JP2003149820A - Pattern forming method and bilayer film for pattern formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming method capable of forming a dense pattern independently of standing waves and capable of further forming a resist pattern having a high aspect ratio by using an underlayer film excellent in dry etching resistance and usable as a thin film in combination with a specified polysiloxane-base radiation-sensitive resin composition having high transparency at <=193 nm wavelength, and to provide a bilayer film for pattern formation. SOLUTION: In the pattern forming method, a coating film comprising a radiation-sensitive resin composition comprising an acid-dissociable group- containing polysiloxane which is made alkali-soluble when the acid-dissociable group is dissociated is formed on an underlayer film comprising a polymer having >=80 wt.% carbon content and a weight average molecular weight (expressed in terms of polystyrene) of 500-100,000 and irradiation with radiation is carried out. The bilayer film for pattern formation is obtained by forming a coating film comprising the radiation-sensitive resin composition on the underlayer film.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a film containing a radiation-sensitive resin composition containing an acid-dissociable group-containing polysiloxane, which is formed on a film having a high carbon content, and is used for deep ultraviolet rays, electron beams, and X-rays. The present invention relates to a pattern forming method suitable for a lithographic process and a multiphase film for pattern formation, which has a step of irradiating radiation such as

[0002]

2. Description of the Related Art In recent years, demands for higher density and higher integration of LSIs (highly integrated circuits) have increased more and more, and along with this, miniaturization of wiring patterns has been rapidly progressing. As one of means for dealing with such miniaturization of the wiring pattern, there is a method of shortening the wavelength of exposure light used in the lithography process, and in recent years, g-line (wavelength 436n
m) or i rays (wavelength 365 nm), etc.
rF excimer laser (wavelength 248 nm) or Ar
Far-ultraviolet rays such as F excimer laser (wavelength 193 nm), electron beams, X-rays, etc. are used. By the way, novolak resins, poly (vinylphenol), etc. have been used as resin components in conventional resist compositions, but these materials contain an aromatic ring in the structure, and
Due to the strong absorption at the wavelength of 93 nm, the lithography process using the ArF excimer laser cannot provide high accuracy corresponding to high sensitivity, high resolution, and high aspect ratio. Therefore, a wavelength of 193 nm or less, particularly a wavelength of 193n
There is a demand for a resist resin material which is transparent to the wavelengths of m and 157 nm and has a dry etching resistance equal to or higher than that of an aromatic ring. A siloxane polymer is considered as one of them, and MIT RRKunz et al. Present the measurement result that the polysiloxane polymer has excellent transparency at a wavelength of 193 nm or less, particularly at 157 nm, and this polymer emits a wavelength of 193 nm or less. It is reported that it is suitable as a resist material in the lithography process used (J. Photopolym. Sci. Technol., Vol.
12, No. 4, 1999). It is also known that polysiloxane-based polymers have excellent dry etching resistance, and above all, a resist containing polyorganopolysilsesquioxane having a ladder structure has high plasma resistance.

On the other hand, some resist materials using siloxane polymers have already been reported. That is,
JP-A-5-323611 discloses a polycarboxylic acid having an acid-dissociable group in a side chain in which an acid-dissociable group such as a carboxylic acid ester group and a phenol ether group is bonded to a silicon atom through at least one carbon atom. A radiation sensitive resin composition using siloxane is disclosed. However, since this polysiloxane is a homopolymer, the resolution cannot be improved unless the side-chain acid-dissociable carboxylic acid ester groups are efficiently dissociated, and when many acid-dissociable groups are dissociated, the resist There is also a problem that the curing shrinkage stress of the coating film becomes large and cracks or peeling of the resist coating film are likely to occur. In addition, in Japanese Patent Laid-Open No. 8-160623, poly (2
-Carboxyethyl siloxane) to t
-A positive resist using a polymer protected with an acid dissociable group such as a butyl group is disclosed. However, in this resist, since the protection rate of the carboxyl group is low, a large amount of carboxylic acid component is present in the unexposed portion, and it is difficult to develop with a normal alkali developing solution. Further, JP-A-11-6073
Japanese Patent Publication No. 3 discloses a resist resin composition using a polyorganosilsesquioxane having an acid dissociable ester group. However, this polyorganosilsesquioxane is produced by subjecting a condensation product such as vinyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane to an addition reaction of an acid dissociable group-containing (meth) acrylic monomer. Since the unsaturated group remains on the polymer side chain, there is a problem in terms of transparency at a wavelength of 193 nm or less. Further, in the publication, polyhydroxycarbonylethylsilsesquioxane is referred to as t-
A resist resin composition using a polymer esterified with butyl alcohol is also described, but this polymer also has a low protection rate of carboxyl groups and has the same problem as that of JP-A-8-160623 as a resist.

Against the background of the above situation, the present applicant also
A lot of studies have been conducted on a resist material using a highly transparent siloxane polymer at a wavelength of 193 nm or less. However, with this resist material, the effect of standing waves, which is considered to be due to its high transparency to short-wavelength radiation, cannot be ignored, and it became clear that this resist material impedes the formation of fine patterns. As one measure for suppressing the influence of such standing waves, a method of providing an underlayer film capable of suppressing the influence of standing waves and having sufficient dry etching resistance can be considered. In order to impart dry etching resistance to the lower layer film, the content of highly reactive elements such as hydrogen atoms and nitrogen atoms in the polymer that composes the lower layer film should be reduced and the reaction with etching gas should be reduced. It is necessary to increase the content of carbon atoms having a relatively low property, and i-line resists made of novolac resin have been mainly used conventionally. However, it cannot be said that the i-line resist also has sufficient resistance to dry etching, and it is inevitable that the i-line resist is considerably corroded during the processing of the lower layer film for processing the silicon-based oxide film to cause film reduction. Therefore, today, the thickness of the lower layer film is increased to accommodate it. However, KrF excimer laser, ArF excimer laser, and F ₂ excimer laser (wavelength 157 nm)
Since the pattern size is small in the process of processing a fine silicon-based oxide film by, the method of increasing the film thickness inevitably increases the aspect ratio of the pattern, resulting in erosion by the etching gas from the pattern sidewall. It progresses easily, and pattern thinning and pattern collapse are likely to occur, making it difficult to perform precise pattern transfer.

[0005]

An object of the present invention is to provide an underlayer film which has excellent dry etching resistance and can be used as a thin film, and a wavelength of 193 nm or less, particularly wavelengths of 193 nm and 157.
When used in combination with a specific polysiloxane-based radiation-sensitive resin composition having high transparency at a wavelength of nm, a dense pattern can be formed without being affected by standing waves, and dry To provide a pattern forming method and a pattern forming multilayer film capable of forming a resist pattern having a high aspect ratio by appropriately selecting an etching gas in an etching step.

[0006]

Means for Solving the Problems The present invention is, firstly, a polymer having a carbon content of 80% by weight or more and a polystyrene reduced weight average molecular weight of 500 to 100,000 (hereinafter referred to as "polymer for lower layer film"). .) Containing an acid-dissociable group, the alkali-insoluble or sparingly-soluble acid-dissociable group-containing polysiloxane that becomes alkali-soluble when the acid-dissociable group dissociates (hereinafter, simply referred to as “acid-dissociable group-containing polysiloxane”). And a radiation-sensitive resin composition containing the radiation-sensitive resin composition.

The pattern forming method of the present invention is preferably an underlayer film comprising a polymer having a structural unit represented by the following general formula (1) (hereinafter referred to as "polymer for underlayer film (1)"). A radiation-sensitive resin composition containing an alkali-insoluble or sparingly-soluble acid-dissociable group-containing polysiloxane, which becomes alkali-soluble when the acid-dissociable group dissociates on a film containing the polymer Characterized in that it has a step of forming a coating and irradiating with radiation.
Pattern formation method

[0008]

[Chemical 3] [In the general formula (1), R ¹ represents a monovalent atom or a monovalent group, m is an integer of 0 to 4, and when m is 2 to 4, a plurality of R ¹ are the same or different from each other. Alternatively, R ² and R ³ each independently represent a monovalent atom or a monovalent group. ]]

Secondly, the present invention comprises an alkali-insoluble or sparingly-soluble alkali-dissociable group-containing acid-dissociable group, which becomes alkali-soluble when the acid-dissociable group is dissociated on the film containing the lower layer polymer. A multilayer film for pattern formation, which is formed by forming a coating film of a radiation-sensitive resin composition containing polysiloxane.

The pattern forming multilayer film of the present invention is preferably alkali-soluble when the acid-labile group is dissociated on the film containing the underlayer polymer consisting of the underlayer polymer (1). And a pattern-forming multilayer film formed by forming a coating film of a radiation-sensitive resin composition containing an alkali-insoluble or sparingly alkali-soluble acid-labile group-containing polysiloxane.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Polymer for lower layer film The polymer for the lower layer film is preferably a polymer having a carbon content of 85% by weight or more, more preferably 90% by weight, and having an aromatic hydrocarbon structure in the molecule. Examples of the lower layer polymer include, for example, the lower layer polymer (1),
A polymer having a structural unit represented by the following general formula (4) (hereinafter referred to as "polymer for underlayer film (4)"), a polymer having a structural unit represented by the following general formula (5) ( Less than,
It is referred to as "polymer for lower layer film (5)". ), A polymer having a structural unit represented by the following general formula (6) (hereinafter referred to as “polymer (6) for lower layer film”), and the like, and particularly polymer (1) for lower layer film. Is preferred.

[0012]

[Chemical 4] [In the general formula (4), R ¹ , m, R ² and R ³ are respectively as defined in the general formula (1). ]

[0013]

[Chemical 5] [In the general formula (5), R ¹ , m, R ² and R ³ are respectively as defined in the general formula (1), and R ⁵ and R ⁶ are independently a monovalent atom or a monovalent atom. Indicates a group. ]

[0014]

[Chemical 6] [In the general formula (6), R ¹ , m, R ² and R ³ are respectively as defined in the general formula (1). ]

In the general formula (1), the monovalent atom or group of R ¹ is, for example, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a nitro group, a sulfonic acid group, a phenyl group, an alkyl group or an alkenyl. A group, an amino group, an acyl group, or a phenyl group, an alkyl group or an alkenyl group thereof, is substituted with one or more or one or more kinds such as a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a nitro group or a sulfonic acid group. A group etc. can be mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, i
-Propyl group, n-butyl group, i-butyl group, sec-
A linear or branched alkyl group having 1 to 6 carbon atoms such as a butyl group and a t-butyl group is more preferable. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and a straight chain or branched chain having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a 1-butenyl group and a 2-butenyl group. The alkenyl group of is more preferable. As the amino group, a primary amino group is preferable, and an aminomethyl group, a 2-aminoethyl group, a 3-aminopropyl group,
A linear or branched primary amino group having 1 to 6 carbon atoms such as a 4-aminobutyl group is more preferable. The acyl group is preferably an acyl group having 2 to 10 carbon atoms, and more preferably an aliphatic or aromatic acyl group having 2 to 6 carbon atoms such as acetyl group, propionyl group, butyryl group, benzoyl group.

In the general formula (1), examples of the monovalent atom or group of R ² and R ³ include the same as those exemplified for the monovalent atom or monovalent group of R ¹ , respectively. be able to. However, R ² or R ³
The monovalent atom or monovalent group of R ¹ and the monovalent atom or monovalent group of R ¹ may be the same or different from each other.

In the general formula (5), the monovalent atom or monovalent group of R ⁵ and R ⁶ is, for example, the monovalent atom or monovalent group of R ¹ in the general formula (1). The same groups as those exemplified for the group can be mentioned. However, in the general formula (5), a monovalent atom or a monovalent group of R ⁵ or R ^6, a monovalent atom or a monovalent group of R ^{1, and} a monovalent atom of R ² or R ^3. Alternatively, the monovalent group may be the same or different from each other.

More specifically, the lower layer polymer (1) is a polymer having a structural unit represented by the following general formula (7) (hereinafter, "lower layer polymer (1-1)"). ".)
As the polymer (4) for the lower layer film,
More specifically, a polymer having a structural unit represented by the following general formula (8) (hereinafter referred to as “polymer for lower layer film (4-1)”) can be mentioned, and for a lower layer film. As the polymer (5), more specifically, a polymer having a structural unit represented by the following general formula (9) (hereinafter, referred to as “polymer for underlayer film (5-1)”) is given. be able to.

[0020]

[Chemical 7] [In the general formula (7), R ¹ , m, R ² and R ³ are as defined in the general formula (1), and R ⁷ represents a hydrogen atom or a monovalent organic group. ]

[0021]

[Chemical 8] [In the general formula (8), R ¹ , m, R ² and R ³ are respectively as defined in the general formula (1), and R ⁵ and R ⁶ are respectively as defined in the general formula (5). , R ⁷ are as defined in the general formula (7). ]

[0022]

[Chemical 9] [In the general formula (9), R ¹ , m, R ² and R ³ are as defined in the general formula (1), and R ⁷ is as defined in the general formula (7). ]

In the general formulas (7), (8) and (9), examples of the monovalent organic group represented by R ⁷ include an alkyl group, an alkenyl group, an alicyclic group and an aromatic hydrocarbon. Groups, heterocyclic groups and the like. Examples of the alkyl group of R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group,
A linear or branched alkyl group having 1 to 6 carbon atoms such as a sec-butyl group and a t-butyl group is preferable. As the alkenyl group for R ^7, a linear or branched alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a 1-butenyl group and a 2-butenyl group is preferable. As the alicyclic group for R ^7, an alicyclic group having 4 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group is preferable. The aromatic hydrocarbon group for R ⁷ is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms such as a phenyl group, a 1-naphthyl group or a 2-naphthyl group. Further, the heterocyclic group for R ⁷ is, for example, 2
-Furanyl group, tetrahydro-2-furanyl group, furfuryl group, tetrahydrofurfuryl group, thiofurfuryl group, 2-pyranyl group, tetrahydro-2-pyranyl group,
A 4- to 10-membered heterocyclic group such as a 2-pyranylmethyl group and a tetrahydro-2-pyranylmethyl group is preferable.

