JP2008158002A - Composition for resist underlayer film, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a resist underlayer film superior in preservation stability by having excellent adhesion with a resist film, improving reproduction of a resist pattern, and forming the resist underlayer film having resistance to alkali solution used for development or the like and oxygen ashing during removing a resist. <P>SOLUTION: The composition for the resist underlayer film contains: a silane compound denoted by [A-1]: R<SP>1</SP><SB>b</SB>R<SP>2</SP><SB>c</SB>Si(OR<SP>3</SP>)<SB>4-a</SB>; a silane compound denoted by [B]: R<SP>4</SP><SB>e</SB>R<SP>5</SP><SB>f</SB>Si(OR<SP>6</SP>)<SB>4-d</SB>; and polysiloxane (hydrolyzate and/or condensate or the like of a mixture of the silane compounds of [A-1], [B] and [C]) derived from a silane compound denoted by [C]:R<SP>7</SP><SB>g</SB>Si(OR<SP>8</SP>)<SB>4-g</SB>. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resist underlayer film composition and a method for producing the same, and more specifically, when forming a resist pattern on a substrate, a resist underlayer film composition for forming an underlayer film serving as an underlayer and the production thereof. Regarding the method.

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 lower layer film for processing 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 oxide film or interlayer insulating film is formed using the lower layer film for processing as a mask. A dry etching process 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, a solution It is required to have excellent storage stability.
However, a processing underlayer film proposed so far, for example, a processing underlayer film composed of a composition containing a hydrolyzate of a specific silane compound and / or a condensate thereof (see Patent Documents 1 and 2), However, it was not a material satisfying all of the above characteristics such as poor adhesion of the resist pattern.

JP 2000-356854 A JP-A-3-45510

  An object of the present invention is to form a resist underlayer film that has excellent adhesion to a resist film, improves the reproducibility of a resist pattern, and is resistant to an alkaline solution used for development and oxygen ashing during resist removal. Another object of the present invention is to provide a resist underlayer film composition that can be used and has excellent storage stability.

  The present inventors have intensively studied to solve the above problems. As a result, the resist underlayer film made of a composition containing a polysiloxane derived from a specific silane compound is excellent on the resist underlayer film by increasing the crosslink density after curing and reducing the amount of residual silanol. It has been found that a resist pattern shape can be obtained and the adhesion to the resist is improved, and the present invention has been completed.

That is, the means for solving the above problems are as follows.
[1] A resist underlayer film composition comprising polysiloxane derived from the following silane compounds [A-1], [B] and [C].
[A-1] Silane compound represented by the following general formula (1-1) [B] Silane compound represented by the following general formula (2) [C] Silane compound represented by the following general formula (3) R ¹ _b R ² _c Si (OR ³ ) _4-a (1-1)
R ⁴ _e R ⁵ _f Si (OR ⁶ ) _4-d (2)
R ⁷ _g Si (OR ⁸ ) _4-g (3)
[In General Formula (1-1), R ¹ independently represents an epoxy group, an oxetanyl group, or an alkylhydroxyl group, and R ² independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted group having 1 to 6 carbon atoms. R ³ independently represents a monovalent organic group, a represents an integer of 1 to 3, b represents an integer of 1 to 3, c represents an integer of 0 to 2, and a = b + c. R ¹ is a group other than the OR ³ group. ]
[In General Formula (2), R ⁴ independently represents a group having an aromatic ring, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ⁵ independently represents a hydrogen atom, a halogen atom, or a carbon number of 1-6. A substituted or unsubstituted alkyl group, R ⁶ independently represents a monovalent organic group, d represents an integer of 1 to 3, e represents an integer of 1 to 3, and f represents 0 to 2 Indicates an integer and d = e + f. R ⁴ is a group other than the R ¹ , R ⁵ and OR ⁶ groups. ]
[In General Formula (3), R ⁷ independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁸ independently represents a monovalent organic group, g Represents an integer of 1 to 3. R ⁷ is a group other than R ¹ , R ^4, and OR ⁸ groups. ]

[2] The polysiloxane is [A-1] a silane compound represented by the general formula (1-1), [B] a silane compound represented by the general formula (2), and [C] the above The composition for a resist underlayer film according to the above [1], which is a hydrolyzate and / or a condensate of a mixture of the silane compound represented by the general formula (3).

[3] The polysiloxane is
[A-1] Hydrolyzate and / or condensate of a mixture of the silane compound represented by the general formula (1-1) and the silane compound represented by [B] the general formula (2) ,as well as,
[C] The resist underlayer film composition according to the above [1], which is a resin containing a hydrolyzate of the silane compound represented by the general formula (3) and / or a condensate thereof.

[4] A resist underlayer film composition comprising a polysiloxane derived from a silane compound of the following [A-2], [B] and [D].
[A-2] Silane compound represented by the following general formula (1-2) [B] Silane compound represented by the following general formula (2) [D] Silane compound represented by the following general formula (4) R ⁹ _b R ¹⁰ _c Si (OR ¹¹ ) _4-a (1-2)
R ⁴ _e R ⁵ _f Si (OR ⁶ ) _4-d (2)
Si (OR ¹² ) ₄ (4)
[In General Formula (1-2), R ⁹ independently represents an oxetanyl group or an alkyl hydroxyl group, and R ¹⁰ independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. R ¹¹ independently represents a monovalent organic group, a represents an integer of 1 to 3, b represents an integer of 1 to 3, c represents an integer of 0 to 2, and a = b + c is there. R ⁹ is a group other than the OR ¹¹ group. ]
[In General Formula (2), R ⁴ independently represents a group having an aromatic ring, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ⁵ independently represents a hydrogen atom, a halogen atom, or a carbon number of 1-6. A substituted or unsubstituted alkyl group, R ⁶ independently represents a monovalent organic group, d represents an integer of 1 to 3, e represents an integer of 1 to 3, and f represents 0 to 2 Indicates an integer and d = e + f. R ⁴ is a group other than the R ¹ , R ⁵ and OR ⁶ groups. ]
[In General Formula (4), R ¹² independently represents a monovalent organic group. ]

[5] The polysiloxane is [A-2] a silane compound represented by the general formula (1-2), [B] a silane compound represented by the general formula (2), and [D] the above The composition for a resist underlayer film according to the above [4], which is a hydrolyzate of a mixture of the silane compound represented by the general formula (4) and / or a condensate thereof.

[6] Hydrolysis of a mixture of [A-2] the silane compound represented by the general formula (1-2) and [B] the silane compound represented by the general formula (2). Decomposition products and / or condensates thereof, and
[D] The resist underlayer film composition according to the above [4], which is a resin containing a hydrolyzate of the silane compound represented by the general formula (4) and / or a condensate thereof.

[7] The resist underlayer film composition according to any one of [1] to [6], further containing at least one selected from the following [a] to [g].
[A] Hydrolyzate of compound represented by general formula (2) and / or condensate thereof [b] Hydrolyzate of compound represented by general formula (3) and / or condensate thereof [c] ] Hydrolyzate of compound represented by general formula (4) and / or condensate thereof [d] Silane compound represented by general formula (2) and silane represented by general formula (3) Hydrolyzate and / or condensate of mixture thereof [e] Hydrolysis of mixture of silane compound represented by general formula (2) and silane compound represented by general formula (4) Decomposition product and / or condensate thereof [f] Hydrolyzate and / or condensation product of mixture of silane compound represented by general formula (3) and silane compound represented by general formula (4) [G] Silane compound represented by the general formula (2) and the general formula (3) In the silane compound represented hydrolyzate of the general formula (4) silane represented by the Mixtures of a compound and / or its condensate

[8] The resist underlayer film according to any one of [1] to [7], further comprising a vinyl polymer containing at least one of an epoxy group, an oxetanyl group, an alkyl hydroxyl group, a carboxyl group, and an ester bond. Composition.

[9] The resist underlayer film according to any one of [1] to [8], further comprising a polyfunctional crosslinking agent containing at least one of an epoxy group, an oxetanyl group, an alkylhydroxyl group, and a carboxyl group. Composition.

[10] The resist underlayer film composition according to any one of [1] to [9], further including an acid generating compound that generates an acid upon irradiation with ultraviolet light and / or heating.

[11] A method for producing the resist underlayer film composition according to any one of [1] to [10] above, wherein a silane compound used in the resist underlayer film composition is contained in an organic solvent, A method for producing a resist underlayer film composition comprising a step of hydrolysis and / or condensation in the presence of water and a catalyst.

  The resist underlayer film composition of the present invention has excellent adhesion to the resist film, improves the reproducibility of the resist pattern, and has resistance to an alkaline solution used for development and oxygen ashing during resist removal. A resist underlayer film can be formed, and the storage stability is excellent. Furthermore, the baking temperature for obtaining a required cured film can be set lower than before.

Hereinafter, embodiments of the present invention will be described in detail.
[1] Composition for resist underlayer film (1)
Composition for resist underlayer film of the present invention [hereinafter also referred to as “composition (I)”. ] Is a polysiloxane derived from the following silane compounds [A-1], [B] and [C] [hereinafter also referred to as “polysiloxane (I)”. ] Is contained.
[A-1] Silane compound represented by general formula (1-1); R ¹ _b R ² _c Si (OR ³ ) _4-a [hereinafter also referred to as “silane compound (A1)”. ]
[B] Silane compound represented by general formula (2); R ⁴ _e R ⁵ _f Si (OR ⁶ ) _4-d [hereinafter also referred to as “silane compound (B)”. ]
[C] Silane compound represented by general formula (3); R ⁷ _g Si (OR ⁸ ) _4-g [hereinafter also referred to as “silane compound (C)”. ]

<Silane compound (A1)>
R ¹ in the general formula (1-1) is an epoxy group, an oxetanyl group, or an alkylhydroxyl group. In addition, all or some of the hydrogen atoms in the cyclic structure part of the epoxy group and the oxetanyl group may be substituted with a methyl group, an ethyl group, a phenyl group, or the like.
Specific alkyl hydroxyl groups include, for example, hydroxymethyl group, hydroxyethyl group, hydroxybutyl group, dihydroxyethyl group, dihydroxypropyl group and the like.
Among these, a hydroxymethyl group, a hydroxyethyl group, a dihydroxyethyl group, and a dihydroxypropyl group are preferable. This R ¹ is a group other than the OR ³ group described later. When a plurality of R ¹ are present, all R ¹ may be the same, or all or part of them may be different.

