

[In General Formula (2), R ² represents a fluorine atom, an alkylcarbonyloxy group, or an optionally substituted monovalent hydrocarbon group, X represents a chlorine atom, a bromine atom or OR (where R is 1) A valent organic group). ] (1) A step of applying the silicon-containing film forming composition according to any one of claims 1 to 4 on a substrate to be processed to form a silicon-containing film;
(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.