The polymer for the lower layer film can be produced, for example, by the following method. However, the method for producing the polymer for the lower layer film is not limited to these methods. Production method (a): (a-1) After condensing acenaphthylenes and aldehydes together with other aromatic compounds capable of co-condensing in the presence of an acid catalyst, this polymer is used alone or in co-polymerization. After polymerizing with other polymerizable monomers or (a-2) acenaphthylenes alone or with other copolymerizable monomers, this polymer and aldehydes can be optionally co-condensed. Acenaphthylene, which is condensed with the aromatic compound described above in the presence of an acid catalyst or is substituted with a (a-3) group —CH ₂ —OR (wherein R represents a hydrogen atom or a monovalent organic group). A polymer having a repeating unit represented by the following formula (i), which is obtained by polymerizing the compounds with other acenaphthylenes or other copolymerizable monomers (hereinafter,
It is called "polymer (i)". ) Is used to prepare a composition for forming an underlayer film described below, and then the composition is applied to a substrate and heated to further condense the polymer (i), whereby the underlayer polymer (1- How to get 1).

[0025]

[Chemical 10] [In the formula (i), R represents a hydrogen atom or a monovalent organic group, and R ¹ , m, R ² and R ³ are respectively as defined in the general formula (1). ]

Production method (b): Acenaphthylenes and aldehydes are optionally condensed with other aromatic compounds capable of co-condensation in the presence of an acid catalyst to give a polymer (4-1) for lower layer film. How to get. Production method (c): Acenaphthenes and aldehydes, optionally together with other aromatic compounds capable of co-condensing,
A method of obtaining a polymer (5-1) for lower layer film by condensation in the presence of an acid catalyst. The lower layer polymer (6) can be obtained by the step of polymerizing the acenaphthylenes alone or together with another copolymerizable monomer in the method (a-2).
In particular, the method (a-3) is preferable because the storage stability of the composition for forming an underlayer film described below is good and the degree of crosslinking of the polymer for the underlayer film can be easily adjusted.

Examples of the acenaphthylenes used in the production method (a) include acenaphthylene; 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1- Bromoacenaphthylene, 3-bromoacenaphthylene, 4-bromoacenaphthylene, halogenated acenaphthylenes such as 5-bromoacenaphthylene; 1-hydroxyacenaphthylene, 3-hydroxyacenaphthylene, 4-hydroxyacena Hydroxyacenaphthylenes such as butylene, 5-hydroxyacenaphthylene; 1-mercaptoacenaphthylene, 3-mercaptoacenaphthylene, 4-mercaptoacenaphthylene, 5-mercaptoacenaphthylene and other mercaptoacenaphthylenes Kind;

Acenaphthylene-1-carboxylic acids such as acenaphthylene-1-carboxylic acid, acenaphthylene-3-carboxylic acid, acenaphthylene-4-carboxylic acid, acenaphthylene-5-carboxylic acid; 1-nitroacenaphthylene, 3-
Nitroacenaphthylene, 4-Nitroacenaphthylene, 5
-Nitroacenaphthylenes such as nitroacenaphthylene;
Acenaphthylene-1-sulfonic acid, acenaphthylene-3
-Acenaphthylenesulfonic acids such as sulfonic acid, acenaphthylene-4-sulfonic acid, acenaphthylene-5-sulfonic acid; 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacena Alkylacenaphthylenes such as butylene, 1-ethylacenaphthylene, 3-ethylacenaphthylene, 4-ethylacenaphthylene, 5-ethylacenaphthylene;

1-Vinylacenaphthylene, 3-vinylacenaphthylene, 4-vinylacenaphthylene, 5-alkenylacenaphthylenes such as 5-vinylacenaphthylene; 1-
Aminoacenaphthylene, 3-Aminoacenaphthylene, 4
-Aminoacenaphthylene such as aminoacenaphthylene, 5-aminoacenaphthylene; acyl such as 1-acetylacenaphthylene, 3-acetylacenaphthylene, 4-acetylacenaphthylene, 5-acetylacenaphthylene Acenaphthylenes; 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5
-Phenylacenaphthylenes such as phenylacenaphthylene,

Examples of the acenaphthylenes substituted with the group —CH ₂ —OR include, for example, 3-hydroxymethylacenaphthylene, 4-hydroxymethylacenaphthylene, 5-hydroxymethylacenaphthylene, 1-methyl-3-hydroxy. Methylacenaphthylene, 1-methyl-4-hydroxymethylacenaphthylene, 1-methyl-5-hydroxymethylacenaphthylene, 1-methyl-6-hydroxymethylacenaphthylene, 1-methyl-7-hydroxymethylacena Fullylene, 1-methyl-8-hydroxymethylacenaphthylene, 1,2-dimethyl-3-hydroxymethylacenaphthylene, 1,2-dimethyl-4-hydroxymethylacenaphthylene, 1,2-dimethyl-5 -Hydroxymethyl acenaphthylene, 1-phenyl-3-hydroxymethyl Naphthylene, 1-phenyl-4-hydroxymethylacenaphthylene, 1-phenyl-5-hydroxymethylacenaphthylene, 1-phenyl-6-hydroxymethylacenaphthylene, 1-phenyl-7-hydroxymethylacenaphthylene, 1-phenyl-8-hydroxymethylacenaphthylene, 1,2-diphenyl-
3-hydroxymethylacenaphthylene, 1,2-diphenyl-4-hydroxymethylacenaphthylene, 1,2-
Hydroxymethylacenaphthylenes such as diphenyl-5-hydroxymethylacenaphthylene;

3-methoxymethylacenaphthylene, 4-
Methoxymethylacenaphthylene, 5-methoxymethylacenaphthylene, 1-methyl-3-methoxymethylacenaphthylene, 1-methyl-4-methoxymethylacenaphthylene, 1-methyl-5-methoxymethylacenaphthylene, 1-methyl-6-methoxymethylacenaphthylene,
1-methyl-7-methoxymethylacenaphthylene, 1-
Methyl-8-methoxymethylacenaphthylene, 1,2-
Dimethyl-3-methoxymethylacenaphthylene, 1,2
-Dimethyl-4-methoxymethylacenaphthylene, 1,
2-dimethyl-5-methoxymethylacenaphthylene, 1
-Phenyl-3-methoxymethylacenaphthylene, 1-
Phenyl-4-methoxymethylacenaphthylene, 1-phenyl-5-methoxymethylacenaphthylene, 1-phenyl-6-methoxymethylacenaphthylene, 1-phenyl-7-methoxymethylacenaphthylene, 1-phenyl- 8-methoxymethylacenaphthylene, 1,2-diphenyl-3-methoxymethylacenaphthylene, 1,2-diphenyl-4-methoxymethylacenaphthylene, 1,2
Examples thereof include methoxymethylacenaphthylenes such as diphenyl-5-methoxymethylacenaphthylene. These acenaphthylenes can be used alone or in admixture of two or more.

The aldehydes used in the production method (a) include, for example, saturated aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde and propyl aldehyde; unsaturated aliphatic aldehydes such as acrolein and methacrolein; Heterocyclic aldehydes such as furfural; aromatic aldehydes such as benzaldehyde, 1-naphthalaldehyde, 9-anthraldehyde and the like. Of these aldehydes, formaldehyde and paraformaldehyde are particularly preferable. . The aldehydes may be used alone or in admixture of two or more. The amount of aldehydes used in the production method (a) is usually 1 to 1,000 with respect to 100 parts by weight of acenaphthylenes.
Parts by weight, preferably 5 to 500 parts by weight.

Further, other co-condensable aromatic compounds optionally used in the production method (a) are not particularly limited as long as they can be co-condensed with acenaphthylenes, and for example, benzene, naphthalene, Anthracene,
Unsubstituted aromatic hydrocarbons such as phenanthrene and acenaphthene; alkyl-substituted aromatic hydrocarbons such as toluene, m-xylene, p-xylene, 1-methylnaphthalene; phenol, cresol, 1-naphthol, bisphenols, polyvalent Hydroxy-substituted aromatic hydrocarbons such as phenols; benzoic acid, carboxyl-substituted aromatic hydrocarbons such as 1-naphthalenecarboxylic acid, 9-anthracenecarboxylic acid; amino such as aniline, 1-aminonaphthalene, 9-aminoanthracene Substituted aromatic hydrocarbons; chlorobenzene, bromobenzene, 1-chloronaphthalene, 1
Examples thereof include halogen-substituted aromatic hydrocarbons such as bromonaphthalene. These other aromatic compounds may be used alone or in combination of two or more. The amount of the other aromatic compound used in the production method (a) is usually 10,000 parts by weight or less based on 100 parts by weight of the acenaphthylene compound.

Further, as the other copolymerizable monomer optionally used in the production method (a), for example, styrene, α-methylstyrene, o-methylstyrene, m-
Methylstyrene, p-methylstyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxymethylstyrene, m-hydroxymethylstyrene, p-hydroxymethylstyrene, o
-Acetoxystyrene, m-acetoxystyrene, p
-(Substituted) styrene compounds such as acetoxystyrene and pt-butoxystyrene; carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate and vinyl caproate;

Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate,
Unsaturated carboxylic acid ester compounds such as t-butyl (meth) acrylate, n-hexyl (meth) acrylate and glycidyl (meth) acrylate; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, (meth) Unsaturated group-containing unsaturated carboxylic acid ester compounds such as vinyl acrylate and dimethyl vinyl vinyl methacryloyloxymethylsilane; 2
-Halogen-containing vinyl compounds such as chloroethyl vinyl ether, vinyl chloroacetate and allyl chloroacetate;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Hydroxyl group-containing vinyl compounds such as (meth) allyl alcohol; Amide group-containing vinyl compounds such as (meth) acrylamide and crotonic acid amide; succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2
-(Meth) acryloyloxyethyl], mono- [2- (meth) acryloyloxyethyl] phthalate, etc., carboxyl group-containing vinyl compounds; 1-vinylnaphthalene,
2-vinylnaphthalene, 9-vinylanthracene, 9-
Other vinyl aryl compounds such as vinyl carbazole can be cited. These other copolymerizable monomers may be used alone or in admixture of two or more.

In the production method (a), the ratio of the acenaphthylene compound to the other copolymerizable monomer is preferably 5 to 100 mol%, more preferably 10 to 100 mol% of the total amount of both. 100 mol%,
More preferably, it is 20 to 100 mol%. The polymerization in the production method (a) can be carried out in an appropriate polymerization mode such as bulk polymerization or solution polymerization by, for example, radical polymerization, anionic polymerization, cationic polymerization or the like.

In the production method (a), the polymer M condensed with the acenaphthylenes and the aldehydes in the step (a-1), optionally together with other aromatic compounds capable of co-condensation
The Mw of the polymer obtained by polymerizing w and acenaphthylenes in the step (a-2) alone or together with other copolymerizable monomers is appropriately selected according to the desired characteristics of the lower layer film, but is usually 100. ~ 10,000, preferably 2,000
It is 0 to 5,000.

Next, the aldehydes and other aromatic compounds optionally used in the production method (b) are, for example, the same as the aldehydes and other aromatic compounds exemplified in the production method (a). You can list the following. The amount of the aldehyde used in the production method (b) is usually 1 to 1,000 parts by weight, preferably 5 to 50 parts by weight based on 100 parts by weight of the acenaphthylene.
0 parts by weight, and the amount of the other aromatic compound used is usually 10,0 per 100 parts by weight of the acenaphthylenes.
It is not more than 00 parts by weight.

Next, the acenaphthenes used in the production method (c) include, for example, acenaphthene; 1-chloroacenaphthene, 3-chloroacenaphthene, 4-chloroacenaphthene, 5-chloroacenaphthene, 1-bromo. Halogenated acenaphthenes such as acenaphthene, 3-bromoacenaphthene, 4-bromoacenaphthene, 5-bromoacenaphthene; 1-hydroxyacenaphthene, 3-hydroxyacenaphthene, 4-hydroxyacenaphthene, 5-hydroxyacenaphthene Hydroxyacenaphthenes such as;
Mercaptoacenaphthenes such as 1-mercaptoacenaphthene, 3-mercaptoacenaphthene, 4-mercaptoacenaphthene, 5-mercaptoacenaphthene;

Acenaphthene carboxylic acids such as acenaphthene-1-carboxylic acid, acenaphthene-3-carboxylic acid, acenaphthene-4-carboxylic acid, acenaphthene-5-carboxylic acid; 1-nitroacenaphthene, 3-nitroacenaphthene, 4-nitroacenaphthene 5-Nitroacenaphthenes such as nitroacenaphthene; acenaphthene-1-
Acenaphthene sulfonic acids such as sulfonic acid, acenaphthene-3-sulfonic acid, acenaphthene-4-sulfonic acid, acenaphthene-5-sulfonic acid; 1-methylacenaphthene, 3-methylacenaphthene, 4-methylacenaphthene, 5-methylacenaphthene Alkylacenaphthenes such as 1-ethylacenaphthene, 3-ethylacenaphthene, 4-ethylacenaphthene, 5-ethylacenaphthene and the like;

Alkenylacenaphthenes such as 1-vinylacenaphthene, 3-vinylacenaphthene, 4-vinylacenaphthene, 5-vinylacenaphthene; 1-aminoacenaphthene, 3-aminoacenaphthene, 4-aminoacenaphthene Aminoacenaphthenes such as 5-aminoacenaphthene; 1-acetylacenaphthenes, 3-acetylacenaphthenes, 4-acetylacenaphthenes, acylacenaphthenes such as 5-acetylacenaphthenes, 1-phenylacenaphthenes, 3 Examples include phenylacenaphthenes such as -phenylacenaphthene, 4-phenylacenaphthene, and 5-phenylacenaphthene. These acenaphthenes can be used alone or in admixture of two or more.

The aldehydes used in the production method (c) and other aromatic compounds optionally used are the same as the aldehydes and other aromatic compounds exemplified in the production method (a). I can list things. The amount of aldehydes used in the production method (c) is 100 parts by weight of acenaphthenes,
Usually, it is 1 to 1,000 parts by weight, preferably 5 to 500 parts by weight. The amount of the other aromatic compound used in the production method (c) is usually 10,000 parts by weight or less based on 100 parts by weight of the acenaphthenes.

The condensation reaction in the production methods (a) to (c) is carried out by heating without a solvent or in a solvent, preferably in a solvent, in the presence of an acid catalyst. Examples of the acid catalyst include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid;
Organic sulfonic acids such as p-toluenesulfonic acid; formic acid,
Examples thereof include carboxylic acids such as oxalic acid. The amount of the acid catalyst used is appropriately adjusted depending on the type of acid used, but is usually 0.001 to 10,000 parts by weight, preferably 0.01 to 1 part by weight, relative to 100 parts by weight of acenaphthylene or acenaphthene. 1,000 parts by weight.