R ² in the general formula (1-1) is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an astatine atom. Examples of the substituted or unsubstituted alkyl group having 1 to 6 carbon atoms 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. , N-pentyl group, iso-pentyl group, neopentyl group, n-hexyl group, vinyl group, allyl group and the like. Among these, a methyl group, an ethyl group, a vinyl group, and an allyl group are preferable. In the case where R ² there are a plurality, each R ² may be the same or may be different.

R ³ in the general formula (1-1) is a monovalent organic group. Specific examples of the monovalent organic group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a γ-aminopropyl group, Examples thereof include an alkyl group which may have a substituent such as γ-glycidoxypropyl group and γ-trifluoropropyl group. Among these, a methyl group and an ethyl group are preferable. In addition, when two or more R < ³ > exists, all R < ³ > may be the same, and all or one part may differ.

  Moreover, in the said General formula (1-1), a is an integer of 1-3, b is an integer of 1-3, c is an integer of 0-2, Especially, a is an integer of 1-2, b is 1 It is preferable that it is an integer of -2, c is an integer of 1-2. Note that a, b, and c satisfy the relationship of a = b + c.

  Specific examples of the silane compound (A1) represented by the general formula (1-1) include 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 2- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane silane, bis (2- (3,4-epoxycyclohexyl) ethyl) diethoxysilane, bis (2- (3,4-epoxycyclohexyl) ethyl) dimethoxysilane silane, 5,6 epoxy-hexyltri Ethoxysilane, 3-glycidoxypropyldimethylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3-ethyl (triethoxysilylpropoxymethyl) oxetane etc. It is below.

  Among these, from the viewpoint of polymerization reactivity, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane silane, bis (2- (3,4-epoxycyclohexyl) ethyl) diethoxysilane, bis (2- (3,4-epoxycyclohexyl) ethyl) dimethoxysilane silane, 5,6 epoxy-hexyltriethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3 -Ethyl (triethoxysilylpropoxymethyl) oxetane is preferred.

<Silane compound (B)>
R ⁴ in the general formula (2) is a group having an aromatic ring, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group.
Specific examples of the group having an aromatic ring include groups including a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an acenaphthyl group, and an anthryl group.
Moreover, as a cyanoalkyl group, a cyanoethyl group, a cyanopropyl group, etc. are mentioned, for example.
Furthermore, examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butylcarbonyloxy group, a vinylcarbonyloxy group, and an allylcarbonyloxy group.
Among these, a methylcarbonyloxy group, an ethylcarbonyloxy group, a vinylcarbonyloxy group, and an allylcarbonyloxy group are preferable. The R ⁴ is a group other than the R ¹ and R ⁵ and OR ⁶ groups described later. When a plurality of R ⁴ are present, all R ⁴ may be the same, or all or part of them may be different.

R ⁵ in the general formula (2) is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the description of R ² in the general formula (1-1) is as it is. Can be applied. When a plurality of R ⁵ are present, each R ⁵ may be the same or different.

R ⁶ in the general formula (2) is a monovalent organic group, and the description of R ³ in the general formula (1-1) can be applied as it is. When a plurality of R ⁶ are present, all R ⁶ may be the same, or all or part of them may be different.

  Moreover, in the said General formula (2), d is an integer of 1-3, e is an integer of 1-3, f is an integer of 0-2, Especially, d is an integer of 1-2, e is 1-2. It is preferable that f is an integer of 1-2. Note that d, e, and f satisfy the relationship d = e + f.