The solvent used in the condensation reaction of the production methods (a) to (c) is not particularly limited as long as it does not inhibit the condensation reaction, and examples thereof include phenol resins, melamine resins and amino resins. , A solvent conventionally used in the synthesis of a resin using an aldehyde as a raw material, more specifically, in addition to the solvent described below used in the pattern forming composition solution in the present invention, tetrahydrofuran,
Examples thereof include cyclic ethers such as dioxane. When the acid catalyst used is a liquid such as formic acid, the acid catalyst can also serve as a solvent. The reaction temperature of the condensation reaction in the production methods (a) to (c) is usually 40 ° C to 200 ° C.
Is. The reaction time is appropriately adjusted depending on the reaction temperature, but is usually 30 minutes to 72 hours.

The Mw of the lower layer polymer in the present invention is
Usually 500 to 100,000, preferably 5,000
~ 50,000. In the present invention, the polymer for the lower layer film may be used alone or in combination of two or more kinds.

Composition for Forming Underlayer Film When the underlayer film is formed using the polymer for underlayer film of the present invention, the polymer for underlayer film is usually dissolved in a solvent together with an additive to be described later. The prepared solution (hereinafter, referred to as "underlayer film forming composition") is used. The polymer (i) is further condensed to obtain a polymer (1-1) for lower layer film.
In order to obtain the above, a composition for forming an underlayer film, in which the polymer (i) is dissolved in a solvent, optionally together with the additives described below, is used. The solvent used in the composition for forming the lower layer film is not particularly limited as long as it can dissolve the polymer for the lower layer film and the additive component, and examples thereof include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether and the like; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene Ethylene glycol monoalkyl ether acetates such as glycol mono-n-butyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether and the like; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether Propylene glycol monoalkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n
Propylene glycol dialkyl ethers such as propyl ether and propylene glycol di-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol monoalkyl ether acetates such as;

Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, n-butyl lactate, i-butyl lactate; methyl formate, ethyl formate, n-propyl formate, i-propyl formate, N-Butyl formate, i-butyl formate, n-amyl formate, i-amyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate , I-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate, methyl butyrate, ethyl butyrate, butyrate Aliphatic carboxylic acid esters such as n-propyl, i-propyl butyrate, n-butyl butyrate, i-butyl butyrate; hydroxyacetate , Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, 3-methyl-3-
Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl pyruvate,
Other esters such as ethyl pyruvate;

Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N-methylformamide, N, N Examples include amides such as -dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-butyrolactone.

Among these solvents, preferred solvents are ethylene glycol monoethyl ether acetates, ethyl lactate, methyl 3-methoxypropionate, and 3
-Ethyl ethoxypropionate, 2-heptanone, cyclohexanone, etc. can be mentioned. The said solvent can be used individually or in mixture of 2 or more types.

The amount of the solvent used in the lower layer film-forming composition is such that the total solid content concentration in the lower layer film-forming composition is usually
The range is 0.01 to 70% by weight, preferably 0.05 to 60% by weight, and more preferably 0.1 to 50% by weight.

In the composition for forming the lower layer film, a crosslinking agent and a polymer other than the polymer for the lower layer film (hereinafter, referred to as "other polymer") may be added, if necessary, as long as the intended effect of the present invention is not impaired. ".), Radiation absorbers, surfactants, acid generators, and other various additives. The cross-linking agent has, for example, an effect of preventing an intermixing between an underlayer film obtained by applying a composition for forming an underlayer to a substrate and a pattern forming layer formed thereon, Further, it is a component that also has the function of preventing cracks after application of the lower layer forming composition.

As such a crosslinking agent, polynuclear phenols and various commercially available curing agents can be used.
Examples of the polynuclear phenols include binuclear phenols such as 4,4′-biphenyldiol, 4,4′-methylenebisphenol, 4,4′-ethylidenebisphenol, and bisphenol A; 4,4 ′, 4 ″. -Methylidene trisphenol, 4,4 '-[1- {4- (1-
Examples include trinuclear phenols such as [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol; and polyphenols such as novolac. Of these polynuclear phenols, 4,4'-
[1- {4- (1- [4-hydroxyphenyl] -1-
Methylethyl) phenyl} ethylidene] bisphenol, novolac and the like are preferable. The polynuclear phenols may be used alone or in combination of two or more.

The curing agent is, for example, 2,
3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 3,4-tolylene diisocyanate,
Diisocyanates such as 3,5-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and 1,4-cyclohexane diisocyanate, and Epicoat 8 as a commercial product.
12, Same 815, Same 826, Same 828, Same 834, Same 8
36, ibid 871, ibid 1001, ibid 1004, ibid 100
7, the same 1009, the same 1031 (trade name, made of oiled shell epoxy), Araldite 6600, the same 6700, the same 68
00, 502, 6071, 6084, 609
7 and 6099 (trade name, manufactured by Ciba Geigy), DER3
31, 332, 333, 661, 644, 6
67 (trade name, manufactured by Dow) and other epoxy compounds; Cymel 300, 301, 303, 350, 370,
771, 325, 327, 703, 712,
701, 272, 202, Mycoat 506, 508 (trade name, manufactured by Mitsui Cyanamid) and the like melamine-based curing agents; Cymel 1123, 1123-10, 1
128, My Court 102, 105, 106, 1
Benzoguanamine-based curing agents such as 30 (trade name, manufactured by Mitsui Cyanamid); Cymel 1170, 1172 (trade name, manufactured by Mitsui Cyanamid), Nikarac N-2702
(Trade name, manufactured by Sanwa Chemical Co., Ltd.) and other glycoluril-based curing agents. Of these hardeners,
Melamine-based curing agents and glycoluril-based curing agents are preferred. The curing agents may be used alone or in combination of two or more. Further, a polynuclear phenol and a curing agent can be used in combination as a cross-linking agent.

The amount of the cross-linking agent to be compounded is usually 5,000 parts by weight or less, preferably 1,000 parts by weight or less, per 100 parts by weight of the total solid content in the composition for forming an underlayer film.

As the other polymer, various thermoplastic resins and thermosetting resins can be used. Examples of the thermoplastic resin include poly (1,4-pentadiene), poly (1,4-hexadiene), poly (1,5-
Hexadiene) and other non-conjugated diene polymers; α, β-unsaturated ketone polymers such as poly (methyl vinyl ketone), poly (aromatic vinyl ketone) and poly (cyclic vinyl ketone);

Polymers of α, β-unsaturated carboxylic acid or its derivative such as (meth) acrylic acid, (meth) acrylic acid salt, (meth) acrylic acid ester and (meth) acrylic acid halide; poly ( Polymers of α, β-unsaturated carboxylic acid anhydrides such as (meth) acrylic acid anhydride and copolymers of maleic anhydride; unsaturated polybasic carboxylic acid esters such as methylenemalonic acid diester and itaconic acid diester Polymers; Polymers of diolefincarboxylic acid ester such as sorbic acid ester and muconic acid ester; Polymers of α, β-unsaturated carboxylic acid thioester such as (meth) acrylic acid thioester and α-chloroacrylic acid thioester Polymers of (meth) acrylonitrile such as (meth) acrylonitrile and α-chloroacrylonitrile or derivatives thereof; (Meth) acrylamide, N, N
-Polymers of (meth) acrylamide such as dimethyl (meth) acrylamide or derivatives thereof; polymers of styryl metal compounds; polymers of vinyloxy metal compounds;

Polyimines; polyphenylene oxide,
Polyethers such as poly (1,3-dioxolane), polyoxirane, polytetrahydrofuran, polytetrahydropyran; polysulfides; polysulfonamides; polypeptides; polyamides such as nylon 66 and nylon 1 to nylon 12; aliphatic Polyesters such as polyesters, aromatic polyesters, alicyclic polyesters, and polycarbonates; polyureas; polysulfones;
Polyazines; Polyamines; Polyaromatic ketones; Polyimides; Polybenzimidazoles; Polybenzoxazoles; Polybenzothiazoles; Polyaminotriazoles; Polyoxadiazoles; Polypyrazoles; Polytetrazoles; Polyquinoxalines Examples thereof include polytriazines, polybenzoxazinones, polyquinolines, polyanthrazolines and the like.

The thermosetting resin is a component which is cured by heating after being applied to the substrate and becomes insoluble in a solvent, and has a function of preventing intermixing between the lower layer film and the pattern forming layer. Can be preferably used as the polymer of Examples of such thermosetting resins include thermosetting acrylic resins, phenol resins, urea resins, melamine resins, amino resins, aromatic hydrocarbon resins, epoxy resins and alkyd resins.

These other polymers can be used alone or in admixture of two or more. The amount of the other polymer compounded is usually 20 per 100 parts by weight of the polymer for the lower layer film.
It is not more than 10 parts by weight, preferably not more than 10 parts by weight.

Examples of the radiation absorber include dyes such as oil-soluble dyes, disperse dyes, basic dyes, methine dyes, pyrazole dyes, imidazole dyes and hydroxyazo dyes; bixine derivatives, norbixin, stilbene, Fluorescent whitening agents such as 4,4′-diaminostilbene derivatives, coumarin derivatives and pyrazoline derivatives; UV absorbers such as hydroxyazo dyes, Tinuvin 234 (trade name, manufactured by Ciba Geigy), Tinuvin 1130 (trade name, manufactured by Ciba Geigy) And aromatic compounds such as anthracene derivatives and anthraquinone derivatives. These radiation absorbers can be used alone or in admixture of two or more. The content of the radiation absorber is usually 100 parts by weight or less, preferably 50 parts by weight or less, per 100 parts by weight of the total solid content in the composition for forming an underlayer film.

The above-mentioned surfactant is a component having an effect of improving coating property, striation, wettability, developability and the like. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, polyethylene. Nonionic surfactants such as glycol dilaurate and polyethylene glycol distearate, and commercially available organosiloxane polymers KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth) acrylic acid (co) polymers. Polyflow No. 75, the same No. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), F-top EF101, EF204, EF303, EF
352 (trade name, manufactured by Tochem Products), Megafac F171, F172, F173 (trade name, manufactured by Dainippon Ink and Chemicals), Florard FC430, FC4
31, FC135, FC93 (trade name, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S38
2, the same SC101, the same SC102, the same SC103, the same S
Examples thereof include C104, SC105, SC106 (trade name, manufactured by Asahi Glass Co., Ltd.). These surfactants may be used alone or in admixture of two or more. The content of the surfactant is usually 15 parts by weight or less based on 100 parts by weight of the total solid content in the composition for forming an underlayer film.
It is preferably 10 parts by weight or less.

As the acid generator, a radiation sensitive acid generator or a thermal acid generator can be used. As the radiation-sensitive acid generator, the radiation-sensitive acid generator used in the pattern forming composition described later can be used.

The thermal acid generator may be, for example,
2,4,4,6-tetrabromocyclohexadienone,
Examples thereof include benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl sulfonate. These thermal acid generators can be used alone or in admixture of two or more, and a photoacid generator and a thermal acid generator can be used in combination.

The amount of the acid generator compounded is usually 5,000 parts by weight or less, preferably 0.1 to 1,000 parts by weight, based on 100 parts by weight of the total solid content in the composition for forming an underlayer film. In particular, in the lower layer film-forming composition containing the polymer (i), it is preferable to add an acid generator for the purpose of promoting the condensation reaction of the polymer (i) after coating the composition.

The composition for forming the lower layer film may further contain a storage stabilizer, a defoaming agent, an adhesion aid and the like. The composition for forming the lower layer film is usually used for forming the lower layer film after being filtered with a filter having a pore size of about 0.1 μm, for example.

Acid-Dissociable Group-Containing Polysiloxane The acid-dissociable group-containing polysiloxane in the present invention includes an alkali-insoluble or alkali-insoluble acid-dissociable group-containing alkali-dissolvable group when the acid-dissociable group is dissociated. As long as it is a polysiloxane, it is not particularly limited, but in particular, (I) a structural unit represented by the following general formula (2) (hereinafter referred to as “structural unit (2)”) and / or the above-mentioned general. Structural unit represented by formula (3) (hereinafter,
It is called “Structural Unit (3)”. ) Containing a polymer (hereinafter,
It is called "polysiloxane (I)". ) Is preferred.

[0068]

[Chemical 11] [In the general formula (2) and the general formula (3), A ¹ and A ² each independently represent a monovalent organic group having an acid dissociable group which is dissociated by an acid, and R ⁴ has 1 to 10 carbon atoms. Linear, branched or cyclic alkyl group of, or having 1 carbon atom
10 represents a linear, branched or cyclic halogenated alkyl group. ]

In the general formulas (2) and (3), the monovalent organic group having an acid dissociable group which is dissociated by an acid of A ¹ and A ² is preferably a carboxyl group which is dissociated by an acid. A linear or branched hydrocarbon group having 1 to 20 carbon atoms having one or more acid dissociable groups which generate a phenolic hydroxyl group or an alcoholic hydroxyl group, and a carbon group having 4 to 30 carbon atoms having the acid dissociable group Mention may be made of groups which are stable under the reaction conditions for producing polysiloxane (I), such as monovalent cyclic hydrocarbon groups.

The acid dissociable group is represented by the following general formula (1
The group represented by 0) is preferable.

[Chemical 12] [In the general formula (10), P is a single bond, a methylene group,
Difluoromethylene group, optionally substituted carbon number 2
To C20 linear or branched alkylene group, an optionally substituted divalent aromatic group having 6 to 20 carbon atoms, or an optionally substituted divalent alicyclic group having 3 to 20 carbon atoms. represents a group, Q is shows a -COO- or -O-, R ⁸ is a monovalent organic group which produces a hydrogen atom is dissociated by acid. ]

In the general formula (10), the carbon number of P is 2 to 2
As the linear or branched alkylene group of 20,
For example, ethylene group, propylene group, trimethylene group,
Examples thereof include a tetramethylene group, which has 6 to 2 carbon atoms.
As the divalent aromatic group of 0, for example, a phenylene group,
A naphthylene group and the like can be mentioned, and the number of carbon atoms is 3 to 2.
Examples of the divalent alicyclic group of 0 include a cycloalkylene group such as a cyclopropylene group, a cyclobutylene group and a cyclohexylene group, a norbornane skeleton, a tricyclodecane skeleton,
Examples thereof include a divalent hydrocarbon group having a bridged alicyclic skeleton such as a tetracyclodecane skeleton and an adamantane skeleton.