As a specific silane compound (B) represented by the general formula (2), for example,
Acetoxyethyltrimethoxysilane, acetoxyethylmethyldimethoxysilane,
Acetoxyethyldimethylmethoxysilane, acetoxyethyltriethoxysilane,
Acetoxyethylmethyldiethoxysilane, acetoxyethyldimethylethoxysilane, acetoxymethyltrimethoxysilane, acetoxymethylmethyldimethoxysilane,
Acetoxymethyldimethylmethoxysilane, acetoxymethyltriethoxysilane,
Acetoxymethylmethyldiethoxysilane, acetoxymethyldimethylethoxysilane, acetoxypropyltrimethoxysilane, acetoxypropylmethyldimethoxysilane, acetoxypropyldimethylmethoxysilane, acetoxypropyltriethoxysilane, acetoxypropylmethyldiethoxysilane,
Acetoxypropyldimethylethoxysilane,
N-3- (acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane,
(3-acryloxypropyl) trimethoxysilane,
(3-acryloxypropyl) methyldimethoxysilane,
(3-acryloxypropyl) dimethylmethoxysilane,
(3-acryloxypropyl) triethoxysilane,
(3-acryloxypropyl) methylethoxysilane,
(3-acryloxypropyl) dimethylethoxysilane,
3- (N-allylamino) propyltrimethoxysilane,
3- (N-allylamino) propylmethyldimethoxysilane,
3- (N-allylamino) propyldimethylmethoxysilane,
3- (N-allylamino) propyltriethoxysilane,
3- (N-allylamino) propylmethyldiethoxysilane,
3- (N-allylamino) propyldimethylethoxysilane,
Allyl (chloropropyl) dimethoxysilane,
Allyl (chloropropyl) diethoxysilane,
Allyl [(3-cyclohexenyl-2-ethyl)] dimethoxysilane,
Allyl [(3-cyclohexenyl-2-ethyl)] diethoxysilane,
Allyldimethoxysilane, allyldiethoxysilane,
Allylmethyldimethoxysilane, allylmethyldiethoxysilane,
Allyldimethylmethoxysilane, allyldimethylethoxysilane,
Allylhexyldimethoxysilane, allylhexyldiethoxysilane,
Allyloxytrimethoxysilane, 2-allyloxyethylthiomethyltrimethoxysilane, O-allyloxy (polyethyleneoxy) trimethoxysilane,
Allylphenyldimethoxylane, allylphenyldiethoxysilane,
(Aminoethylaminomethyl) phenethyltrimethoxysilane,
(Aminoethylaminomethyl) phenethyltriethoxysilane,
3- (m-aminophenoxy) propyltrimethoxysilane,
3- (m-aminophenoxy) propyltriethoxysilane,
m-aminophenyltrimethoxysilane, m-aminophenyltriethoxysilane,
p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane,
Benzoyloxypropyltrimethoxysilane,
Benzoylpropyltriethoxysilane,
Benzyltrimethoxysilane, benzyltriethoxysilane,
Benzylmethyldimethoxysilane, benzylmethyldiethoxysilane,
Benzyloxytrimethoxysilane, benzyloxytriethoxysilane,
5- (bicycloheptenyl) trimethoxysilane,
5- (bicycloheptenyl) triethoxysilane,
5- (bicycloheptenyl) methyldimethoxysilane,
5- (bicycloheptenyl) methyldiethoxysilane,
5- (bicycloheptenyl) dimethylmethoxysilane,
5- (bicycloheptenyl) dimethylethoxysilane,
Bis (cyanopropyl) dimethoxysilane, bis (cyanopropyl) diethoxysilane, bis (N-methylbenzamido) ethoxymethylsilane,
Bis (trimethoxysilyl) acetylene, bis (triethoxysilyl) acenaphthylene, bis (triethoxysilyl) ethylene, bis (trimethoxysilyl) ethylene,
Bis (triethoxysilyl) 1,7-octadiene,
Bis [3- (triethoxysilyl) propyl] urea,
Bis (trimethoxysilylethyl) benzene,
Bis (triethoxysilylethyl) benzene,
Bromophenyltrimethoxysilane,
Butenyltrimethoxysilane, butenyltriethoxysilane,
Butenylmethyldimethoxysilane, butenylmethyldiethoxysilane,
2- (chloromethyl) allyltrimethoxysilane,
2- (chloromethyl) allyltriethoxysilane,
(Chloromethylphenyl) ethyltrimethoxysilane,
(Chloromethylphenyl) ethyltriethoxysilane,
(Chloromethylphenyl) ethylmethyldimethoxysilane,
(Chloromethylphenyl) ethylmethyldiethoxysilane,
Chloromethylphenyltrimethoxysilane, chloromethylphenyltriethoxysilane, chloromethylphenylmethyldimethoxysilane,
Chloromethylphenylmethyldiethoxysilane,
Chlorophenyltriethoxysilane, chlorophenyltrimethoxysilane,
2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane,
2- (4-chlorosulfonylphenyl) ethyltriethoxysilane,
3-cyanobutyltrimethoxysilane, 3-cyanobutyltriethoxysilane,
(3-cyanobutyl) methyldimethoxysilane, (3-cyanobutyl) methyldiethoxylane,
2-cyanoethylmethyldimethoxysilane, 2-cyanoethylmethyldiethoxysilane,
2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane,
3-cyanopropylmethyldimethoxysilane, 3-cyanopropylmethyldiethoxysilane,
3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane,
3-cyanopropylphenyldimethoxysilane,
3-cyanopropylphenyldiethoxysilane,
11-cyanoundecyltrimethoxysilane,
[2- (3-cyclohexenyl) ethyl] dimethylmethoxysilane,
[2- (3-cyclohexenyl) ethyl] dimethylethoxysilane,
[2- (3-cyclohexenyl) ethyl] methyldimethoxysilane,
[2- (3-cyclohexenyl) ethyl] methyldiethoxysilane,
[2- (3-cyclohexenyl) ethyl] trimethoxysilane,
[2- (3-cyclohexenyl) ethyl] triethoxysilane,
Cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane,
Cyclooctenyltrimethoxysilane, cyclooctenyltriethoxysilane,
(3-cyclopentadienylpropyl) triethoxysilane,
Diallyldimethoxysilane, diallyldiethoxysilane,
Dibenzyloxydimethoxysilane, dibenzyloxydiethoxysilane,
Dichlorophenyltrimethoxysilane, dichlorophenyltriethoxysilane,
Dimethoxydivinylsilane, diethoxydimethylsilane,
1,1-diethoxy-1-silacyclopent-3-ene,
Diethyl phosphate ethyltriethoxysilane,
Dimesityldimethoxysilane, dimesityldiethoxysilane,
Dimethoxyphenylphenyl-2-piperidinoethoxysilane,
Dimethylethoxyethynylsilane,
3- (2,4-dinitrophenylamino) propyltriethoxysilane,
Diphenyldimethoxysilane, diphenyldiethoxysilane,
Diphenylmethylethoxysilane,
Diphenylphosphinoethyldimethylethoxysilane,
Diphenylphosphinoethyltriethoxysilane,
Di (p-tolyl) diethoxysilane,
1,3-divinyltetraethoxydisiloxane,
(Furfuryloxymethyl) triethoxysilane,
5-hexenyltrimethoxysilane, 5-hexenyltriethoxysilane,
2-hydroxy-4- (3-triethoxysilylpropoxy) diphenyl ketone,
3-isocyanatopropyldimethylmethoxysilane,
3-isocyanatopropyldimethylethoxysilane,
3-isocyanatopropyltrimethoxysilane,
3-isocyanatopropyltriethoxysilane,
O- (methacryloxyethyl) -N- (triethoxysilylpropyl) urethane,
N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane,
(Methacryloxymethyl) dimethylmethoxysilane,
(Methacryloxymethyl) dimethylethoxysilane,
Methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyldimethoxysilane, methacryloxymethyldiethoxysilane,
(Methacryloxypropyl) dimethylmethoxysilane,
(Methacryloxypropyl) dimethylethoxysilane,
Methacryloxypropyltrimethoxysilane,
Methacryloxypropyltriethoxysilane,
Methacryloxypropylmethyldimethoxysilane,
Methacryloxypropylmethyldiethoxysilane,
Methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane,
Methoxyphenylmethyldimethoxysilane, methoxyphenylmethyldiethoxysilane, methylphenethylmethyldimethoxysilane, methylphenethylmethyldiethoxysilane, 1,7-octadienyltriethoxysilane,
Octenyltrimethoxysilane, octenyltriethoxysilane,
7-octenyldimethylmethoxysilane, 7-octenyldimethylethoxysilane,
Phenethyltrimethoxysilane, phenethyltriethoxysilane,
Phenethyldimethylmethoxysilane, phenethylmethylethoxysilane,
3-phenoxypropyltrimethoxysilane,
3-phenoxypropyltriethoxysilane,
m-phenoxyphenyldimethylmethoxysilane,
m-phenoxyphenyldimethylethoxysilane,
N-phenylaminopropyltrimethoxysilane,
N-phenylaminopropyltriethoxysilane,
Phenyldimethoxysilane, phenyldiethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane,
Phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,
Phenyldimethylmethoxysilane, phenyldimethylethoxylane,
N-1-phenylethyl-N′-triethoxysilylpropylurea,
(3-phenylpropyl) dimethylmethoxysilane,
(3-phenylpropyl) dimethylethoxysilane,
(3-phenylpropyl) methyldimethoxysilane,
(3-phenylpropyl) methyldiethoxysilane,
O- (propargyloxy) -N- (triethoxysilylpropyl) urethane,
Styrylethyltrimethoxysilane, styrylethyltriethoxysilane,
3-thiocyanate propyltrimethoxysilane,
3-thiocyanate propyltriethoxysilane,
p-tolyltrimethoxysilane, p-tolyltriethoxysilane,
Tribenzylmethoxylane, tribenzylethoxysilane,
2- (trimethoxysilyl) ethylpyridine, 2- (triethoxysilyl) ethylpyridine,
3- (triethoxysilylpropyl) -t-butylcarbamate,
3- (triethoxysilylpropyl) -ethyl carbamate,
3- (triethoxysilylpropyl) -methylcarbamate,
N- [3- (triethoxysilyl) propyl] -2-carbomethoxyaziridine,
N- (triethoxysilylpropyl) dansilamide,
N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole,
2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane,
N- (3-triethoxysilylpropyl) gluconamide,
N- (3-triethoxysilylpropyl) -4-hydroxybutyramide,
N-triethoxysilylpropyl-O-menth carbamate,
3- (triethoxysilylpropyl) -p-nitrobenzamide,
N- (triethoxysilylpropyl) -O-polyethylene oxide urethane,
N-triethoxysilylpropylquinine urethane,
3- (triethoxysilyl) propyl succinic anhydride,
N- [5- (trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam,
2- (trimethoxysilylethyl) pyridine, 2- (triethoxysilylethyl) pyridine,
N- (3-trimethoxysilylpropyl) pyrrole,
N- (3-triethoxysilylpropyl) pyrrole,
Tris (3-trimethoxysilylpropyl) isocyanurate,
Tris (3-triethoxysilylpropyl) isocyanurate,
Ureapropyltriethoxysilane, ureapropyltriethoxysilane,
O- (vinyloxyethyl) -N- (triethoxysilylpropyl) urethane,
Examples thereof include vinyl diphenylethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

Among these, from the viewpoint of improving adhesion with a resist film, storage stability, trialkoxysilane having a cyano group such as cyanoethyltriethoxysilane, trialkoxysilane having a phenyl group such as phenyltriethoxysilane, N An alkoxysilane having an amide group such as-(3-triethoxysilylpropyl) -4-hydroxycarbamate is preferable.
In addition, from the viewpoint of an antireflection function that absorbs reflected light from the base, phenyltriethoxysilane, 3-phenoxypropyltrimethoxysilane, phenethyltriethoxysilane, benzoylpropyltriethoxysilane, benzyltriethoxysilane, bis (triethoxy Trialkoxysilanes having a phenyl group such as (silylethyl) benzene and methoxyphenyltriethoxysilane are preferred.

<Silane compound (C)>
R ⁷ in the general formula (3) is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the description of R ² in the general formula (1-1) is applied as it is. can do. R ⁷ is a group other than R ¹ , R ⁴ , and an OR ⁸ group described later. When a plurality of R ⁷ are present, all R ⁷ may be the same, or all or part of them may be different.

R ⁸ in the general formula (3) is a monovalent organic group, and the description of R ³ in the general formula (1-1) can be applied as it is. In the case where R ⁸ there are a plurality, it may be all the R ⁸ are same or different for all or part.
Moreover, in the said General formula (3), g is an integer of 1-3, and it is preferable that it is an integer of 1-2.

  Specific examples of the silane compound (C) represented by the general formula (3) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, and tri-n-. Butoxysilane, tri-sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane, fluorotri- n-butoxysilane, fluorotri-sec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-pro Xysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxy Silane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxy Silane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-but Sisilane, n-propyltriphenoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, iso-propyltri-n-propoxysilane, iso-propyltri-iso-propoxysilane, iso-propyltri-n- Butoxysilane, iso-propyltri-sec-butoxysilane, iso-propyltri-tert-butoxysilane, iso-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, sec-butyltrimethoxysilane, sec-butyl-iso-triethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri- iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, tert-butyltri Methoxysila Tert-butyltriethoxysilane, tert-butyltri-n-propoxysilane, tert-butyltri-iso-propoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert- Butoxysilane, tert-butyltriphenoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoro Propyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propo Sisilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxy Silane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-tert-butoxysilane, diethyldiphenoxysilane,

  Di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di -N-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-propyldimethoxysilane Di-iso-propyl-diethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxysilane, di -Iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-i o-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso-propoxy Silane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di-tert-butoxysilane, di-n-butyl-di-phenoxy Silane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane, di-sec-butyl -Di-n-butoxysilane, di-sec-butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane Di-sec-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso -Propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di -Phenoxysilane,

  Diγ-aminopropyldimethoxysilane, diγ-aminopropyldiethoxysilane, diγ-glycidoxypropyldimethoxysilane, diγ-glycidoxypropyldiethoxysilane, diγ-trifluoropropyldimethoxysilane, diγ- Trifluoropropyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-iso-propoxysilane, trimethylmono-n-butoxysilane, trimethylmono-sec-butoxysilane , Trimethylmono-tert-butoxysilane, trimethylmonophenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmono-n-propoxysilane, triethylmono-iso-pro Xysilane, triethylmono-n-butoxysilane, triethylmono-sec-butoxysilane, triethylmono-tert-butoxysilane, triethylmonophenoxysilane, tri-n-propylmono-n-propylmethoxysilane, tri-n-propylmono -N-ethoxysilane, tri-n-propylmono-n-propoxysilane, tri-n-propylmono-iso-propoxysilane, tri-n-propylmono-n-butoxysilane, tri-n-propylmono-tert -Butoxysilane, tri-n-propylmono-sec-butoxysilane, tri-n-propylmonophenoxysilane, tri-iso-propylmonomethoxysilane, tri-iso-propylmono-n-propoxysilane, tri-iso- Propyl mono-iso- Roxyxysilane, tri-iso-propylmono-n-butoxysilane, tri-iso-propylmono-sec-butoxysilane, tri-iso-propylmono-tert-butoxysilane, tri-iso-propylmonophenoxysilane N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, and the like. .