The alkylene group, the divalent aromatic group or the divalent alicyclic group has a fluorine atom or a linear or branched fluorinated alkyl group having 1 to 10 carbon atoms. Is preferred. The divalent aromatic group or divalent alicyclic group is a methylene group, a difluoromethylene group, a linear or branched alkylene group having 1 to 10 carbon atoms, or a linear chain having 1 to 10 carbon atoms. It may have a branched or branched fluorinated alkylene group.

P in the general formula (10) is preferably a single bond, a methylene group, a difluoromethylene group, a divalent hydrocarbon group having a tricyclodecane skeleton, a fluorinated product thereof, or a divalent hydrocarbon having an adamantane skeleton. Group, its fluorinated compound, a divalent hydrocarbon group having a norbornane skeleton, its fluorinated compound, and the like.
A divalent hydrocarbon group having a norbornane skeleton and a fluorinated product thereof are preferable.

Examples of the monovalent organic group which is dissociated by the acid of R ⁸ to generate a hydrogen atom include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i- Butyl group, sec-butyl group, t-butyl group,
Cyclopentyl group, 1-methylcyclopentyl group, 1-
Ethylcyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 4
A linear, branched or cyclic alkyl group such as -t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group; alkyl-substituted adamantyl group such as 1-methyladamantyl group, 1-ethyladamantyl group; benzyl group, 4 -T-butylbenzyl group, phenethyl group, 4-t
-Aralkyl group such as butylphenethyl group; t-butoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, 2- (trimethylsilyl) ethylcarbonyl group, i-butylcarbonyl group, vinylcarbonyl group, allylcarbonyl group Groups, organic carbonyl groups such as benzylcarbonyl group, 4-ethoxy-1-naphthylcarbonyl group;

Methoxymethyl group, methylthiomethyl group,
Ethoxymethyl group, t-butoxymethyl group, (phenyldimethylsilyl) methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, siloxymethyl group, 2-
Methoxyethoxymethyl group, 2,2,2-trichloroethoxymethyl group, bis (2-chloroethoxy) methyl group, 1-methoxycyclohexyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, 1 -Methoxyethyl group, 1-ethoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1
General formula (-methyl-1-methoxyethyl group, 1-methyl-1-benzyloxyethyl group, 1- (2-chloroethoxy) ethyl group, 1-methyl-1-benzyloxy-2-fluoroethyl group, etc. 10) an organic group which is bonded to an oxygen atom in the group to form an acetal structure; a trimethylsilyl group,
Examples thereof include a silyl group such as a triethylsilyl group, a dimethylethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group and a t-butylmethoxyphenylsilyl group. .

Among the monovalent organic groups which are dissociated by these acids to generate hydrogen atoms, t-butyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, A 1-ethoxyethyl group, a t-butyldimethylsilyl group and the like are preferable.

In the general formula (3), examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ⁴ include, for example, methyl group, ethyl group, n-propyl group and i- Examples thereof include a propyl group, a cyclopentyl group, a cyclohexyl group, a straight chain having 1 to 10 carbon atoms,
As the branched or cyclic halogenated alkyl group,
For example, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoro-i-propyl group, a perfluorocyclohexyl group and the like can be mentioned. R ⁴ in the general formula (3) is preferably a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group or the like.

The polysiloxane (I) can also have at least one other structural unit having no acid dissociable group. Examples of such other structural unit include structural units represented by the following general formula (11) (hereinafter referred to as “structural unit (11)”) and structural units represented by the following general formula (12) (hereinafter referred to as “structural unit (11)”). , "Structural unit (12)") and the like,

[0079]

[Chemical 13] [In the general formula (11) and the general formula (12), each R
⁹ are, independently of one another, of the formula --P--H, --P--F or --P--
A monovalent group represented by Q-H (however, each P is independently of each other, as defined in the general formula (10), and Q is as defined in the general formula (10)). And R ⁴ is as defined in the general formula (3). ]

In the general formula (11) and the general formula (12), preferred specific examples of the monovalent group of R ⁹ include groups represented by the following general formulas (13) to (18) and methyl groups. Group, ethyl group, norbornyl group, tetracyclodecanyl group and the like.

[0081]

[Chemical 14] [In the general formula (13), each R ¹⁰ is independently a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a halogen atom other than a fluorine atom, an alkyl group having 1 to 10 carbon atoms, or A monovalent organic group having an acid-dissociable group dissociated by an acid is shown, and each R ¹¹ is independently a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom,
A halogen atom other than a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and 5 R ¹⁰ and 2i R ¹¹
At least one of them is a fluorine atom or a fluorinated alkyl group having 1 to 10 carbon atoms, and i is an integer of 0 to 10. ]

[0082]

[Chemical 15] [In the general formula (14), each R ¹⁰ is independently a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a halogen atom other than a fluorine atom, an alkyl group having 1 to 10 carbon atoms, or A monovalent organic group having an acid-dissociable group dissociated by an acid is shown, and each R ¹¹ is independently a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom,
A halogen atom other than a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and 7 R ¹⁰ and 2i R ¹¹
At least one of them is a fluorine atom or a fluorinated alkyl group having 1 to 10 carbon atoms, and i is an integer of 0 to 10. ]

[0083]

[Chemical 16] [In the general formula (15), each R ¹⁰ is independently a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a halogen atom other than a fluorine atom, an alkyl group having 1 to 10 carbon atoms, or A monovalent organic group having an acid-dissociable group dissociated by an acid is shown, and each R ¹¹ is independently a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom,
A halogen atom other than a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and 7 R ¹⁰ and 2i R ¹¹
At least one of them is a fluorine atom or a fluorinated alkyl group having 1 to 10 carbon atoms, and i is an integer of 0 to 10. ]

[0084]

[Chemical 17] [In the general formula (16), each R ¹⁰ is independently a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a halogen atom other than a fluorine atom, an alkyl group having 1 to 10 carbon atoms, or A monovalent organic group having an acid-dissociable group dissociated by an acid is shown, and each R ¹¹ is independently a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom,
A halogen atom other than a fluorine atom or an alkyl group having 1 to 10 carbon atoms, and (3 + 2j) R ¹⁰ and 2
At least one of i R ¹¹ is a fluorine atom or a fluorinated alkyl group having 1 to 10 carbon atoms, i is an integer of 0 to 10, and j is an integer of 1 to 18. ]

[0085]

[Chemical 18] [In the general formula (17), one of the (12 + 6k) R ¹⁰ 's represents a group — [C (R ¹¹ ) ₂ ] _i — and the remaining R 10
¹⁰ independently has a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a halogen atom other than a fluorine atom, an alkyl group having 1 to 10 carbon atoms, or an acid dissociable group dissociated by an acid. Represents a monovalent organic group, and each R ¹¹ independently represents a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms, a hydrogen atom, a halogen atom other than a fluorine atom, or an alkyl group having 1 to 10 carbon atoms. , And (11+
6k) at least one of the remaining R ¹⁰ and 2i R ¹¹ is a fluorine atom or a fluorinated alkyl group having 1 to 10 carbon atoms, i is an integer of 0 to 10, and k is 0 to 3
Is an integer. ]

[0086]

[Chemical 19] [In the general formula (18), one of 16 R ¹⁰ 's represents a group-[C (R ¹¹ ) ₂ ] _i- , and each of the remaining R ¹⁰ 's independently represents a fluorine atom, a carbon number of 1 to 1]. 10 fluorinated alkyl groups, hydrogen atoms, halogen atoms other than fluorine atoms, alkyl groups having 1 to 10 carbon atoms, or monovalent organic groups having an acid dissociable group that dissociates with an acid, and each R ¹¹ is mutually Independently, a fluorine atom, a fluorinated alkyl group having 1 to 10 carbon atoms,
It represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms other than a fluorine atom, and 15 of the remaining R ¹⁰
And at least one of 2i R ¹¹ is a fluorine atom or a fluorinated alkyl group having 1 to 10 carbon atoms. ]

The polysiloxane (I) is, for example, a compound represented by the following general formula (19) (hereinafter referred to as "silane compound (19)"), a linear chain obtained by partially condensing the silane compound (19), or A cyclic oligomer, a compound represented by the following general formula (20) (hereinafter referred to as "silane compound (2
0) ”. ) And at least one member of the group consisting of linear or cyclic oligomers partially condensed with the silane compound (20) in the presence of an acidic catalyst or a basic catalyst.
It can be produced by a method having a step of polycondensing, preferably in the presence of an acidic catalyst.

[0088]

[Chemical 20] [In the general formula (19) and the general formula (20), A ¹
Is as defined in the general formula (2), and A ² and R
⁴ is as defined in the general formula (3), and each R ¹² independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. R in the general formula (19) and the general formula (20)
¹² is preferably an alkyl group having 1 to 10 carbon atoms,
Particularly, a methyl group and an ethyl group are preferable.

The "linear or cyclic oligomer partially condensed with the silane compound (19)" referred to herein is a linear chain formed by condensation between two R ¹² O-Si groups in the silane compound (19). In the case of a linear oligomer, it is usually a dimer to a dimer,
In the case of a cyclic oligomer, which preferably forms a dimer to a pentamer, it usually means an oligomer which forms a dimer to a trimer, preferably a trimer to a pentamer, and also "silane compound (20)"
Is a partially condensed linear or cyclic oligomer ",
In the case of a straight-chain oligomer, it is condensed between two R ¹² O-Si groups in the silane compound (20) to usually form a 2- to 10-mer, preferably a 2- to 5-mer, and form a ring. In the case of the oligomer of (3), it usually means an oligomer which forms a 3 to 10 mer, preferably a 3 to 5 mer.

The silane compound (19) and the silane compound (20) can be used alone or in admixture of two or more. Further, in the present invention, one or more kinds of other silane compounds can be used together with the silane compound (19) and the silane compound (20) or a partial condensate of these silane compounds. Examples of the other silane compound include a silane compound represented by the following general formula (21) (hereinafter referred to as “silane compound (21)”), a silane compound represented by the following general formula (22) (hereinafter referred to as “silane compound (21)”). , "Silane compound (22)") and partial condensates of these silane compounds. The "partial condensate" referred to here is a linear oligomer in which each silane compound usually forms a dimer to a dimer, preferably a dimer to a pentamer, or usually a dimer to a trimer, Preferably, it means a cyclic oligomer having a trimer to pentamer.

[0091]

[Chemical 21]

[In the general formulas (21) and (22), R ⁴ is as defined in the general formula (3),
R ⁹ is as defined in the general formula (11) and the general formula (12), and each R ¹² is as defined in the general formula (19) and the general formula (20). ] As R < ¹² > in General formula (21) and General formula (22), a C1-C10 alkyl group is preferable, Especially,
A methyl group and an ethyl group are preferred.

In the present invention, the silane compound (21)
And at least one selected from the group of silane compounds (22) or their partial condensates, preferably silane compounds (2
1) or a partial condensate thereof is converted into a silane compound (19)
And the silane compound (20) or a partial condensate thereof can be co-condensed to control the molecular weight and the glass transition temperature (Tg) of the resulting polysiloxane (I), and can be 193 nm or less, particularly 193 nm and 157.
The transparency at the wavelength of nm can be further improved. The total amount of the silane compound (21), the silane compound (22) or a partial condensate thereof is usually 1 mol% or more, preferably 5 to 9 based on the total amount of the silane compounds.
It is 5 mol%, more preferably 10 to 90 mol%.
In this case, if the total amount used is less than 1 mol%, especially 1
Transparency at wavelengths of 93 nm and 157 nm tends to decrease.

Among the acidic catalysts used in the production of polysiloxane (I), examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, aluminum chloride and the like. Examples of the organic acids include formic acid, acetic acid, n-propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid,
Acetic anhydride, maleic anhydride, citric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and the like can be mentioned. Of these acidic catalysts, hydrochloric acid,
Preference is given to sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, maleic anhydride and the like. The acidic catalysts may be used alone or in combination of two or more. The amount of acidic catalyst used is 1 total amount of silane compound.
It is usually 0.01 to 10,000 parts by weight, preferably 0.1 to 100 parts by weight, based on 00 parts by weight.

Among the basic catalysts used in the production of polysiloxane (I), inorganic bases include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and hydrogen carbonate. sodium,
Examples thereof include potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like.

Examples of organic bases include n-
Linear, branched or cyclic monoalkylamines such as hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n-butylamine, di-n-pentyl Linear, branched or amine-, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Cyclic dialkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine,
Straight-chain such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine and tricyclohexylamine,
Branched or cyclic trialkylamines;

Aniline, N-methylaniline, N, N-
Aromatic amines such as dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine; ethylenediamine, N, N, N ',
N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4 '
-Diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl)-
2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1, 4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-
Bis [1- (4-aminophenyl) -1-methylethyl
] Aromatic diamines such as benzene;

Imidazole, benzimidazole, 4-
Imidazoles such as methylimidazole and 4-methyl-2-phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-
Pyridines such as ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline and acridine; piperazine , Piperazine such as 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinozalin, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine,
1,4-dimethylpiperazine, 1,4-diazabicyclo
[2.2.2] Other nitrogen-containing heterocyclic compounds such as octane can be mentioned.

Of these basic catalysts, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and the like are preferable. The basic catalysts may be used alone or in combination of two or more. The amount of the basic catalyst used is usually 0.01 to 10,000 parts by weight, preferably 0.1 to 1,000 parts by weight, based on 100 parts by weight of the total amount of the silane compound.

In the polycondensation reaction for producing the polysiloxane (I), it is preferable that the silane compound is polycondensed in the presence of an acidic catalyst, and then a basic catalyst is added to further advance the reaction. By carrying out such a reaction, a crosslinking reaction can be caused even when a silane compound having an acid dissociable group which is unstable under acidic conditions is used, and the molecular weight and the glass transition temperature (Tg) are high. Thus, it becomes possible to obtain the polysiloxane (I) having good characteristics. Further, the solubility of the resulting polysiloxane (I) in a developing solution can be adjusted by controlling the degree of crosslinking by adjusting the reaction conditions under basic conditions.

The polycondensation reaction under the acidic conditions and the basic conditions is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, which makes it difficult for the pattern formation layer to be negative during pattern formation. .