  Among these, from the viewpoint of improving the storage stability of the composition, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane iso-propyltriethoxy Silane, iso-propyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltrimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane are preferred. .

<Polysiloxane (I)>
The polysiloxane (I) contained in the composition (I) of the present invention is derived from the silane compound (A1), the silane compound (B), and the silane compound (C). Specifically, And polysiloxanes such as the following (I-1) to (I-5).
(I-1): Resin comprising a hydrolyzate and / or condensate of a mixture of the silane compound (A1), the silane compound (B), and the silane compound (C) (I-2); a silane compound A resin comprising a hydrolyzate of a mixture of (A1) and a silane compound (B) and / or a condensate thereof, and a hydrolyzate of the silane compound (C) and / or a condensate thereof (I-3) A resin comprising a hydrolyzate and / or condensate of a mixture of the silane compound (A1) and the silane compound (C), and a hydrolyzate and / or condensate of the silane compound (B) (I -4); comprising a hydrolyzate and / or condensate of a mixture of the silane compound (B) and the silane compound (C), and a hydrolyzate and / or condensate of the silane compound (A1). Resin (I-5); Silane compound (A 1) Hydrolyzate and / or condensate thereof, silane compound (B) hydrolyzate and / or condensate thereof, and resin comprising silane compound (C) hydrolyzate and / or condensate thereof Each of the silane compounds (A1), (B) and (C) may be used alone or in combination of two or more.

Among these polysiloxanes (I), the polysiloxane of the above (I-1) or (I-2) is preferable from the viewpoint of the uniformity of polymerization reactivity and the uniformity of the coating film.
In addition, the composition (I) of this invention may contain only 1 type of polysiloxane (I), and may contain 2 or more types.

In polysiloxane (I), the content ratio of the component derived from the silane compound (A1) is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, still more preferably 10 to 90 mol%. . Moreover, it is preferable that the content rate of the component originating in a silane compound (B) is 1-90 mol%, More preferably, it is 5-50 mol%, More preferably, it is 5-30 mol%. Furthermore, it is preferable that the content rate of the component derived from a silane compound (C) is 1-90 mol%, More preferably, it is 1-80 mol%, More preferably, it is 1-70 mol%. However, the sum total of the content rate of each component originating in a silane compound (A1), a silane compound (B), and a silane compound (C) shall be 100 mol%.
When the proportion of the component derived from each silane compound in polysiloxane (I) is within the above range, a resist underlayer film having excellent adhesion to the resist film, antireflection function of the resist underlayer film, and storage stability is formed. can do.

[2] Composition for resist underlayer film (2)
Composition for resist underlayer film of the present invention [hereinafter also referred to as “composition (II)”. ] Is a polysiloxane derived from the following silane compounds [A-2], [B] and [D] [hereinafter also referred to as “polysiloxane (II)”. ] Is contained.
[A-2] Silane compound represented by the following general formula (1-2); R ⁹ _b R ¹⁰ _c Si (OR ¹¹ ) _4-a [hereinafter also referred to as “silane compound (A2)”. ]
[B] A silane compound represented by the following general formula (2); R ⁴ _e R ⁵ _f Si (OR ⁶ ) _4-d [hereinafter also referred to as “silane compound (B)”. ]
[D] Silane compound represented by the following general formula (4); Si (OR ¹² ) ₄ [hereinafter also referred to as “silane compound (D)”. ]

<Silane compound (A2)>
R ⁹ in the general formula (1-2) is an oxetanyl group or an alkylhydroxyl group. All or some of the hydrogen atoms in the cyclic structure part of the oxetanyl group may be substituted with a methyl group, an ethyl group, a phenyl group, or the like.
Specific alkyl hydroxyl groups include, for example, hydroxymethyl group, hydroxyethyl group, hydroxybutyl group, dihydroxyethyl, dihydroxypropyl and the like.
Among these, a hydroxymethyl group, a hydroxyethyl group, dihydroxyethyl, and dihydroxypropyl are preferable. R ⁹ is a group other than the OR ¹¹ group described later. When a plurality of R ⁹ are present, all R ⁹ may be the same, or all or part of them may be different.

R ¹⁰ in the general formula (1-2) represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the general formula (1-1) of the composition (I) described above. The description of R ² in) can be applied as it is. In the case a plurality ^of R ¹⁰ s exist, each R ¹⁰ may be the same or different.

R ¹¹ in the general formula (1-2) is a monovalent organic group, and the description of R ³ in the general formula (1-1) of the composition (I) can be applied as it is. In addition, when two or more R < ¹¹ > exists, all R < ¹¹ > may be the same, and all or one part may differ.

  In the above general formula (1-2), a is an integer of 1 to 3, b is an integer of 1 to 3, c is an integer of 0 to 2, and in particular, a is an integer of 1 to 2, and b is 1. It is preferable that it is an integer of -2, c is an integer of 1-2. Note that a, b, and c satisfy the relationship of a = b + c.

  Specific examples of the silane compound (A2) represented by the general formula (1-2) include 3-ethyl (triethoxysilylpropoxymethyl) oxetane, hydroxymethyltriethoxysilane, hydroxymethyltrimethoxysilane, Hydroxyethyltriethoxysilane, hydroxyethyltrimethoxysilane, dihydroxyethyltriethoxysilane, dihydroxyethyltrimethoxysilane, dihydroxypropyltriethoxysilane, dihydroxypropyltrimethoxysilane, N- (3-triethoxysilylpropyl) gluconamide, etc. Can be mentioned.

  Among these, hydroxyethyltriethoxysilane, hydroxyethyltrimethoxysilane, dihydroxyethyltriethoxysilane, dihydroxyethyltrimethoxysilane, dihydroxypropyltriethoxysilane, dihydroxypropyltrimethoxysilane, N- (3-triethoxysilylpropyl) ) Gluconamide is preferred.

<Silane compound (B)>
As the silane compound (B) in the composition (II) of the present invention, the description of the silane compound (B) in the composition (I) can be applied as it is.

<Silane compound (D)>
R ¹² in the general formula (4) is a monovalent organic group, and the description of R ³ in the general formula (1) of the composition (I) can be applied as it is. In the case where R ¹² there are a plurality, it may be the R ¹² is all the same, may be different for all or part.

  Specific examples of the silane compound (D) represented by the general formula (4) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, and tetra-n-. Examples include butoxylan, tetra-sec-butoxysilane, tetra-tert-butoxysilane, and tetraphenoxysilane. Among these, tetramethoxysilane, tetraethoxysilane, and tetra-n-propoxysilane are preferable from the viewpoint of polymerization reactivity.

<Polysiloxane (II)>
The polysiloxane (II) contained in the composition (II) of the present invention is derived from the silane compound (A2), the silane compound (B), and the silane compound (D), and specifically, And polysiloxanes such as the following (II-1) to (II-5).
(II-1); a resin comprising a hydrolyzate and / or a condensate of a mixture of the silane compound (A2), the silane compound (B), and the silane compound (D) (II-2); a silane compound A resin comprising a hydrolyzate of a mixture of (A2) and a silane compound (B) and / or a condensate thereof, and a hydrolyzate of the silane compound (D) and / or a condensate thereof (II-3) A resin comprising a hydrolyzate and / or condensate of a mixture of the silane compound (A2) and the silane compound (D), and a hydrolyzate and / or condensate of the silane compound (B) (II) -4); consisting of a hydrolyzate and / or condensate of a mixture of the silane compound (B) and the silane compound (D), and a hydrolyzate and / or condensate of the silane compound (A2). Resin (II-5); Silane It consists of the hydrolyzate of compound (A2) and / or its condensate, the hydrolyzate of silane compound (B) and / or its condensate, and the hydrolyzate of silane compound (D) and / or its condensate. Resin The silane compounds (A2), (B), and (D) may be used alone or in combination of two or more.

Among these polysiloxanes (II), the polysiloxane of the above (II-1) or (II-2) is preferable from the viewpoint of the uniformity of polymerization reactivity and the uniformity of the coating film.
In addition, the composition (II) of this invention may contain only 1 type of polysiloxane (II), and may contain 2 or more types.

In polysiloxane (II), the content ratio of the component derived from the silane compound (A2) is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, still more preferably 10 to 90 mol%. . Moreover, it is preferable that the content rate of the component originating in a silane compound (B) is 1-90 mol%, More preferably, it is 5-50 mol%, More preferably, it is 5-30 mol%. Furthermore, it is preferable that the content rate of the component derived from a silane compound (D) is 1-90 mol%, More preferably, it is 1-80 mol%, More preferably, it is 1-70 mol%. However, the sum total of the content rate of each component originating in a silane compound (A2), a silane compound (B), and a silane compound (D) shall be 100 mol%.
When the proportion of the component derived from each silane compound in polysiloxane (II) is within the above range, a resist underlayer film excellent in adhesion to the resist film, antireflection function of the resist underlayer film, and storage stability is formed. can do.

[3] Other polysiloxanes The composition (I) and the composition (II) of the present invention contain at least one other polysiloxane selected from the following [a] to [g]. Is preferred. When such other polysiloxane is contained, it is preferable from the viewpoint of coating surface roughness.
[A] Hydrolyzate and / or condensate thereof of the compound represented by the general formula (2) [the silane compound (B)] [b] Compound represented by the general formula (3) [the silane compound (C)] hydrolyzate and / or condensate thereof [c] hydrolyzate of compound [silane compound (D)] and / or condensate thereof [d] silane Hydrolyzate of mixture of compound (B) and silane compound (C) and / or condensate thereof [e] Hydrolyzate of mixture of silane compound (B) and silane compound (D) and / or Or a condensate thereof [f] a hydrolyzate of a mixture of the silane compound (C) and the silane compound (D) and / or a condensate thereof [g] a silane compound (B), a silane compound (C), Hydrolyzate of the mixture of silane compound (D) and / or Condensates

[4] Other components (1)
<Vinyl polymer>
In addition, the composition (I) and the composition (II) of the present invention include an epoxy group, an oxetanyl group, an alkylhydroxyl group, a carboxyl group, and an ester bond in order to improve adhesion to a resist and a pattern shape. A vinyl polymer containing at least one kind may be contained. The above description can be applied to the epoxy group, oxetanyl group, and alkylhydroxyl group as they are.