The polycondensation reaction can be carried out without a solvent or in a solvent. Examples of the solvent include 2-butanone, 2-pentanone, and 3-methyl-2.
-Linear or branched ketones such as butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone Kinds; cyclopentanone,
3-methylcyclopentanone, cyclohexanone, 2-
Cyclic ketones such as methylcyclohexanone, 2,6-dimethylcyclohexanone and isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate , Propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-
Propylene glycol monoalkyl ether acetates such as butyl ether acetate and propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, 2-
Alkyl 2-hydroxypropionate such as i-propyl hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, and t-butyl 2-hydroxypropionate. Kinds; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-
Alkyl 3-alkoxypropionates such as methyl ethoxypropionate and ethyl 3-ethoxypropionate;

N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-
Alcohols such as propyl ether; Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monoalkyl ether acetates such as ethylene glycol mono-n-propyl ether acetate;

Aromatic hydrocarbons such as toluene and xylene; ethyl 2-hydroxy-2-methylpropionate,
Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate,
In addition to other esters such as 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate, N- Methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol , Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and the like. These solvents may be used alone or in admixture of two or more. The amount of the solvent used is usually 2,0 per 100 parts by weight of the total amount of the silane compound.
It is not more than 00 parts by weight.

The polycondensation reaction is carried out in the absence of a solvent or in 2
-Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3
-Methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone, cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, Implemented in a solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate. Preferably.

Further, in the polycondensation reaction, water may be added to the reaction system. The amount of water added in this case is usually 100 parts by weight of the total amount of the silane compound.
It is 10,000 parts by weight or less. Further, in the polycondensation reaction, hexamethyldisiloxane can be added in order to control the molecular weight of the obtained polysiloxane (I) and improve the stability. The amount of hexamethyldisiloxane added is usually 500 parts by weight or less, preferably 5 parts by weight, based on 100 parts by weight of the total amount of silane compounds.
It is 0 parts by weight or less. In this case, when the amount of hexamethyldisiloxane added exceeds 500 parts by weight, the molecular weight of the obtained polymer tends to be small, and the glass transition temperature (Tg) tends to decrease. The reaction temperature in the polycondensation is
Usually, it is -50 to 300 ° C, preferably 20 to 100 ° C, and the reaction time is usually about 1 minute to 100 hours.

In the polysiloxane (I), the total content of the structural unit (2) and the structural unit (3) is usually from 1 to 99 mol%, preferably from 1 to 95, based on all structural units.
Mol%, more preferably 5 to 80 mol%, particularly preferably 10 to 60 mol%. In this case, if the total content is less than 1 mol%, the resolution at the time of pattern formation tends to decrease, while if it exceeds 99 mol%, the adhesion to the underlayer film tends to decrease.

The content of the structural unit (2) is preferably 1 to 95 mol%, more preferably 5 to 80 mol%, and particularly preferably 10 to 60 mol%, based on all structural units. In this case, if the content of the structural unit (2) is less than 1 mol%, the resolution at the time of pattern formation may decrease, while if it exceeds 95 mol%, the transparency of the resulting polymer to radiation tends to decrease. There is.

The content of the structural unit (3) is preferably 95 mol% or less, more preferably 80 mol% or less, particularly preferably 30 mol% or less, based on all structural units. In this case, when the content of the structural unit (3) exceeds 95 mol%, the glass transition temperature (T
g) and the transparency to radiation tend to decrease.

The total content of the structural unit (11) and the structural unit (12) optionally contained in the polysiloxane (I) is preferably 5 to 9 with respect to all structural units.
It is 5 mol%, more preferably 20 to 95 mol%, and particularly preferably 40 to 90 mol%. In this case, if the content of the structural unit is less than 5 mol%, the transparency of the resulting polymer to radiation may be decreased, while 95
If it exceeds mol%, the resolution during pattern formation may decrease. Polysiloxane (I) partially has a ladder structure. This ladder structure is basically introduced by the structural unit (2) and the structural unit (11).

The Mw of the acid-labile group-containing polysiloxane is
Usually, 500 to 100,000, preferably 500 to 5
30,000, particularly preferably 1,000 to 10,000
Is. In this case, M of the acid dissociable group-containing polysiloxane
When w is less than 500, the glass transition temperature (Tg) of the obtained polymer tends to decrease, while 100,000 is obtained.
When it exceeds, the solubility of the obtained polymer in a solvent tends to decrease. The Mw / Mn of the acid-dissociable group-containing polysiloxane is 2.5 or less, preferably 2 or less, more preferably 1.8 or less. The glass transition temperature (Tg) of the acid-dissociable group-containing polysiloxane is usually 0.
-500 degreeC, Preferably it is 50-250 degreeC. In this case, if the glass transition temperature (Tg) of the acid-dissociable group-containing polysiloxane is less than 0 ° C, it may be difficult to form a pattern. On the other hand, if it exceeds 500 ° C, the solubility of the obtained polymer in a solvent is increased. Tends to decrease. In the present invention, the acid-dissociable group-containing polysiloxane can be used alone or in admixture of two or more.

Multilayer Film for Pattern Formation In the present invention, when a pattern is formed, a radiation-sensitive resin composition containing an acid dissociable group-containing polysiloxane (hereinafter referred to as a radiation-sensitive resin composition) is formed on a film containing a polymer for an underlayer film. , "The composition for pattern formation") to form a multilayer film for pattern formation, and then the multilayer film for pattern formation is used to form a pattern by a conventional method.

Pattern-Forming Composition The pattern-forming composition used in the invention is usually
A composition containing an acid-dissociable group-containing polysiloxane and a radiation-sensitive acid generator (hereinafter, simply referred to as “acid generator”) and, if necessary, further containing an additive to be described later is used. The composition is usually a solution dissolved in a solvent (hereinafter, referred to as “pattern forming composition solution”).
Is prepared as.

The acid generator is a component that generates an acid upon irradiation with radiation (hereinafter referred to as "exposure"), and the action of the acid causes the acid dissociable group present in the acid dissociable group-containing polysiloxane. Is dissociated, and as a result, the exposed part of the film (hereinafter referred to as “resist film”) formed from the composition for pattern formation becomes soluble in the alkali developing solution and has the function of forming a positive pattern. Examples of such an acid generator include onium salts, halogen-containing compounds, diazoketone compounds, sulfone compounds,
A sulfonic acid compound etc. can be mentioned. Hereinafter, these acid generators will be described.

Onium salt: Examples of the onium salt include iodonium salt, sulfonium salt (including tetrahydrothiophenium salt), phosphonium salt, diazonium salt, pyridinium salt and the like. Specific examples of preferable onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium heptadecafluoro-n-octanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyl. Iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-
t-butylphenyl) iodonium nonafluoro-n-
Butane sulfonate, bis (4-t-butylphenyl)
Iodonium heptadecafluoro-n-octane sulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzene sulfonate, bis (4-t-
Butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium naphthalene sulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium heptadecafluoro-n-octane Sulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium 10-camphor sulfonate,

4-hydroxyphenyl phenyl methylsulfonium p-toluene sulfonate, cyclohexyl 2-oxocyclohexyl methylsulfonium trifluoromethane sulfonate, cyclohexyl
2-oxocyclohexyl-methylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl-2
-Oxocyclohexyl-methylsulfonium heptadecafluoro-n-octane sulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium nonafluoro-n-butanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium heptadeca Fluoro-n-octane sulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium nonafluoro-
n-butane sulfonate, 2-oxocyclohexyl dimethyl sulfonium heptadecafluoro-n-octane sulfonate, 4-hydroxyphenyl benzyl methyl sulfonium p-toluene sulfonate, 1-naphthyl dimethyl sulfonium trifluoro methane sulfonate, 1-naphthyl dimethyl sulfonium nonafluoro -N-butanesulfonate, 1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 1-naphthyldiethylsulfonium heptadecafluoro -N-octane sulfonate,

4-Cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-
1-naphthyldimethylsulfonium nonafluoro-n-
Butanesulfonate, 4-cyano-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1
-Naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-
Naphthyl dimethyl sulfonium nonafluoro-n-butane sulfonate, 4-nitro-1-naphthyl dimethyl sulfonium heptadecafluoro-n-octane sulfonate, 4-nitro-1-naphthyl diethyl sulfonium trifluoromethane sulfonate, 4-nitro-1-naphthyl diethyl Sulfonium nonafluoro-n-butane sulfonate, 4-nitro-1-naphthyl diethyl sulfonium heptadecafluoro-n-octane sulfonate,

4-Methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-
1-naphthyldimethylsulfonium nonafluoro-n-
Butanesulfonate, 4-methyl-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1
-Naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyl Dimethylsulfonium nonafluoro-
n-butanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4
-Hydroxy-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-hydroxy-
1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate,

(1-4-hydroxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthalene) -1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxymethoxynaphthalene-
1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (1-methoxyethoxy) naphthalen-1-yl] Tetrahydrothiophenium trifluoromethanesulfonate, 1- [4-
(2-Methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxycarbonyloxynaphthalene-
1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-propoxycarbonyloxynaphthalen-1-yl) Tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothio Phenium trifluoromethanesulfonate, 1- (4
-T-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4 -(2
-Tetrahydropyranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-benzyloxynaphthalene-1
-Yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl)
Tetrahydrothiophenium nonafluoro-n-butane sulfonate etc. can be mentioned.

Halogen-containing compound: Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferable halogen-containing compounds include phenylbis (trichloromethyl) -s-triazine and 4-methoxyphenylbis (trichloromethyl)-.
(Trichloromethyl) -s- such as s-triazine and 1-naphthylbis (trichloromethyl) -s-triazine
Examples thereof include triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane. Diazoketone compound: Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Specific examples of preferred diazoketones include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphtho of 2,3,4,4′-tetrahydroxybenzophenone. Quinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-
5-sulfonic acid ester; 1,1,1-tris (4-hydroxyphenyl) ethane 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester You can

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Specific examples of preferable sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane. Sulfonic acid compound: Examples of the sulfonic acid compound include alkyl sulfonic acid ester, alkyl sulfonic acid imide, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, and imino sulfonate. Specific examples of preferable sulfonic acid compounds include benzoin tosylate, tris (trifluoromethanesulfonate) of pyrogallol, and nitrobenzyl-.
9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.
1] hept-5-ene-2,3-dicarbodiimide, N
-Hydroxysuccinimide trifluoromethane sulfonate, 1,8-naphthalene dicarboximide trifluoromethane sulfonate, etc. can be mentioned.

Among these acid generators, particularly diphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl)
Iodonium nonafluoro-n-butane sulfonate,
Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-
Oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) Tetrahydrothiophenium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, 1,
8-naphthalene dicarboximide trifluoromethane sulfonate and the like are preferable.

The acid generators may be used alone or in admixture of two or more. The amount of the acid generator used in the composition for pattern formation is usually 0.1 to 10 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the acid-dissociable group-containing polysiloxane, from the viewpoint of ensuring sensitivity and developability. It is 0.5 to 7 parts by weight. In this case, if the amount of the acid generator used is less than 0.1 parts by weight, the sensitivity and developability tend to decrease, while if it exceeds 10 parts by weight, the transparency to radiation decreases and the pattern shape is impaired. May be

The solvent used in the pattern forming composition solution is not particularly limited as long as it can dissolve the acid-dissociable group-containing polysiloxane, the acid generator and the additive component, but for example, 2 -Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-
Linear or branched ketones such as methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone; cyclopentanone, 3-methyl Cyclopentanone,
Cyclohexanone, 2-methylcyclohexanone, 2,
Cyclic ketones such as 6-dimethylcyclohexanone and isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono- Propylene glycol monoalkyl ether acetates such as n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, 2- Ethyl hydroxypropionate, n-propyl 2-hydroxypropionate 2-hydroxypropionic acid i- propyl, n- butyl 2-hydroxypropionic acid, 2-
Alkyl 2-hydroxypropionates such as i-butyl hydroxypropionate, sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate,
In addition to alkyl 3-alkoxypropionates such as ethyl 3-ethoxypropionate,

N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, N-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzylethyl ether, di -N-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid,
Examples thereof include 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate and propylene carbonate.

These solvents may be used alone or in admixture of two or more, but among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates , Alkyl 2-hydroxypropionates and alkyl 3-alkoxypropionates are preferred.

The amount of the solvent used in the pattern forming composition solution is such that the total solid content concentration in the solution is usually 1 to 25% by weight, preferably 2 to 15% by weight.

Various additives such as an acid diffusion control agent, a dissolution control agent and a surfactant can be added to the pattern forming composition of the present invention. The acid diffusion control agent is a component having an action of controlling the diffusion phenomenon of the acid generated from the acid generator upon exposure in the resist film and suppressing an undesired chemical reaction in the non-exposed region. By adding such an acid diffusion controller, the storage stability of the resulting composition is further improved and the resolution is improved, and the retention time (PED) from exposure to post-baking changes. The change in the line width of the pattern due to the above can be suppressed, and a composition having extremely excellent process stability can be obtained. As the acid diffusion controller, a nitrogen-containing organic compound whose basicity does not change due to exposure or baking during the pattern forming step is preferable. As such a nitrogen-containing organic compound, for example, the following general formula (23)

[0129]

[Chemical formula 22] [In the general formula (23), each R ¹³ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. ]

A compound represented by the following (hereinafter referred to as "nitrogen-containing compound (a)"), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen-containing compound (b)"),
Examples thereof include polymers having three or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (c)”), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

As the nitrogen-containing compound (a), for example, n
-Linear, branched or cyclic monoalkylamines such as -hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; di-n-butylamine, di-n- Linear or branched such as pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine Or cyclic dialkylamines; triethylamine,
Tri-n-propylamine, tri-n-butylamine,
Tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexyl Linear form such as amine,
Branched or cyclic trialkylamines; aniline, N-methylaniline, N, N-dimethylaniline,
2-methylaniline, 3-methylaniline, 4-methylaniline, 2,6-di-t-butylaniline, 2,6-
Di-t-butyl-N-methylaniline, 2,6-di-t
Aromatic amines such as -butyl-N, N-dimethylaniline, 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine can be mentioned.

Examples of the nitrogen-containing compound (b) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4 -Aminophenyl) propane, 2- (4-aminophenyl) -2-
(3-Hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-
Methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like can be mentioned. Examples of the nitrogen-containing compound (c) include polyethyleneimine, polyallylamine, and a polymer of 2-dimethylaminoethylacrylamide.

Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-
Adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4 ′ -Diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N'N'-tetra-t-butoxycarbonylhexamethylenediamine,
N, N'-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxycarbonyl- 1,9-diaminononane, N, N'-
Di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12
-Diaminododecane, N, N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt
-Butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, N
In addition to Nt-butoxycarbonyl group-containing amino compounds such as -t-butoxycarbonyl-2-phenylbenzimidazole, formamide, N-methylformamide,
Examples thereof include N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone and N-methylpyrrolidone.