  Specific examples of the vinyl polymer include a repeating unit represented by the following general formula (5-1) (hereinafter referred to as “repeating unit (5-1)”), and a general formula (5-2) below. At least one of a repeating unit (hereinafter referred to as “repeating unit (5-2)”) and a repeating unit represented by the following general formula (6) (hereinafter referred to as “repeating unit (6)”) is used. The thing etc. to contain are mentioned.

〔一般式（５−１）及び（５−２）において、Ｒ^１３は水素原子又はメチル基を示し、Ｒ^１４はメチレン基又は炭素数２〜６のアルキレン基を示し、Ｒ^１５〜Ｒ^１７は互いに独立に水素原子又は炭素数１〜４のアルキル基を示し、Ａは単結合又はメチレン基を示す。〕

[In General Formulas (5-1) and (5-2), R ¹³ represents a hydrogen atom or a methyl group, R ¹⁴ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ^{15 to} R ¹⁷ represent A hydrogen atom or a C1-C4 alkyl group is shown independently of each other, and A is a single bond or a methylene group. ]

〔一般式（６）において、Ｒ^１８は水素原子又はメチル基を示し、Ｒ^１９はメチレン基又は炭素数２〜６のアルキレン基を示す。〕

In [Formula ^{(6), R 18} represents a hydrogen atom or a methyl ^{group, R 19} represents a methylene group or an alkylene group having 2 to 6 carbon atoms. ]

Specific monomers that give the repeating units (5-1) and (5-2) include, for example, glycidyl acrylate, glycidyl methacrylate, 1-ethyl-1-methyloxetanyl acrylate, 1-ethyl-1-methyloxetanyl. Examples include methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, tetrahydrofurfuryl acrylate, and tetrahydrofurfuryl methacrylate.
In addition, when the said vinyl polymer contains both repeating unit (5-1) and (5-2), R < ¹³ > -R < ¹⁷ > and A in the said general formula (5-1) are respectively the said general formula ( It may be the same as or different from R ^{13 to} R ¹⁷ and A in 5-2).

  Specific monomers that give the repeating unit (6) include, for example, hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, phenoxymethyl hydroxyethyl acrylate, Examples include phenoxymethyl hydroxyethyl acrylate, allyloxymethyl hydroxyethyl acrylate, allyloxymethyl hydroxyethyl acrylate, acryloyl polypropylene glycol, methacryloyl polypropylene glycol, acryloyl polyethylene glycol, and methacryloyl polyethylene glycol.

Furthermore, the vinyl polymer may contain other repeating units.
Examples of the monomer that gives other repeating units include methacryloylpropyltrimethoxysilane, methacryloylpropyltrimethoxysilane, methyl acrylate, methyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, styrene, vinyl naphthalene, and the like.

These vinyl polymers may be used alone or in combination of two or more.
The method for preparing the vinyl polymer is not particularly limited. For example, it can be obtained by heating and stirring acrylic acid, hydroxyethyl methacrylate, and t-butoxystyrene in the presence of a normal radical initiator. it can.

  When the solid content of the polysiloxane is 100% by mass, the vinyl polymer content is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, and still more preferably 10 to 90% by mass. Especially preferably, it is 15-85 mass%. When the content ratio of the vinyl polymer is in the above range, it has excellent adhesion to the resist film, improves the reproducibility of the resist pattern, and against oxygen solution used for development and the like and oxygen ashing during resist removal. Thus, a resist underlayer film having resistance can be formed, and a composition for a resist underlayer film excellent in storage stability can be obtained.

<Multifunctional crosslinking agent>
In addition, the composition (I) and the composition (II) of the present invention are polyfunctional crosslinks containing at least one of an epoxy group, an oxetanyl group, an alkylhydroxyl group and a carboxyl group in order to improve curing reactivity. An agent may be contained. The above description can be applied to the epoxy group, oxetanyl group, and alkylhydroxyl group as they are.

Specific polyfunctional crosslinking agents include, for example, sorbitol polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether. Epoxy crosslinking agents such as diglycerol polyglycidyl ether, diglycidyl terephthalate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutadiene diglycidyl ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy Oxetane crosslinking agent methyl] benzene, and the like.
Among these, sorbitol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether and the like are preferable from the viewpoint of crosslinking efficiency.
In addition, these polyfunctional crosslinking agents may be used independently and may be used in mixture of 2 or more types.

  The content ratio of the polyfunctional crosslinking agent is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, and still more preferably 10 to 90% when the solid content of the polysiloxane is 100% by mass. % By mass, particularly preferably 15 to 85% by mass. When the content ratio of the polyfunctional crosslinking agent is within the above range, the adhesive property with the resist film is excellent, the reproducibility of the resist pattern is improved, and the alkali solution used for development and the oxygen ashing at the time of resist removal are used. It is possible to form a resist underlayer film having resistance to the above, and to obtain a resist underlayer film composition having excellent storage stability.

<Other cross-linking agents>
In addition, the composition (I) and the composition (II) of the present invention may contain a crosslinking agent other than the polyfunctional crosslinking agent in order to improve film curability at low temperatures. Examples of such a crosslinking agent include tetramethoxyglycoluril, tetrabutoxyglycoluril, 1,4-butanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and the like. These may be used alone or in combination of two or more.
The other crosslinking agent is used in an amount in the range of 0.01 to 50% by mass, preferably 0.1 to 30% by mass, when the solid content of the polysiloxane is 100% by mass.

<Acid generator>
The composition (I) and the composition (II) of the present invention contain a compound that generates an acid by performing an ultraviolet irradiation treatment and / or a heat treatment (hereinafter, also simply referred to as “acid generator”). Is preferred. By containing such an acid generator, an acid is generated in the resist underlayer film by exposing the resist or heating after the exposure, and an acid is generated at the interface between the resist underlayer film and the resist film. Supplied. As a result, a resist pattern excellent in resolution and reproducibility can be formed in the alkali development treatment of the resist film.
Examples of the acid generator include a compound that generates an acid by performing ultraviolet irradiation treatment (hereinafter also referred to as “latent photoacid generator”) and a compound that generates an acid by performing a heat treatment (hereinafter “latent”). Also referred to as “thermal acid generator”.
Examples of the latent photoacid generator include onium salt photoacid generators, halogen-containing compound photoacid generators, diazoketone compound photoacid generators, sulfonic acid compound photoacid generators, Examples thereof include sulfonate compound-based photoacid generators. Examples of the latent thermal acid generator include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. Among these, sulfonium salts and benzothiazolium salts are used. preferable. More specific compounds include compounds described in Patent Document 1 and the like.

<β-diketone>
Furthermore, the composition (I) and the composition (II) of the present invention may contain a β-diketone in order to improve the uniformity of the formed coating film and the storage stability. Examples of such β-diketones 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 -Hexafluoro-2,4-heptanedione and the like. These may be used alone or in combination of two or more.
The β-diketone is used in an amount in the range of 1 to 50 parts by mass, preferably 3 to 30 parts by mass with respect to 100 parts by mass in total of the β-diketone and the organic solvent.

[5] Other components (2)
The composition (I) and the composition (II) of the present invention may further contain components such as colloidal silica, colloidal alumina, an organic polymer (excluding the vinyl polymer), a surfactant and the like. Good. As the organic polymer, for example, a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylate compound, an aromatic vinyl compound, a dendrimer, polyimide, polyamic acid, polyarylene, polyamide, Examples thereof include polyquinoxaline, polyoxadiazole, and a fluorine polymer. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing interfaces. Examples include activators.

[6] Method for Producing Resist Underlayer Film Composition The method for producing a resist underlayer film composition of the present invention comprises hydrolyzing each of the above silane compounds or a mixture thereof in an organic solvent in the presence of water and a catalyst. And / or a step of condensing. More specifically, a predetermined silane compound is dissolved in an organic solvent, and water is intermittently or continuously added to this solution. 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 reaction and / or a condensation reaction is 0-100 degreeC normally.

  Although it does not specifically limit as water for performing the said hydrolysis and / or condensation, It is preferable to use ion-exchange water. Moreover, the said water is used in the quantity used as 0.25-3 mol with respect to 1 mol of alkoxyl groups of the whole silane compound used, Preferably it is 0.3-2.5 mol. By using water in an amount in the above range, the uniformity of the formed coating film is not likely to be reduced, and the storage stability of the composition is less likely to be reduced.

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, propylene glycol monopropyl ether and the like. .
As said catalyst, a metal chelate compound, an organic acid, an inorganic acid, an organic base, an inorganic base, etc. can be used.
Examples of the metal chelate compound include a titanium chelate compound, a zirconium chelate compound, and an aluminum chelate compound. Specifically, compounds described in Patent Document 1 (Japanese Patent Laid-Open No. 2000-356854) and the like can be used.

  Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, Gallic acid, butyric acid, merit acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene Examples include sulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diaza Bicyclononane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
Of these, metal chelate compounds, organic acids and inorganic acids are preferred. The said catalyst may be used independently or may be used in combination of 2 or more type. Further, the catalyst, a total of 100 parts by weight of the silane compound relative to (SiO ₂ basis), usually from 0.001 to 10 parts by weight, preferably in a range of 0.01 to 10 parts by weight.