Examples of the urea compound include urea, methylurea, 1,1-dimethylurea and 1,3-
Examples thereof include dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea and tri-n-butylthiourea. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine and 2-ethylpyridine. , 4-ethylpyridine, 2-phenylpyridine, 4-
Pyridines such as phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline and acridine; piperazine, 1- (2-hydroxyethyl) piperazine In addition to piperazines such as pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, etc. Can be mentioned.

Of these nitrogen-containing organic compounds, the nitrogen-containing compounds (a) and the nitrogen-containing heterocyclic compounds are preferable, and among the nitrogen-containing compounds (a), tri (cyclo) alkylamines are particularly preferable. Among the nitrogen heterocycles,
Pyridines and piperazines are particularly preferable. The acid diffusion control agent may be used alone or in combination of two or more. The compounding amount of the acid diffusion controlling agent is usually 15 parts by weight or less, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the acid dissociable group-containing polysiloxane. In this case, if the compounding amount of the acid diffusion controller exceeds 15 parts by weight, the sensitivity and the developability of the exposed area tend to decrease. The compounding amount of the acid diffusion control agent is 0.0
If the amount is less than 01 parts by weight, the pattern shape and dimensional fidelity may be reduced depending on the process conditions.

Examples of the dissolution control agent include compounds represented by the following general formula (24) or general formula (25).

[0137]

[Chemical formula 23] [In the general formula (24) and the general formula (25), each R
^14's each independently represent a hydrogen atom, a t-butyl group, a t-butoxycarbonyl group, a methoxymethyl group, an ethoxymethyl group, a 1-ethoxyethyl group or a tetrahydropyranyl group. ]

The content of the dissolution control agent is usually 2 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the acid-dissociable group-containing polysiloxane.

The above-mentioned surfactant is a component having an effect of improving the coating property, the developing property and the like. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene n-.
In addition to nonionic surfactants such as octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether, polyethylene glycol dilaurate and polyethylene glycol distearate, KP341 under the trade name
(Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, the same No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF3
01, the same EF303, the same EF352 (manufactured by Tochem Products Co., Ltd.), Megafax F171, the same F173
(Manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC4
30, the same FC431 (Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, the same SC-
101, same SC-102, same SC-103, same SC-1
04, SC-105, SC-106 (Asahi Glass Co., Ltd.
Manufactured) and the like. These surfactants are
They can be used alone or in combination of two or more. The content of the surfactant is usually 100 parts by weight based on 100 parts by weight of the acid dissociable group-containing polysiloxane and the acid generator.
It is 2 parts by weight or less. Further, as additives other than the above,
An antihalation agent, an adhesion aid, a storage stabilizer, an antifoaming agent and the like can be added. The composition solution for pattern formation is usually used for pattern formation after being filtered with a filter having a pore size of about 0.2 μm, for example.

Pattern Forming Method As the pattern forming method of the present invention, for example, 1) a step of applying a composition for forming an underlayer film on a substrate and baking the obtained coating film to form an underlayer film, 2 ) A step of applying a pattern forming composition solution on the lower layer film, baking the obtained coating film to form a film (hereinafter referred to as “resist film”), and obtaining a pattern forming multilayer film, 3) a step of selectively exposing the resist coating to radiation through an exposure mask; and 4) a step of developing the exposed resist coating to form a resist pattern, and 5) if necessary. A method including a step of etching the lower layer film using the resist pattern as a mask can be mentioned.

As the substrate used for pattern formation,
Although not particularly limited, for example, an inorganic substrate such as a silicon oxide film or an interlayer insulating film can be used.

In the step 1), the composition for forming the lower layer film is applied onto the substrate by an appropriate method such as spin coating, cast coating or roll coating, and the obtained coating film is baked. The lower layer film is formed by volatilizing the solvent in the coating film. The baking temperature at this time is, for example, 90 to 5
The temperature is 00 ° C, preferably 200 to 450 ° C. The thickness of the lower layer film is usually 10 to 10,000 nm, preferably 5
It is 0 to 1,000 nm.

Then, in the step 2), the composition solution for pattern formation is applied onto the lower layer film by, for example, spin coating, cast coating, roll coating or the like so that the resulting resist coating has a predetermined film thickness. After applying by a suitable method, the resulting coating film is pre-baked to volatilize the solvent in the coating film to form a resist coating film and obtain a multilayer film for pattern formation. The temperature of the prebaking at this time is appropriately adjusted depending on the composition of the pattern forming composition used, etc., but is usually 30 to 200 ° C., preferably 50 to 160.
℃. The film thickness of the resist film is usually 10 to 10,
000 nm, preferably 50 to 1,000 nm, particularly preferably 70 to 300 nm.

Then, in step 3), the resist film is selectively exposed to radiation through an exposure mask.
As the radiation used for exposure, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, γ rays, molecular beams, ion beams, etc. are appropriately selected and used according to the composition of the pattern forming composition used. However, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 15)
7 nm), far ultraviolet rays such as extreme far ultraviolet rays (EUV), or X-rays are preferable, and ArF excimer laser and F ₂ excimer laser are more preferable.

Next, in step 4), the resist film after exposure is developed to form a resist pattern.
Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0]-
7-undecene, 1,5-diazabicyclo- [4.3.
Examples thereof include an alkaline aqueous solution in which 0] -5-nonene and the like are dissolved. Further, to these alkaline aqueous solutions, a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, and a surfactant can be added in appropriate amounts. Then, by washing and drying, a desired resist pattern is formed. In this process, the resolution,
In order to improve the pattern shape, developability, etc., post-baking may be performed before development.

Further, if necessary, in the step 5), the resist pattern obtained is used as a mask and gas plasma such as fluorine plasma, chlorine plasma or bromine plasma is used to etch the lower layer film to obtain a desired pattern. To form. However, the pattern forming method of the present invention is not limited to the above method.

[0147]

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In the following description, parts and% are by weight unless otherwise specified. In the following synthesis examples, Mw of the obtained polymer is GP manufactured by Tosoh Corporation.
C column (G0000H _XL L: 2 pieces, G3000H
_XL L: 1), flow rate: 1.0 ml / min,
Gel permeation chromatograph method (detector: differential refractometer) using monodisperse polystyrene as standard under analysis conditions of eluting solvent: tetrahydrofuran, column temperature: 40 ° C.
It was measured by.

Production Example 1-1 (Production of Polymer for Underlayer Film) In a separable flask equipped with a thermometer, under a nitrogen atmosphere,
Charge 100 parts of acenaphthylene, 78 parts of toluene, 52 parts of dioxane, 3 parts of azobisisobutyronitrile, and
The mixture was stirred at 0 ° C for 5 hours. Then, 5.2 parts of p-toluenesulfonic acid monohydrate and 40 parts of paraformaldehyde were added, the temperature was raised to 120 ° C., and the mixture was further stirred for 6 hours. Then, the reaction solution was poured into a large amount of isopropanol, the precipitated polymer was separated by filtration, and dried under reduced pressure at 40 ° C. to obtain a polymer. This polymer has an Mw of 2,0.
00, and as a result of ¹ H-NMR analysis, the following formula (26)
It was confirmed to have a structural unit represented by

[0149]

[Chemical formula 24]

Production Example 1-2 (Production of Polymer for Underlayer Film) In a separable flask equipped with a thermometer, under a nitrogen atmosphere, 6 parts of acenaphthylene, 5 parts of p-hydroxymethylstyrene, 48 parts of n-butyl acetate. , 4 parts of azobisisobutyronitrile were charged and polymerized at 75 ° C. for 7 hours while stirring. Then, the reaction solution was diluted with 100 parts of n-butyl acetate, poured into a large amount of water / methanol (weight ratio = 1/2), the precipitated polymer was filtered off, the solvent was distilled off, and Mw
Of 1,200 polymer was obtained.

Production Example 2 (Synthesis of Silane Compound) In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 76.0 g of triethoxysilane, 8-t-butoxycarbonyltetracyclo [4.4. 0.1 ^2,5 . 1
^7,10 ] Dodeca-3-ene (100 g) was added and the mixture was stirred at room temperature. Then, 5.0 ml of 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction. And heated to reflux at 150 ° C. for 75 hours. Then, the reaction solution was returned to room temperature, diluted with n-hexane, suction filtered on Celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the crude product was subjected to silica gel column chromatography to obtain 53 g of a reaction product as an n-hexane fraction. When the ¹ H-NMR spectrum (chemical shift σ) and the infrared absorption spectrum (IR) of this reaction product were measured, the measured values were as follows and were identified as the compounds represented by the following formula (27). Was done. σ: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group), 1.4 ppm (t-butyl group). IR: 2885 cm ^-1 (ethoxy group), 1726 cm ^-1
(Ester group), 1153 cm ^-1 (siloxane group), 1
080 cm ^-1 (siloxane group).

[0152]

[Chemical 25] [In Formula (27), the silicon atom is tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] bonded to the 3- or 4-position of the dodecane ring. ]

Production Example 3 (Synthesis of silane compound) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 38.8 g of triethoxysilane and 5- [2-hydroxy-2,2-di ( After adding 43.2 g of trifluoromethyl) ethyl] bicyclo [2.2.1] hept-2-ene and stirring at room temperature, 0.2 mol of chloroplatinic acid (H ₂ PtCl ₆ ) i-propyl alcohol. The reaction was started by adding 0.1 ml of the solution, and the mixture was heated under reflux at 100 ° C. for 30 hours. Then, the reaction solution was returned to room temperature, diluted with n-hexane, suction filtered on Celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the crude product was purified by vacuum distillation at 3 mmHg and 105 ° C.,
59.8 g of reaction products were obtained. The ¹ H-NMR spectrum (chemical shift σ) and the infrared absorption spectrum (IR) of this reaction product were measured, and the measured values were as follows and identified as the compound represented by the following formula (28). Was done. σ: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group). IR: 3400 cm ^-1 (hydroxyl group), 2878 cm ^-1 (methoxy group), 1215 cm ^-1 (C-F bond), 1082
cm ^-1 (siloxane group).

[0154]

[Chemical formula 26] [In the formula (28), the silicon atom is bicyclo [2.
2.1] It is bonded to the 2-position or 3-position of the heptane ring. ]

Production Example 4 (Synthesis of Silane Compound) To a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 3.0 g of the compound represented by the above formula (28) and 10 ml of tetrahydrofuran were added, The mixture was stirred under a nitrogen stream under ice-cooling, and when the temperature of the reaction solution reached 5 ° C or lower, 16.7 mg of 4-dimethylaminopyridine was added, and then 1.64 g of di-t-butyl dicarbonate was added to tetrahydrofuran. The solution dissolved in 5 ml was added dropwise over 15 minutes. After stirring for 1 hour after completion of dropping, the reaction solution was returned to room temperature and further stirred for 5 hours. afterwards,
50 ml of n-hexane was added to the reaction solution and the mixture was transferred to a separating funnel, and the organic layer was washed with ice water three times. afterwards,
The organic layer was transferred to a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled under reduced pressure to obtain a crude product. Then, the crude product was subjected to silica gel chromatography to obtain the reaction product 3.5 from the n-hexane fraction.
g was obtained. Nuclear magnetic resonance spectrum (chemical shift σ) and infrared absorption spectrum (I
R) was measured and the measured values were as follows:
It was identified as a compound represented by the following formula (29). σ: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group), 1.5 ppm (t-butyl group). IR: 3400 cm ^-1 (hydroxyl group), 2879 cm ^-1 (methoxy group), 1774 cm ^-1 (carbonic acid ester group), 12
21 cm ^-1 (C-F bond), 1082 cm ^-1 (siloxane group).

[0156]

[Chemical 27] [In the formula (29), the silicon atom is bicyclo [2.
2.1] It is bonded to the 2-position or 3-position of the heptane ring. ]

Production Example 5 (Synthesis of Silane Compound) In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 20.6 g of triethoxysilane and 5-trifluoromethyl-5-t-butoxycarbonylbicyclo were prepared. [2.
2.1] Hept-2-ene (25 g) was added, and the mixture was stirred at room temperature, then 0.2 mol i- of chloroplatinic acid (H ₂ PtCl ₆ ).
Add 1.0 ml of propyl alcohol solution,
The reaction was started and heated to reflux at 140 ° C. for 24 hours. Then, the reaction solution was returned to room temperature, diluted with n-hexane, suction filtered on Celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the crude product was
Purification by vacuum distillation at mHg and 140 ° C. gave 21 g of reaction product. The ¹ H-NMR spectrum (chemical shift σ) and infrared absorption spectrum (IR) of this reaction product were measured and the results were as follows, which was identified as the compound represented by the following formula (30). σ: 3.8 ppm (ethoxy group), 1.4 ppm (t
-Butyl group), 1.2 ppm (ethoxy group). IR: 1730 cm ^-1 (ester group), 1270 cm ^-1
(C—F bond), 1155 cm ⁻¹ (Si—O bond), 1
080 cm ^-1 (Si-O bond).

[0158]

[Chemical 28] [In the formula (30), the silicon atom is bicyclo [2.
2.1] It is bonded to the 2-position or 3-position of the heptane ring. ]

Production Example 6 (Production of Acid-Dissociable Group-Containing Polysiloxane) In a three-necked flask equipped with a stirrer, a cold flow condenser, and a thermometer, 8.34 g of the silane compound obtained in Production Example 2 and Production Example 3
12.92 g of the silane compound obtained in 1., 8.75 g of methyltriethoxysilane, 30 of 4-methyl-2-pentanone
g, and 7.20 g of a 1.75% oxalic acid aqueous solution were added, and the mixture was reacted with stirring at 80 ° C. for 6 hours. Then, cool the reaction vessel with ice to stop the reaction, transfer the reaction solution to a separatory funnel, discard the aqueous layer, further wash with ion-exchanged water to make the reaction solution neutral. Repeated washing with water. Then, the organic layer was distilled off under reduced pressure to obtain the polymer 18.5.
g was obtained. The ¹ H-NMR spectrum (chemical shift σ), Mw and Mn of this polymer were measured and the results were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ group),
1.4 ppm (t-butyl group), 0.2 ppm (SiC
H ₃ group). Mw: 2,300. Mw / Mn: 1.1.