In the present invention, after the hydrolysis and / or condensation of the silane compound, for example, it is preferable to perform a removal treatment of reaction byproducts such as lower alcohols such as methanol and ethanol. Thereby, since the purity of the organic solvent is increased, it is possible to obtain a resist underlayer film composition having excellent coating properties and good storage stability.
The method for removing the reaction by-product is not particularly limited as long as the reaction of the hydrolyzate of the silane compound and / or its condensate does not proceed. For example, the boiling point of the reaction by-product is the above organic solvent. Can be distilled off under reduced pressure.

Each resist underlayer film composition of the present invention can be obtained by mixing the polysiloxane obtained as described above with other additives as required.
Moreover, it is preferable that each composition [composition (I) and (II)] is 1-20 mass% in solid content concentration, respectively, especially 1-15 mass%. In order to adjust the solid content concentration, the organic solvent may be further added after removing the reaction by-product.

[7] Method for forming resist underlayer film Each resist underlayer film composition of the present invention forms a coating film of this composition by, for example, applying it to the surface of an antireflection film. A resist underlayer film can be formed by heat treatment or, when a latent photoacid generator is contained, by performing ultraviolet irradiation treatment and heat treatment.
As a method for applying the resist underlayer 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.
The resist underlayer film formed as described above has high adhesion to the resist film, has resistance to oxygen ashing for removing the resist developer and the resist, and provides a highly reproducible resist pattern. It is done.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[1] (A) Polysiloxane
<Synthesis Example 1 (A-1)>
An aqueous maleic acid solution was prepared by heating and dissolving 5.4 g of maleic anhydride in 100.8 g of water. Next, 4.35 g of (3-glycidoxypropyl) trimethoxysilane, 2.40 g of phenyltrimethoxysilane, 12.5 g of methyltrimethoxysilane and 530.5 g of ethyl lactate were placed in the flask. A cooling tube and a dropping funnel containing a maleic acid aqueous solution prepared in advance were set in the flask, heated at 100 ° C. in an oil bath, and then the maleic acid aqueous solution was slowly added dropwise at 100 ° C. for 4 hours. Reacted. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol and excess water generated during the reaction were removed to obtain a reaction product.
The solid content in the obtained reaction product was 16.1% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 2500. Hereinafter, this reaction product is referred to as (A-1).

<Synthesis Example 2 (A-2)>
A monomer solution was prepared by preparing 7.09 g of (3-glycidoxypropyl) trimethoxysilane, 1.98 g of phenyltrimethoxysilane, 10.70 g of methyltriethoxysilane, and 40 g of ethanol. Next, 7.29 g of 25% TMAH aqueous solution, 40 g of ethanol, and 20 g of water are put into a flask, a dropping funnel containing a monomer tube prepared in advance is set with a condenser tube, and heated to 60 ° C. in an oil bath. The monomer solution was slowly added dropwise and reacted at 60 ° C. for 3 hours. After completion of the reaction, the reaction mixture was neutralized with an aqueous maleic acid solution, and the methanol and ethanol purified during the reaction with the solvent ethanol were removed by an evaporator. Thereafter, the concentrated solution was dissolved in 2-butanone and washed twice with water. Next, 50 g of ethyl lactate was added to the organic layer, and 2-butanone was distilled off with an evaporator to obtain a reaction product.
The solid content in the obtained reaction product was 15.9% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 1300. Hereinafter, this reaction product is referred to as (A-2).

<Synthesis Example 3 (A-3)>
A monomer solution was prepared by preparing 10.65 g of 3-ethyl (tri-ethoxysilylpropoxymethyl) oxetane, 1.98 g of phenyltrimethoxysilane, 10.70 g of methyltriethoxysilane, and 40 g of ethanol. Next, 7.29 g of 25% TMAH aqueous solution, 40 g of ethanol, and 20 g of water are put into a flask, a dropping funnel containing a monomer tube prepared in advance is set with a condenser tube, and heated to 60 ° C. in an oil bath. The monomer solution was slowly added dropwise and reacted at 60 ° C. for 3 hours. After completion of the reaction, the reaction mixture was neutralized with an aqueous maleic acid solution, and the methanol and ethanol purified during the reaction with the solvent ethanol were removed by an evaporator. Thereafter, the concentrated solution was dissolved in 2-butanone and washed twice with water. Next, 50 g of ethyl lactate was added to the organic layer, and 2-butanone was distilled off with an evaporator to obtain a reaction product.
The solid content in the obtained reaction product was 17.9% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 1300. Hereinafter, this reaction product is referred to as (A-3).

<Synthesis Example 4 (A-4)>
N- (3-triethoxysilylpropyl) gluconamide 9.65 g, phenyltrimethoxysilane 1.98 g, methyltriethoxysilane 10.70 g, and ethanol 40 g were prepared to prepare a monomer solution. Next, 7.29 g of 25% TMAH aqueous solution, 40 g of ethanol, and 20 g of water are put into a flask, a dropping funnel containing a monomer tube prepared in advance is set with a condenser tube, and heated to 60 ° C. in an oil bath. The monomer solution was slowly added dropwise and reacted at 60 ° C. for 3 hours. After completion of the reaction, the reaction mixture was neutralized with an aqueous maleic acid solution, and methanol and ethanol purified during the reaction with ethanol as a solvent were removed by an evaporator. Thereafter, the concentrated solution was dissolved in 2-butanone and washed twice with water. Next, 50 g of ethyl lactate was added to the organic layer, and 2-butanone was distilled off with an evaporator to obtain a reaction product.
The solid content in the obtained reaction product was 17.9% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 1300. Hereinafter, this reaction product is referred to as (A-4).

<Synthesis Example 5 (A-5)>
A monomer solution was prepared by preparing 10.65 g of 3-ethyl (tri-ethoxysilylpropoxymethyl) oxetane, 1.98 g of phenyltrimethoxysilane, 12.50 g of tetraethoxysilane, and 50 g of methanol. Next, 7.29 g of 25% TMAH aqueous solution, 40 g of methanol, and 10 g of water were put in a flask, a dropping funnel containing a monomer tube prepared in advance with a condenser tube was set, and heated to 40 ° C. in an oil bath. The monomer solution was slowly added dropwise and reacted at 40 ° C. for 3 hours. After completion of the reaction, the reaction mixture was neutralized with an aqueous maleic acid solution, and methanol and ethanol purified during the reaction with ethanol as a solvent were removed by an evaporator. Thereafter, the concentrated solution was dissolved in 2-butanone and washed twice with water. Next, 50 g of ethylene glycol monoethyl ether was added to the organic layer, and 2-butanone was distilled off with an evaporator to obtain a reaction product.
The solid content in the obtained reaction product was 15.2% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 4800. Hereinafter, this reaction product is referred to as (A-5).

<Synthesis Example 6 (A-6)>
A monomer solution was prepared by preparing 7.09 g of (3-glycidoxypropyl) trimethoxysilane, 1.98 g of phenyltrimethoxysilane, 5.35 g of methyltriethoxysilane, 6.25 g of tetraethoxysilane, and 50 g of methanol. Next, 7.29 g of 25% TMAH aqueous solution, 40 g of methanol, and 10 g of water were put in a flask, a dropping funnel containing a monomer tube prepared in advance with a condenser tube was set, and heated to 40 ° C. in an oil bath. The monomer solution was slowly added dropwise and reacted at 40 ° C. for 3 hours. After completion of the reaction, the reaction mixture was neutralized with an aqueous maleic acid solution, and methanol and ethanol purified during the reaction with ethanol as a solvent were removed by an evaporator. Thereafter, the concentrated solution was dissolved in 2-butanone and washed twice with water. Next, 50 g of ethylene glycol monoethyl ether was added to the organic layer, and 2-butanone was distilled off with an evaporator to obtain a reaction product.
The solid content in the obtained reaction product was 14.6% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 4000. Hereinafter, this reaction product is referred to as (A-6).

<Synthesis Example 7 (A-7)>
A monomer solution was prepared by preparing 21.27 g of (3-glycidoxypropyl) trimethoxysilane, 1.98 g of phenyltrimethoxysilane, and 40 g of ethanol. Next, 7.29 g of 25% TMAH aqueous solution, 40 g of ethanol, and 20 g of water are put in a flask, and a dropping funnel containing a monomer tube prepared in advance is set in a cooling tube, and heated to 60 ° C. in an oil bath. The monomer solution was slowly added dropwise and reacted at 60 ° C. for 3 hours, and then 1.47 g of maleic acid was added and reacted for 2 hours. After completion of the reaction, the solvent ethanol and methanol purified during the reaction were removed by an evaporator. Thereafter, the concentrated solution was dissolved in 2-butanone and washed twice with water. Next, 50 g of ethyl lactate was added to the organic layer, and 2-butanone was distilled off with an evaporator to obtain a reaction product.
The solid content in the obtained reaction product was 13.6% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 5200. Hereinafter, this reaction product is referred to as (A-7).

<Synthesis Example 8 (A-8)>
A monomer solution was prepared by preparing 21.27 g of (3-glycidoxypropyl) trimethoxysilane, 1.98 g of phenyltrimethoxysilane, and 40 g of ethanol. Next, 7.29 g of 25% TMAH aqueous solution, 40 g of ethanol, and 20 g of water are put into a flask, a dropping funnel containing a monomer tube prepared in advance is set with a condenser tube, and heated to 60 ° C. in an oil bath. The monomer solution was slowly added dropwise and reacted at 60 ° C. for 3 hours. After completion of the reaction, the reaction mixture was neutralized with an aqueous maleic acid solution, and the solvent ethanol and methanol purified during the reaction were removed by an evaporator. Thereafter, the concentrated solution was dissolved in 2-butanone and washed twice with water. Next, 50 g of ethyl lactate was added to the organic layer, and 2-butanone was distilled off with an evaporator to obtain a reaction product.
The solid content in the obtained reaction product was 15.9% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 1300. Hereinafter, this reaction product is referred to as (A-8).