Production Example 7 (Production of Acid-Dissociable Group-Containing Polysiloxane) In a three-necked flask equipped with a stirrer, a cold flow condenser, and a thermometer, 3.84 g of the silane compound obtained in Production Example 2 and Production Example 3
7.93 g of the silane compound obtained in 1., 3.22 g of methyltriethoxysilane, 15 g of 4-methyl-2-pentanone,
3.32 g of a 1.75% aqueous oxalic acid solution was added, and the mixture was reacted with stirring at 80 ° C. for 6 hours. Then, cool the reaction vessel with ice to stop the reaction, transfer the reaction solution to a separatory funnel, discard the aqueous layer, further wash with ion-exchanged water to make the reaction solution neutral. Repeated washing with water.
Then, the organic layer was distilled off under reduced pressure to obtain 8.24 g of a polymer. ¹ H-NMR spectrum (chemical shift σ), Mw and Mn of this polymer were measured,
It was as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ group),
1.4 ppm (t-butyl group), 0.2 ppm (SiC
H ₃ group). Mw: 2,200. Mw / Mn: 1.1.

Production Example 8 (Synthesis of Acid-Dissociable Group-Containing Polysiloxane) In a three-necked flask equipped with a stirrer, a cold flow cooler, and a thermometer, 1.90 g of the silane compound obtained in Production Example 2, Production Example 3
6.89 g of the silane compound obtained in 4., 1.21 g of the silane compound obtained in Production Example 4, 4-methyl-2-pentanone 10.
0 g, 1.75% oxalic acid aqueous solution 1.65 g are added,
The mixture was reacted at 40 ° C. for 10 hours while stirring. Then, after cooling the reaction solution with ice to stop the reaction, transfer it to a separating funnel, discard the aqueous layer, add ion-exchanged water and wash with water, and repeat washing with water until the reaction solution becomes neutral. It was Then, the organic layer was distilled off under reduced pressure to give a viscous oily polymer 7.5.
g was obtained. This polymer has Mw of 1,500 and Mw /
Mn was 1.1. Next, this polymer was dissolved in 22.5 g of 4-methyl-2-pentanone, 2.43 g of distilled water and 3.40 g of triethylamine were added,
The mixture was heated to 60 ° C. in a nitrogen stream and reacted for 5 hours. Then, the reaction solution was stirred while cooling with ice, and then oxalic acid 2.
An aqueous solution prepared by dissolving 83 g in 70 g of distilled water was added and stirring was continued. After that, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was further added to wash with water, and the washing with water was repeated until the reaction solution became neutral. Then, the organic layer was distilled off under reduced pressure to obtain 7.38 g of a solid polymer.
The ¹ H-NMR spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw and Mn of this polymer were measured and the results were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ group),
1.5 ppm (t-butoxycarbonyl group), 1.4 p
pm (t-butoxy group). IR: 1775 cm ^-1 (carbonic acid ester group), 17
26cm ^-1 (ester group), 1221cm ^-1 (C-F bond), 1133cm ^-1 (siloxane group). Mw: 2,300. Mw / Mn: 1.1.

Production Example 9 (Synthesis of Acid-Dissociable Group-Containing Polysiloxane) In a three-necked flask equipped with a stirrer, a cold flow condenser, and a thermometer, 1.28 g of the silane compound obtained in Production Example 2 and Production Example 3
3.30 g of the silane compound obtained in 3., 2.43 g of the silane compound obtained in Production Example 4, and 4-methyl-2-pentanone 7.0
g, and 1.10 g of a 1.75% oxalic acid aqueous solution were added, and the mixture was reacted with stirring at 40 ° C. for 10 hours. Then, after cooling the reaction solution with ice to stop the reaction, transfer it to a separating funnel, discard the aqueous layer, add ion-exchanged water and wash with water, and repeat washing with water until the reaction solution becomes neutral. It was Then, the organic layer was distilled off under reduced pressure to obtain a viscous oily polymer.
2 g was obtained. This polymer has Mw of 1,400, Mw
/ Mn was 1.1. The polymer is then 4-
It was dissolved in 16.0 g of methyl-2-pentanone, 1.63 g of distilled water and 2.28 g of triethylamine were added, and the mixture was heated at 60 ° C. in a nitrogen stream and reacted for 5 hours.
Then, the reaction solution was stirred while cooling with ice, and then an aqueous solution in which 1.90 g of oxalic acid was dissolved in 5 g of distilled water was added and stirring was continued. Then, transfer the reaction solution to a separating funnel,
Discard the aqueous layer, add ion-exchanged water and wash with water,
Washing with water was repeated until the reaction solution became neutral. afterwards,
The organic layer was distilled off under reduced pressure to obtain 5.03 g of a solid polymer. About this polymer, ¹ H-NMR spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw
When Mw / Mn was measured, it was as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ group),
1.5 ppm (t-butoxycarbonyl group), 1.4 p
pm (t-butoxy group). IR: 1776 cm ^-1 (carbonic acid ester group), 17
26cm ^-1 (ester group), 1221cm ^-1 (C-F bond), 1132cm ^-1 (siloxane group). Mw: 2,300. Mw / Mn: 1.1.

Production Example 10 (Synthesis of Acid-Dissociable Group-Containing Polysiloxane) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 17.98 g of the silane compound obtained in Production Example 3, Production Example 5 12.02 g of the silane compound obtained in 1., 4-methyl-2-
Pentanone 30 g, 1.75 wt% oxalic acid aqueous solution 5.
47 g was added and reacted at 80 ° C. for 6 hours while stirring. Then, after cooling the reaction vessel with ice to stop the reaction,
The mixture was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was further added, and the mixture was washed with water, and the washing with water was repeated until the reaction solution became neutral. Then, the organic layer was distilled off under reduced pressure to obtain a polymer. Next, this polymer was dissolved in 65.1 g of 4-methyl-2-pentanone, and further 8.06 g of distilled water was added.
11.31 g of triethylamine was added, and the mixture was heated to 60 ° C. in a nitrogen stream and reacted for 6 hours. Then, the reaction solution was stirred while cooling with ice, and then an aqueous solution in which 9.4 g of oxalic acid was dissolved in 188 g of distilled water was added and stirring was continued. After that, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was further added to wash with water, and the washing with water was repeated until the reaction solution became neutral. Then, the organic layer was distilled off under reduced pressure to obtain 21.2 g of a polymer. The obtained polymer Mw was 2,000 and Mw / Mn was 1.0.

Production Example 11 (Synthesis of Acid-Dissociable Group-Containing Polysiloxane) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 4.05 g of the silane compound obtained in Production Example 2 and Production Example 3
12.54 g of the silane compound obtained in 4., 3.42 g of the silane compound obtained in Production Example 5, and 4-methyl-2-pentanone 20.
g, 3.5 g of 1.75 wt% oxalic acid aqueous solution was added, and the mixture was reacted at 80 ° C. for 6 hours while stirring. Then, after cooling the reaction vessel with ice to stop the reaction, transfer it to a separating funnel, discard the aqueous layer, add ion-exchanged water and wash with water, and wash with water until the reaction solution becomes neutral. I repeated. Then, the organic layer was distilled off under reduced pressure to obtain a polymer. Then
44.1 g of this polymer 4-methyl-2-pentanone
Dissolved in water, 5.15 g of distilled water and 7.23 g of triethylamine were added, and the mixture was heated to 60 ° C. in a nitrogen stream,
Reacted for hours. Then, the reaction solution was stirred while cooling with ice, and then an aqueous solution in which 6.01 g of oxalic acid was dissolved in 120 g of distilled water was added and stirring was continued. After that, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was further added to wash with water, and the washing with water was repeated until the reaction solution became neutral. Then, the organic layer was distilled off under reduced pressure to obtain polymer 1
4.4 g was obtained. The Mw of the obtained polymer is 1,80.
0 and Mw / Mn were 1.0.

Preparation Example 1 (Preparation of composition for forming lower layer film) 10 parts of the polymer for lower layer film obtained in Production Example 1-1, bis (4-
t-Butylphenyl) iodonium 10-camphor-sulfonate 0.5 part, 4,4 ′-[1- {4- (1- [
4-Hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol (0.5 parts) and cyclohexanone (89 parts) were uniformly mixed and then filtered through a membrane filter having a pore size of 0.1 μm to give a composition for forming a lower layer film. Prepared.

Preparation Example 2 (Preparation of composition for forming lower layer film) 10 parts of the polymer for lower layer film obtained in Production Example 1-2, bis (4-
t-Butylphenyl) iodonium 10-camphor-sulfonate 0.5 part, 4,4 ′-[1- {4- (1- [
4-Hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol (0.5 parts) and ethyl lactate (89 parts) were uniformly mixed, and then filtered through a membrane filter having a pore size of 0.1 μm to form a lower layer film-forming composition. Was prepared.

Preparation Example 3 (Preparation of pattern forming composition solution) 50 parts of the acid-labile group-containing polysiloxane obtained in Preparation Example 6,
50 parts of the acid-labile group-containing polysiloxane obtained in Production Example 7,
After uniformly mixing 0.08 parts of tri-n-octylamine, 900 parts of 2-heptanone, and 1 part of triphenylsulfonium heptadecafluoro-n-octanesulfonate, the mixture was filtered with a membrane filter having a pore size of 0.45 μm to obtain a pattern. A forming composition solution was prepared.

Preparation Example 4 (Preparation of pattern forming composition solution) Acid dissociable group-containing polysiloxane 100 obtained in Preparation Example 8
Parts, tri-n-octylamine 0.08 parts, 2-heptanone 900 parts, and triphenylsulfonium heptadecafluoro-n-octanesulfonate 1 part were uniformly mixed, and then filtered through a membrane filter having a pore size of 0.45 μm. A pattern forming composition solution was prepared.

Preparation Example 5 (Preparation of pattern forming composition solution) Acid dissociable group-containing polysiloxane 100 obtained in Preparation Example 9
Parts, tri-n-octylamine 0.08 parts, 2-heptanone 900 parts, and triphenylsulfonium heptadecafluoro-n-octanesulfonate 1 part were uniformly mixed, and then filtered through a membrane filter having a pore size of 0.45 μm. A pattern forming composition solution was prepared.

Preparation Example 6 (Preparation of Composition Solution for Pattern Formation) Acid-Dissociable Group-Containing Polysiloxane 100 Obtained in Preparation Example 10
Part, 2-phenylbenzimidazole 0.32 part, 2-
Heptanone (900 parts), triphenylsulfonium nonafluoro-n-butanesulfonate (3 parts) and triphenylsulfonium 10-camphorsulfonate (1 part) were uniformly mixed and then filtered through a membrane filter having a pore size of 0.45 μm to obtain a pattern-forming composition. A solution was prepared.

Preparation Example 7 (Preparation of pattern forming composition solution) Acid dissociable group-containing polysiloxane 100 obtained in Preparation Example 11
Part, 2-phenylbenzimidazole 0.32 part, 2-
Heptanone (900 parts), triphenylsulfonium nonafluoro-n-butanesulfonate (3 parts) and triphenylsulfonium 10-camphorsulfonate (1 part) were uniformly mixed and then filtered through a membrane filter having a pore size of 0.45 μm to obtain a pattern-forming composition. A solution was prepared.

Evaluation Example 1 (Evaluation of SiO ₂ Etching Resistance) On a silicone wafer, the composition for forming an underlayer film obtained in Preparation Example 1, the composition for forming an underlayer film obtained in Preparation Example 2, or a general novolak resin was used. For each film formed from
The O ₂ etching rate was measured. The measurement was performed using an IEM etcher device manufactured by Tokyo Electron Ltd., etching gas C ₄ F ₈ / Ar / O ₂ = 11/400 / 8SCCM, vacuum degree 30 mTorr, cathode power Top / Bott.
om = 2000 / 1200w, substrate temperature Bottom /
Top / Wall = −20 / −30 / −40 ° C. and etching time was 30 seconds. As a result, the film formed from the composition for forming an underlayer film obtained in Preparation Example 1 had an etching rate of 50.1 nm / min, and the film formed from the composition for forming an underlayer film obtained in Preparation Example 2 had an etching rate of 52. 0.7 nm
/ Min, the film formed from the novolak resin has an etching rate of 63.7 nm / min, and the etching resistance of the film formed from the underlayer film-forming composition obtained in Preparation Example 1 and Preparation Example 2 is 1.27 and 1.21, respectively, based on the formed film, and the films formed from the lower layer film-forming compositions obtained in Preparation Example 1 and Preparation Example 2,
It has been revealed that the silicon wafer has extremely excellent dry etching resistance under the etching conditions for forming the contact hole.

Evaluation Example 2 (Evaluation of Etching Resistance of Organic Film) About each coating formed on the silicone wafer from the underlayer film forming composition obtained in Preparation Example 1 and the pattern forming composition solution obtained in Preparation Example 2 The etching rate of the organic film was measured. The measurement is Lam TCP-9400 manufactured by Lam
Etching gas O ₂ / SO ₂ = 230/1
0SCCM, vacuum degree 5mTorr, cathode power To
p / Bottom = 200 / 5w, substrate temperature = −5 ° C.,
The etching time was 30 seconds. As a result, the film formed from the pattern forming composition solution has an etching rate of 19.3 nm / min, and the film formed from the lower layer film forming composition has an etching rate of 512.0 nm / min. The etching resistance of the film formed from the composition composition solution is 26.5 based on the film formed from the lower layer film forming composition, and the film formed from the pattern forming composition solution is an organic film etching film. It was revealed that under the conditions, the film formed from the composition for forming an underlayer film had an extremely high dry etching resistance.

From the above evaluation results of the SiO ₂ etching resistance and the organic film etching resistance, the pattern forming method and the pattern forming multilayer film of the present invention were
It has been shown to be extremely useful in future lithography processes.

Evaluation Example 3 (n value and k value) The optical coefficient n value and k value of the film formed from the composition for forming an underlayer film obtained in Preparation Example 1 were measured. Table 1 shows the measured values at each wavelength.

[0176]

[Table 1]

As a result, it was revealed that the lower layer film formed from the lower layer film forming composition had an excellent antireflection effect even at a wavelength of 193 nm or less.

Comparative Example 1 (Evaluation by ArF Excimer Laser Exposure) The pattern forming composition solution obtained in Preparation Example 3 was applied onto a silicon wafer treated with hexamethyldisilazane by spin coating and then heated to 140 ° C. Prebaking is performed for 90 seconds on the retained hot plate to obtain a film thickness of 1
A 00 nm resist film was formed. Then, an ArF excimer laser (wavelength 19
(3 nm) to change the exposure amount, and post-bake for 90 seconds on a hot plate kept at 110 ° C., and then develop with a 2.38% tetramethylammonium hydroxide aqueous solution to obtain a line and -A space pattern (1L / 1S) was formed. As a result of observing the obtained pattern with a scanning electron microscope, although the image was resolved up to 0.16 μm, the roughness on the side surface of the pattern due to the standing wave was remarkable.