<Synthesis Example 9 (A-9)>
Maleic anhydride aqueous solution was prepared by dissolving 0.54 g of maleic anhydride in 10.8 g of water by heating. Next, 4.35 g of cyanoethyltriethoxysilane, 2.40 g of phenyltriethoxysilane, 12.5 g of methyltriethoxysilane, and 53.5 g of ethyl lactate were placed in the flask. A cooling tube and a dropping funnel containing a maleic acid aqueous solution prepared in advance were set in the flask, heated at 100 ° C. in an oil bath, and then the maleic acid aqueous solution was slowly added dropwise at 100 ° C. for 4 hours. Reacted. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol produced during the reaction was removed to obtain a reaction product.
The solid content in the obtained reaction product was 16.1% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 1000. Hereinafter, this reaction product is referred to as (A-9).

<Synthesis Example 10 (A-10)>
Maleic anhydride aqueous solution was prepared by dissolving 0.54 g of maleic anhydride in 10.8 g of water by heating. Next, 16.18 g of butyltriethoxysilane and 53.5 g of propylene glycol monopropyl ether were placed in the flask. A cooling tube and a dropping funnel containing a maleic acid aqueous solution prepared in advance were set in the flask, heated at 100 ° C. in an oil bath, and then the maleic acid aqueous solution was slowly added dropwise at 100 ° C. for 4 hours. Reacted. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol produced during the reaction was removed to obtain a reaction product.
The solid content in the obtained reaction product was 14.9% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 1800. Hereinafter, this reaction product is referred to as (A-10).

<Synthesis Example 11 (A-11)>
To the flask were added 8.93 g of methacryloxypropyltrimethoxysilane, 4.98 g of glycidyl methacrylate, 4.56 g of hydroxyethyl methacrylate, 3.65 g of styrene and 88.76 g of propylene glycol monomethyl ether acetate (PGMEA), and a nitrogen introduction tube and a cooling tube. And stirred at 50 ° C. for 15 minutes. Thereafter, 0.32 g of 2,2-azobisisobutyronitrile was added and reacted at 75 ° C. for 6 hours, then heated to 95 ° C. and reacted for 1 hour. After completion of the reaction, the reaction solution was poured into n-heptane to solidify the polymer, and the solid content was filtered off. Then, the obtained polymer was dissolved in 80 g of PGMEA to prepare a resin solution.
The solid content in the obtained reaction product was 18.64% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 23000. Hereinafter, this reaction product is referred to as (A-11).

[2] Preparation of resist underlayer film composition
<Example 1>
To 5.0 g of the reaction product (A-1) obtained in Synthesis Example 1, 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), 100 mg of tetramethoxyglycoluril (crosslinking agent), and 30 g of ethyl lactate were added. The resulting solution was further filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 2>
30 g of ethyl lactate is added to 5.0 g of the reaction product (A-1) obtained in Synthesis Example 1 and dissolved, and this solution is filtered through a filter having a pore size of 0.2 μm to form a resist underlayer film composition. Got.

<Example 3>
To 5.0 g of the reaction product (A-2) obtained in Synthesis Example 2, 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), 100 mg of tetramethoxyglycoluril (crosslinking agent), and 30 g of ethyl lactate were added. The resulting solution was further filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 4>
30 g of ethyl lactate is added to 5.0 g of the reaction product (A-2) obtained in Synthesis Example 2 and dissolved, and this solution is filtered through a filter having a pore size of 0.2 μm to form a resist underlayer film composition. Got.

<Example 5>
To 5.0 g of the reaction product (A-3) obtained in Synthesis Example 3, 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), 100 mg of tetramethoxyglycoluril (crosslinking agent), and 30 g of ethyl lactate were added. This was dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 6>
30 g of ethyl lactate is added to 5.0 g of the reaction product (A-3) obtained in Synthesis Example 3 and dissolved, and this solution is filtered through a filter having a pore size of 0.2 μm to form a resist underlayer film composition. Got.

<Example 7>
To 5.0 g of the reaction product (A-4) obtained in Synthesis Example 4, 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), 100 mg of tetramethoxyglycoluril (crosslinking agent), and 30 g of ethyl lactate were added. The resulting solution was further filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 8>
30 g of ethyl lactate is added to 5.0 g of the reaction product (A-4) obtained in Synthesis Example 4 and dissolved, and this solution is filtered through a filter having a pore size of 0.2 μm to form a resist underlayer film composition. Got.

<Example 9>
To 5.0 g of the reaction product (A-5) obtained in Synthesis Example 5, 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), 100 mg of tetramethoxyglycoluril (crosslinking agent), and 30 g of ethyl lactate were added. The resulting solution was further filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 10>
30 g of ethyl lactate is added to 5.0 g of the reaction product (A-5) obtained in Synthesis Example 5 and dissolved, and this solution is filtered through a filter having a pore size of 0.2 μm to form a resist underlayer film composition. Got.

<Example 11>
To 5.0 g of the reaction product (A-6) obtained in Synthesis Example 6, 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), 100 mg of tetramethoxyglycoluril (crosslinking agent), and 30 g of ethyl lactate were added. The resulting solution was further filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 12>
30 g of ethyl lactate is added to 5.0 g of the reaction product (A-6) obtained in Synthesis Example 6 and dissolved, and this solution is filtered through a filter having a pore size of 0.2 μm to form a resist underlayer film composition. Got.

<Example 13>
To 2.5 g of the reaction product (A-1) obtained in Synthesis Example 1 and 2.5 g of the reaction product (A-9) obtained in Synthesis Example 9, diphenyliodonium nonafluorobutanesulfonate (acid generator) 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and ethyl lactate 30 g were added and dissolved, and the solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 14>
Diphenyliodonium nonafluorobutanesulfonate (acid generator) was added to 2.5 g of the reaction product (A-2) obtained in Synthesis Example 2 and 2.5 g of the reaction product (A-9) obtained in Synthesis Example 9. 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and ethyl lactate 30 g were added and dissolved, and the solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 15>
2.5 g of the reaction product (A-1) obtained in Synthesis Example 1 and 2.5 g of the reaction product resin solution (A-10) obtained in Synthesis Example 10 were added to diphenyliodonium nonafluorobutanesulfonate (acid generation). Agent) 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and ethyl lactate 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 16>
2.5 g of the reaction product (A-2) obtained in Synthesis Example 2 and 2.5 g of the reaction product resin solution (A-10) obtained in Synthesis Example 10 were added to diphenyliodonium nonafluorobutanesulfonate (acid generation). Agent) 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and ethyl lactate 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 17>
2.5 g of the reaction product (A-1) obtained in Synthesis Example 1 and 2.5 g of the reaction product resin solution (A-11) obtained in Synthesis Example 11 were added to diphenyliodonium nonafluorobutanesulfonate (acid generation). Agent) 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and ethyl lactate 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 18>
2.5 g of the reaction product (A-2) obtained in Synthesis Example 2 and 2.5 g of the reaction product resin solution (A-11) obtained in Synthesis Example 11 were added to diphenyliodonium nonafluorobutanesulfonate (acid generation). Agent) 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and ethyl lactate 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 19>
5.0 g of the reaction product (A-1) obtained in Synthesis Example 1, 0.4 g of sorbitol polyglycidyl ether (polyfunctional crosslinking agent), 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), tetramethoxyglycol 100 mg of uril (crosslinking agent) and 30 g of ethyl lactate were added and dissolved, and this solution was filtered with a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 20>
2.5 g of the reaction product (A-2) obtained in Synthesis Example 2, 0.4 g of sorbitol polyglycidyl ether (polyfunctional crosslinking agent), 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), tetramethoxyglycol 100 mg of uril (crosslinking agent) and 30 g of ethyl lactate were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 21>
To 2.5 g of the reaction product (A-7) obtained in Synthesis Example 7 and 2.5 g of the reaction product (A-9) obtained in Synthesis Example 9, diphenyliodonium nonafluorobutanesulfonate (acid generator) 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and propylene glycol monopropyl ether 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 22>
To 2.5 g of the reaction product (A-7) obtained in Synthesis Example 7 and 2.5 g of the reaction product (A-10) obtained in Synthesis Example 10, diphenyliodonium nonafluorobutanesulfonate (acid generator) 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and propylene glycol monopropyl ether 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 23>
To 2.5 g of the reaction product (A-8) obtained in Synthesis Example 8 and 2.5 g of the reaction product (A-9) obtained in Synthesis Example 9, diphenyliodonium nonafluorobutanesulfonate (acid generator) 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and propylene glycol monopropyl ether 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 24>
2.5 g of the reaction product (A-8) obtained in Synthesis Example 8 and 2.5 g of the reaction product (A-10) obtained in Synthesis Example 10 were added to diphenyliodonium nonafluorobutanesulfonate (acid generator). 50 mg, tetramethoxyglycoluril (crosslinking agent) 100 mg, and propylene glycol monopropyl ether 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Comparative Example 1>
To 5.0 g of the reaction product (A-10) obtained in Synthesis Example 10, 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), 100 mg of tetramethoxyglycoluril (crosslinking agent), and 30 g of ethyl lactate were dissolved. Further, this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

[3] Evaluation of composition for resist underlayer film (Examples 1 to 24 and Comparative Example 1) The following evaluation was performed on the composition for resist underlayer film obtained in the above Examples and Comparative Examples. The results are shown in Tables 1 and 2.
(1) Adhesiveness of resist Adhesiveness between a resist underlayer film composed of a composition for a resist underlayer film as a sample and a resist film formed on the underlayer film was evaluated as follows.
First, an antireflection film material “NFC B200” (manufactured by JSR Corporation) is applied to the surface of a silicon wafer by a spin coater, dried on a 200 ° C. hot plate for 1 minute, and further on a 300 ° C. hot plate. Was used for the substrate for 1 minute to form an antireflection film having a film thickness of 300 nm. The resist underlayer film composition is applied to the surface of the antireflection film of the substrate by a spin coater, dried on a hot plate at 200 ° C. for 1 minute, and further baked on a hot plate at 250 ° C. Formed a 100 nm resist underlayer film.
Next, a resist material “ARF001S” (manufactured by JSR Corporation) was applied on the resist underlayer film and dried at 130 ° C. for 90 seconds. At this time, the resist film thickness was controlled to 300 nm. Next, using an ArF excimer laser irradiation apparatus (manufactured by Nikon Corporation), the substrate was irradiated with 32 mJ of ArF excimer laser (wavelength 193 nm) through a quartz mask having a 0.2 μm line and space pattern. The substrate was heated at 130 ° C. for 90 seconds. Subsequently, the resist pattern was formed by developing with a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds.
When the resist pattern formed on the substrate as described above is observed with a scanning electron microscope (SEM), the case where the resist pattern is not developed and peeled is indicated as “◯”, and the case where the developed film is peeled off. Evaluated as “x”.