Reference Example 1 (Evaluation by ArF Excimer Laser Exposure) The composition solution for pattern formation obtained in Preparation Example 3 was spin-coated on a silicon wafer coated with a commercially available antireflection film DUV-30J to a thickness of 52 nm. After applying with 140
Prebaking was performed for 90 seconds on a hot plate kept at 0 ° C. to form a resist film having a film thickness of 100 nm.
Next, this resist film was exposed with an ArF excimer laser (wavelength 193 nm) while changing the exposure amount, and post-baked for 90 seconds on a hot plate maintained at 110 ° C., and then 2.38% tetra Development was carried out with an aqueous solution of methylammonium hydroxide to form a line and space pattern (1L / 1S). As a result of observing the obtained pattern with a scanning electron microscope, the pattern was resolved up to 0.14 μm, and the roughness of the side surface of the pattern due to the standing wave was hardly observed.

Example 1 (Evaluation by ArF Excimer Laser Exposure) The composition for forming an underlayer film obtained in Preparation Example 1 was applied onto a silicon wafer by spin coating so that an underlayer film with a thickness of 300 nm was obtained. Later on the hot plate 18
The underlayer film was formed by baking at 0 ° C. for 60 seconds and then at 300 ° C. for 120 seconds. Then, the composition solution for pattern formation obtained in Preparation Example 3 was applied onto the silicon wafer on which the lower layer film was formed by spin coating.
Prebaking was performed for 90 seconds on a hot plate kept at 0 ° C. to form a resist film having a film thickness of 100 nm. Then, an ArF excimer laser (wavelength 193 nm, numerical aperture (NA) = 0.5) was applied to this resist film.
5 and σ = 0.60), the exposure amount is changed to perform exposure.
After post-baking for 90 seconds on a hot plate kept at 0 ° C., development was performed with a 2.38% tetramethylammonium hydroxide aqueous solution to form a line-and-space pattern (1L / 1S). . As a result of observing the obtained pattern with a scanning electron microscope, 0.
The resolution was up to 14 μm, and the roughness of the pattern side surface due to the standing wave was hardly observed.

Examples 2 to 5 (Evaluation by ArF excimer laser exposure) In Example 1, instead of the pattern forming composition solution obtained in Preparation Example 3, each pattern forming composition obtained in Preparation Examples 4 to 7 was used. Example 1 except that the material solution was used and the temperature of both prebaking and postbaking was changed to 100 ° C.
Line and space pattern (1L
/ 1S) was formed. As a result of observing each of the obtained patterns with a scanning electron microscope, in each case, the resolution was down to 0.14 μm, and the roughness of the pattern side surface due to the standing wave was hardly observed.

Example 6 (Evaluation by ArF Excimer Laser Exposure) In Example 1, the underlayer film forming composition obtained in Preparation Example 2 was used in place of the underlayer film forming composition obtained in Preparation Example 1. A line and space pattern (1L / 1S) was formed in the same manner as in Example 1 except for the above. As a result of observing each of the obtained patterns with a scanning electron microscope, 0.14 μm
Up to this point, the roughness on the side surface of the pattern due to the standing wave was hardly observed.

Examples 7 to 10 (Evaluation by ArF excimer laser exposure) In Example 6, instead of the pattern forming composition solution obtained in Preparation Example 3, the pattern forming compositions obtained in Preparation Examples 4 to 7 were used. A line-and-space pattern (1 L / L) was used in the same manner as in Example 6 except that the solution was used and the prebaking temperature and the postbaking temperature were both changed to 100 ° C.
1S) was formed. As a result of observing each of the obtained patterns with a scanning electron microscope, in each case, the resolution was down to 0.14 μm, and the roughness of the pattern side surface due to the standing wave was hardly observed.

Comparative Example 2 (Evaluation by F ₂ Excimer Laser Exposure) The pattern forming composition solution obtained in Preparation Example 3 was applied onto a silicon wafer treated with hexamethyldisilazane by spin coating and then at 140 ° C. Prebaking for 90 seconds on the hot plate held at
A 00 nm resist film was formed. Then, an F ₂ excimer laser (wavelength 157) was applied to this resist film.
nm) and the post-baking was performed for 90 seconds on a hot plate maintained at 110 ° C., followed by development with a 2.38% tetramethylammonium hydroxide aqueous solution, and a line and -A space pattern (1L / 1S) was formed. As a result of observing the obtained pattern with a scanning electron microscope, the roughness of the side surface of the pattern due to the standing wave was remarkable, and the resolution was only possible up to 0.13 μm.

Example 11 (Evaluation by F ₂ excimer laser exposure) On a silicon wafer, the composition for forming an underlayer film obtained in Preparation Example 1 was applied by spin coating so that an underlayer film with a thickness of 300 nm was obtained. Later on the hot plate 180
The lower layer film was formed by baking at 60 ° C. for 60 seconds and then at 300 ° C. for 120 seconds. Then, the composition solution for pattern formation obtained in Preparation Example 3 was applied onto the silicon wafer on which the lower layer film was formed by spin coating.
Prebaking was performed for 90 seconds on a hot plate kept at 0 ° C. to form a resist film having a film thickness of 120 nm. Then, using a binary mask as a reticle, an F ₂ excimer laser (wavelength 157 nm, numerical aperture (NA) = 0.60, σ = 0.7) was applied to this resist film.
0), the exposure amount was changed, and post-baking was performed for 90 seconds on a hot plate kept at 110 ° C., followed by development with a 2.38% tetramethylammonium hydroxide aqueous solution, and a line and -A space pattern (1L / 1S) was formed. As a result of observing the obtained pattern with a scanning electron microscope, the pattern was resolved up to 0.10 μm, and the roughness on the side surface of the pattern due to the standing wave was hardly observed.

Examples 12 to 15 (Evaluation by F ₂ excimer laser exposure) In Example 11, instead of the pattern forming composition solution obtained in Preparation Example 3, each pattern forming composition obtained in Preparation Examples 4 to 7 was used. A line-and-space pattern (1L / 1S) was formed in the same manner as in Example 11 except that the composition solution was used and the prebaking temperature and the postbaking temperature were both changed to 100 ° C. As a result of observing the obtained pattern with a scanning electron microscope, the pattern was resolved up to 0.10 μm, and the roughness on the side surface of the pattern due to the standing wave was hardly observed.

Example 16 (Evaluation by F ₂ excimer laser exposure) In Example 11, the composition for forming an underlayer film obtained in Preparation Example 2 was used in place of the composition for forming an underlayer film obtained in Preparation Example 1. A line and space pattern (1L / 1S) was formed in the same manner as in Example 11 except for the above. As a result of observing each of the obtained patterns with a scanning electron microscope, 0.10 was obtained.
The resolution was down to μm, and almost no roughness on the side surface of the pattern due to the standing wave was observed.

Examples 17 to 20 (Evaluation by F ₂ excimer laser exposure) In Example 16, instead of the pattern forming composition solution obtained in Preparation Example 3, the pattern forming compositions obtained in Preparation Examples 4 to 7 were used. Example 1 except that the material solution was used and the temperature of both prebaking and postbaking was changed to 100 ° C.
Line and space pattern (1
L / 1S) was formed. As a result of observing each of the obtained patterns with a scanning electron microscope, it was 0.10 μm in each case.
Up to this point, the roughness on the side surface of the pattern due to the standing wave was hardly observed.

Examples 21 to 25 (Evaluation by F ₂ excimer laser exposure) Example 1 is different from Examples 11 to 15 except that Levenson Mack was used as the reticle.
Line and space patterns (1L / 1S) were formed in the same manner as 1 to 15. As a result of observing the obtained pattern with a scanning electron microscope, it was 0.07 in each case.
The resolution was down to μm, and almost no roughness on the side surface of the pattern due to the standing wave was observed.

Examples 26 to 30 (Pattern transfer test after F ₂ excimer laser exposure) Using the line and space patterns (1L / 1S) obtained in Examples 21 to 25 as masks, etching of the lower layer film was performed. The pattern transfer test by The test uses a Lam TCP-9400 device manufactured by Lam Co.,
Etching gas O ₂ / SO ₂ = 130/10 SCCM,
Vacuum degree 5mTorr, Cathode power Top / Bott
om = 200 / 60w, substrate temperature = −5 ° C., etching time 40 seconds. Then, as a result of observing the obtained patterns of the respective examples with a scanning electron microscope, it was revealed that the pattern transfer was satisfactorily performed up to 0.07 μm in each case. The thickness of each pattern obtained was measured by a scanning electron microscope. As a result, in each case, the lower layer film was about 300 nm, and the pattern portion was about 100 n.
It was confirmed that the film remained, the lower layer film was hardly eroded by etching, and the pattern portion was eroded only by about 20 μm. From these results, when the aspect ratio of the pattern is produced, (100nm + 300n
m) / 70 nm≈5.7, which is a very high value.

Example 31 (Evaluation by electron beam exposure) The composition for forming an underlayer film obtained in Preparation Example 1 was applied onto a silicon wafer by spin coating so that an underlayer film with a thickness of 300 nm was obtained. 180 on the hot plate
The lower layer film was formed by baking at 60 ° C. for 60 seconds and then at 300 ° C. for 120 seconds. Then, the composition solution for pattern formation obtained in Preparation Example 3 was applied onto the silicon wafer on which the lower layer film was formed by spin coating.
Prebaking was performed for 90 seconds on a hot plate kept at 0 ° C. to form a resist film having a film thickness of 100 nm. Then, this resist film was exposed by an electron beam using a simple electron beam direct drawing device (50 keV, current density 4.5 amperes), and post-baked for 90 seconds on a hot plate kept at 110 ° C. After going 2.
Development was performed with a 38% tetramethylammonium hydroxide aqueous solution to form a line and space pattern (1L / 1S). As a result of observing the obtained pattern with a scanning electron microscope, it was resolved to 0.07 μm.

[0192]

INDUSTRIAL APPLICABILITY The polymer for the lower layer film of the present invention has excellent dry etching resistance and can be used as a thin film.
By using a combination of specific pattern forming compositions having high transparency at a wavelength of 3 nm or less, particularly 193 nm and 157 nm, 193 nm or less, especially 19
Even at wavelengths of 3 nm and 157 nm, a dense pattern can be formed without causing roughness on the side surface of the pattern due to a standing wave, and a high aspect ratio can be obtained by appropriately selecting an etching gas in the dry etching process. It is possible to form a resist pattern having Therefore, the pattern forming method and the multilayer film for pattern formation of the present invention are extremely useful for a lithography process, which is expected to be further miniaturized in the future.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/26 511 G03F 7/26 511 5F046 H01L 21/027 C08G 77/14 // C08G 77/14 H01L 21 / 30 502R 573 (72) Inventor Tsutomu Shimokawa 2-11-24 Tsukiji, Chuo-ku, Tokyo, JR S Co., Ltd. (72) Inventor Kazuo Kawaguchi 2-11-24 Tsukiji, Chuo-ku, Tokyo J-SR Co., Ltd. (72) Inventor Masato Tanaka 2-11-21 Tsukiji, Chuo-ku, Tokyo F-term in JSR Corporation (reference) 2H025 AA01 AA02 AA03 AA09 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CB33 CB41 DA40 FA17 2H096 AA25 BA11 CA05 EA03 EA04 EA06 EA07 GA08 KA06 4J033 DA01 DA12 HA02 HB03 4J035 BA04 CA071 CA101 EA01 EB10 LA02 LB16 4J100 AR09P BA03P BA05P BA14P BA16P BA29P BA41P BA52P BA56P BB01P BB03P BC43P CA01 CA04 DA01 DA36 JA38 JA43 5F046 NA19

Claims (7)

[Claims] 1. An alkali, which becomes alkali-soluble when an acid-labile group is dissociated on a film containing a polymer having a carbon content of 80% by weight or more and a polystyrene reduced weight average molecular weight of 500 to 100,000. A pattern forming method, which comprises a step of forming a coating film made of a radiation-sensitive resin composition containing an insoluble or sparingly alkali-soluble acid-labile group-containing polysiloxane and irradiating with radiation. 2. A polymer having a carbon content of 80% by weight or more and a polystyrene-equivalent weight average molecular weight of 500 to 100,000 is composed of a polymer having a structural unit represented by the following general formula (1). The pattern formation method according to claim 1. [Chemical 1] [In the general formula (1), R ¹ represents a monovalent atom or a monovalent group, m is an integer of 0 to 4, and when m is 2 to 4, a plurality of R ¹ are the same or different from each other. Alternatively, R ² and R ³ each independently represent a monovalent atom or a monovalent group. ] 3. The acid-dissociable group-containing polysiloxane is a polymer having a structural unit represented by the following general formula (2) and / or a structural unit represented by the following general formula (3). The pattern forming method according to claim 1 or 2. [Chemical 2] [In the general formula (2) and the general formula (3), A ¹ and A ² each independently represent a monovalent organic group having an acid dissociable group which is dissociated by an acid, and R ⁴ has 1 to 10 carbon atoms. Linear, branched or cyclic alkyl group of, or having 1 carbon atom
10 represents a linear, branched or cyclic halogenated alkyl group. ] 4. The pattern forming method according to claim 1, wherein radiation having a wavelength of 193 nm or 157 nm is used as the radiation. 5. An alkali which becomes alkali-soluble when the acid dissociable group is dissociated on a film containing a polymer having a carbon content of 80% by weight or more and a polystyrene reduced weight average molecular weight of 500 to 100,000. A multilayer film for pattern formation, which is formed by forming a film made of a radiation-sensitive resin composition containing an insoluble or sparingly alkali-soluble acid-labile group-containing polysiloxane. 6. A polymer having a carbon content of 80% by weight or more and a polystyrene reduced weight average molecular weight of 500 to 100,000 is obtained from a polymer having a structural unit represented by the general formula (1) according to claim 2. The multilayer film for pattern formation according to claim 5, wherein 7. The acid dissociable group-containing polysiloxane is a structural unit represented by the general formula (2) according to claim 3, and / or
Alternatively, the pattern forming multilayer film according to claim 5 or 6, comprising a polymer having a structural unit represented by the general formula (3).