(2) Reproducibility of resist pattern The resist pattern formed as described above is observed with an SEM, and there is no resist film residue at the location irradiated with the laser. The case where the space pattern was faithfully reproduced was evaluated as “◯”, and the case where the space pattern was not faithfully reproduced was evaluated as “X”.

(3) Evaluation of alkali resistance In the development step, the film thickness of the resist underlayer film before immersing the substrate in the developer and the film thickness of the resist underlayer film after the immersion are compared, and the difference between them is 2 nm or less. The case of “” was evaluated as “◯”, and the case of exceeding 2 nm was evaluated as “×”.

(4) Oxygen ashing resistance The resist underlayer formed as described above is subjected to oxygen ashing treatment at 300 W for 10 seconds using a barrel type oxygen plasma ashing apparatus “PR-501” (manufactured by Yamato Kagaku Co., Ltd.). The case where the difference between the film thickness of the resist underlayer film before treatment and the film thickness of the resist underlayer film after treatment was 5 nm or less was evaluated as “◯”, and the case where it exceeded 5 nm was evaluated as “x”.

(5) Storage stability of the solution The resist underlayer film composition was applied to the surface of the silicon wafer using a spin coater under the conditions of a rotation speed of 2000 rpm for 20 seconds, and then dried on a hot plate at 190 ° C. for 2 minutes. As a result, a resist underlayer film was formed. About the obtained resist underlayer film, the film thickness was measured in the position of 50 points | pieces using the optical film thickness meter (the product made by KLA-Tencor, "UV-1280SE"), and the average film thickness was calculated | required.
Further, using the resist underlayer film composition after being stored at a temperature of 40 ° C. for 1 month, a resist underlayer film was formed in the same manner as described above, the film thickness was measured, and the average film thickness was determined.
The difference (T−T ₀ ) between the average film thickness T ₀ of the underlayer film by the resist underlayer film composition before storage and the average film thickness T of the underlayer film by the resist underlayer film composition after storage is determined. The ratio [(T−T ₀ ) / T ₀ ] of the magnitude of the difference with respect to the thickness T ₀ is calculated as the film thickness change rate, and the case where the value is 10% or less is “◯”, when it exceeds 10% Was evaluated as “×”.

  As is clear from Tables 1 and 2, the resist underlayer film compositions of Examples 1 to 24 have high adhesion to the resist, excellent alkali resistance and oxygen ashing resistance, and a highly reproducible resist pattern. It is possible to form a resist underlayer film that provides a high storage stability.

Claims (11)

A resist underlayer film composition comprising polysiloxane derived from the following silane compounds [A-1], [B] and [C].
[A-1] Silane compound represented by the following general formula (1-1) [B] Silane compound represented by the following general formula (2) [C] Silane compound represented by the following general formula (3)

R ¹ _b R ² _c Si (OR ³ ) _4-a (1-1)
R ⁴ _e R ⁵ _f Si (OR ⁶ ) _4-d (2)
R ⁷ _g Si (OR ⁸ ) _4-g (3)

[In General Formula (1-1), R ¹ independently represents an epoxy group, an oxetanyl group, or an alkylhydroxyl group, and R ² independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted group having 1 to 6 carbon atoms. R ³ independently represents a monovalent organic group, a represents an integer of 1 to 3, b represents an integer of 1 to 3, c represents an integer of 0 to 2, and a = b + c. R ¹ is a group other than the OR ³ group. ]
[In General Formula (2), R ⁴ independently represents a group having an aromatic ring, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ⁵ independently represents a hydrogen atom, a halogen atom, or a carbon number of 1-6. A substituted or unsubstituted alkyl group, R ⁶ independently represents a monovalent organic group, d represents an integer of 1 to 3, e represents an integer of 1 to 3, and f represents 0 to 2 Indicates an integer and d = e + f. R ⁴ is a group other than the R ¹ , R ⁵ and OR ⁶ groups. ]
[In General Formula (3), R ⁷ independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁸ independently represents a monovalent organic group, g Represents an integer of 1 to 3. R ⁷ is a group other than R ¹ , R ^4, and OR ⁸ groups. ]   The polysiloxane is [A-1] a silane compound represented by the general formula (1-1), [B] a silane compound represented by the general formula (2), and [C] the general formula ( The composition for a resist underlayer film according to claim 1, which is a hydrolyzate and / or a condensate of a mixture of the silane compound represented by 3). The polysiloxane is
[A-1] Hydrolyzate and / or condensate of a mixture of the silane compound represented by the general formula (1-1) and the silane compound represented by [B] the general formula (2) ,as well as,
[C] The resist underlayer film composition according to claim 1, which is a resin containing a hydrolyzate of the silane compound represented by the general formula (3) and / or a condensate thereof. A resist underlayer film composition comprising a polysiloxane derived from a silane compound of the following [A-2], [B] and [D].
[A-2] Silane compound represented by the following general formula (1-2) [B] Silane compound represented by the following general formula (2) [D] Silane compound represented by the following general formula (4)

R ⁹ _b R ¹⁰ _c Si (OR ¹¹ ) _4-a (1-2)
R ⁴ _e R ⁵ _f Si (OR ⁶ ) _4-d (2)
Si (OR ¹² ) ₄ (4)

[In General Formula (1-2), R ⁹ independently represents an oxetanyl group or an alkyl hydroxyl group, and R ¹⁰ independently represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. R ¹¹ independently represents a monovalent organic group, a represents an integer of 1 to 3, b represents an integer of 1 to 3, c represents an integer of 0 to 2, and a = b + c is there. R ⁹ is a group other than the OR ¹¹ group. ]
[In General Formula (2), R ⁴ independently represents a group having an aromatic ring, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ⁵ independently represents a hydrogen atom, a halogen atom, or a carbon number of 1-6. A substituted or unsubstituted alkyl group, R ⁶ independently represents a monovalent organic group, d represents an integer of 1 to 3, e represents an integer of 1 to 3, and f represents 0 to 2 Indicates an integer and d = e + f. R ⁴ is a group other than the R ¹ , R ⁵ and OR ⁶ groups. ]
[In General Formula (4), R ¹² independently represents a monovalent organic group. ]   The polysiloxane is [A-2] a silane compound represented by the general formula (1-2), [B] a silane compound represented by the general formula (2), and [D] the general formula ( The composition for a resist underlayer film according to claim 4, which is a hydrolyzate and / or a condensate of a mixture of the silane compound represented by 4). The polysiloxane is
[A-2] Hydrolyzate and / or condensate of mixture of silane compound represented by general formula (1-2) and [B] silane compound represented by general formula (2) ,as well as,
[D] The resist underlayer film composition according to claim 4, which is a resin containing a hydrolyzate of the silane compound represented by the general formula (4) and / or a condensate thereof. Furthermore, the composition for resist underlayer films in any one of Claims 1 thru | or 6 containing at least 1 sort (s) chosen from the following [a]-[g].
[A] Hydrolyzate of compound represented by general formula (2) and / or condensate thereof [b] Hydrolyzate of compound represented by general formula (3) and / or condensate thereof [c] ] Hydrolyzate of compound represented by general formula (4) and / or condensate thereof [d] Silane compound represented by general formula (2) and silane represented by general formula (3) Hydrolyzate and / or condensate of mixture thereof [e] Hydrolysis of mixture of silane compound represented by general formula (2) and silane compound represented by general formula (4) Decomposition product and / or condensate thereof [f] Hydrolyzate and / or condensation product of mixture of silane compound represented by general formula (3) and silane compound represented by general formula (4) [G] Silane compound represented by the general formula (2) and the general formula (3) In the silane compound represented hydrolyzate of the general formula (4) silane represented by the Mixtures of a compound and / or its condensate   Furthermore, the composition for resist underlayer films in any one of the Claims 1 thru | or 7 containing the vinyl polymer containing at least 1 sort (s) of an epoxy group, oxetanyl group, an alkylhydroxyl group, a carboxyl group, and an ester bond.   Furthermore, the composition for resist underlayer films in any one of the Claims 1 thru | or 8 containing the polyfunctional crosslinking agent containing at least 1 sort (s) of an epoxy group, an oxetanyl group, an alkylhydroxyl group, and a carboxyl group.   The resist underlayer film composition according to any one of claims 1 to 9, further comprising an acid generating compound that generates an acid upon irradiation with ultraviolet light and / or heating.   A method for producing a resist underlayer film composition according to any one of claims 1 to 10, wherein the silane compound used in the resist underlayer film composition is contained in an organic solvent in the presence of water and a catalyst. A process for producing a composition for a resist underlayer film, which comprises a step of hydrolyzing and / or condensing the composition.