JP2007298633A - Composition for antireflection film formation, laminate and resist pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for antireflection film formation having excellent coating property, forming an antireflection film capable of sufficiently reducing standing-wave effect, and capable of suppressing generation of microbubbles. <P>SOLUTION: The composition for antireflection film formation contains (A) a copolymer (salt) of a sulfonic acid group-containing acrylamide derivative typified by 2-(meth)acrylamide-2-methylpropanesulfonic acid and a fluoroalkyl group-containing acrylic ester derivative typified by 2,2,3,3,3-pentafluoropropyl (meth)acrylate and (B) an acetylene compound typified by 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, 5,8-dimethyl-6-dodecyne-5,8-diol or ethylene oxide addition derivatives of these. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antireflection film-forming composition useful for microfabrication by a lithography process using a resist sensitive to various types of radiation, particularly a chemically amplified resist, and an antireflection film formed from the antireflection film-forming composition. The present invention relates to a laminate in which a film is formed on a resist film, and a resist pattern forming method using the composition for forming an antireflection film.

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration of integrated circuits, the processing size in the lithography process has been miniaturized. In recent years, the line width is 0.5 μm or less. Development of a lithography process capable of stably performing high-precision micromachining is strongly advanced.
However, in the conventional method using visible light (wavelength 800 to 400 nm) or near ultraviolet light (wavelength 400 to 300 nm), it is difficult to form such a fine pattern with high accuracy. There has been proposed a lithography process using radiation with a short wavelength (wavelength of 300 nm or less) that can be achieved and is effective for miniaturization of design rules. Lithographic processes using such short-wavelength radiation include deep ultraviolet rays such as KrF excimer laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm), and charged particle beams such as X-rays such as synchrotron radiation or electron beams. A method of using is proposed. So-called “chemically amplified resists” have attracted attention as high-resolution resists that can handle short-wavelength radiation, and improvement and development of these chemically amplified resists are now an important technical theme in the field of lithography processes. Yes.
A chemically amplified resist generates an acid by irradiating a compound that generates an acid upon irradiation with radiation (hereinafter, also referred to as “exposure”), and this acid catalyzes the resist film. Among them, a chemical reaction (for example, change in polarity, cleavage of chemical bond, cross-linking reaction, etc.) occurs, and a pattern is formed by utilizing a phenomenon that the solubility in a developing solution changes in an exposed portion.
For such a chemically amplified resist, a combination of a resin in which an alkali affinity group in an alkali-soluble resin is protected with a t-butyl ester group or a t-butoxycarbonyl group and an acid generator (see, for example, Patent Document 1). A combination of a resin in which an alkali affinity group in an alkali-soluble resin is protected with a silyl group and an acid generator (for example, see Patent Document 2); a combination of an acetal group-containing resin and an acid generator (for example, see Patent Document 3) In addition, a number of proposals have been made such as combinations of alkali-soluble resins, dissolution control agents and acid generators; combinations of novolak resins, crosslinking agents and acid generators.

JP 59-45439 A JP-A-60-52845 JP-A-2-25850

  However, chemically amplified resists are easily affected by moisture, oxygen, basic substances, etc. present in the atmosphere in the lithography process, and there is a problem in terms of process stability. For example, in Non-Patent Document 1, a trace amount of dimethylaniline contained in the atmosphere deactivates the acid in the vicinity of the surface of the acid generated in the resist film by exposure to form a hardly soluble layer on the resist film surface. It has been reported that this poorly soluble layer remains in the shape of a bowl on the surface of the resist pattern after development. Such a poorly soluble layer not only lowers the sensitivity and resolution of the resist, but also wrinkles generated in the resist pattern adversely affect the subsequent etching accuracy. Moreover, the size of this wrinkle tends to increase with an increase in the standing time interposed between each process of exposure-post-exposure baking-development, but this phenomenon is caused by post-exposure time delay ( Hereinafter, it is referred to as “PED”), which is a factor that significantly reduces the time tolerance in the lithography process.

SPIE, Vol. 1466, “Advance in Resist Technology and Processing”, p.2 (1991)

  As a method for solving such problems relating to PED, it has been proposed to laminate a protective film that shields the coating surface from the atmosphere on the chemically amplified resist coating. For example, Non-Patent Document 2 discloses polyacrylic. By laminating a protective film such as acid, polyvinyl butyral, polyvinyl alcohol, polystyrene sulfonic acid, etc. on the chemically amplified resist film, the entry of basic substances into the resist film is suppressed, and the sensitivity and resolution of the resist are reduced. It is described to prevent. However, among such protective films, polyacrylic acid, polyvinyl butyral, and polyvinyl alcohol have a barrier action, but cannot always effectively prevent the formation of the hardly soluble layer as described above. Sulfonic acid is too acidic and has the disadvantage of initiating a chemical reaction due to the catalytic action of the acid in the chemically amplified resist, regardless of the presence or absence of exposure. In addition, these protective films are generally applied as an aqueous solution on the resist film, but the wettability of the aqueous solution with the resist film is not sufficient, and there is a drawback in that uneven coating tends to occur.

WO92 / 05474

In addition, since the radiation normally used in the lithography process has a single wavelength, the incident radiation and the radiation reflected by the upper and lower interfaces of the resist film interfere with each other in the resist film, resulting in a “standing wave effect” or A phenomenon called "multiple interference effect", that is, even if the exposure dose is constant, if the thickness of the resist coating varies, the effective exposure dose to the resist coating varies due to mutual interference within the coating. May occur and adversely affect the formation of the resist pattern. For example, the coating thickness changes due to slight differences in resist composition, viscosity, resist coating conditions, etc., or there is a difference in coating thickness due to the difference in level of the substrate (the concave part is more prominent than the convex part). When the thickness of the resist film is increased, the effective exposure amount to the resist film changes, and the pattern dimension fluctuates or the dimensional accuracy of the resist pattern decreases.
In order to solve such a problem related to the standing wave effect, a method has been proposed in which an antireflection film is formed on a resist film to suppress reflection at the resist film interface and to reduce multiple interference in the film. For example, Non-Patent Document 3 describes that a standing wave effect is reduced by laminating polysiloxane, polyethyl vinyl ether, polyvinyl alcohol or the like as an antireflection film on a resist film. In this case, the anti-reflection effect at the resist film interface mainly depends on the refractive index and the film thickness of the antireflection film, and the ideal antireflective film has the “square root of the refractive index n of the resist”. The thickness of a typical antireflection film is assumed to be an odd multiple of λ / 4n (λ is the wavelength of radiation and n is the refractive index of the antireflection film).

J. Eectrochem. Soc., Vol.137, No.12, p.3900 (1990)

  However, an antireflection film made of polysiloxane, polyethyl vinyl ether, or polyvinyl alcohol has a basic problem that the standing wave effect cannot be sufficiently suppressed because the difference in refractive index from the resist is small. In addition, an antireflection film that is insoluble in water or a developer, such as polysiloxane, requires a separate removal step with an antireflection film removing agent before development, and even in the case of polyethyl vinyl ether or polyvinyl alcohol, Alternatively, the solubility in the developer is not always sufficient, and there are drawbacks such as residues remaining on the resist film and resist performance such as resolution, developability, and pattern shape may deteriorate. In addition, when applied as an aqueous solution onto a resist film, such as polyethyl vinyl ether or polyvinyl alcohol, there is a drawback in that the wettability of the aqueous solution with the resist film is not sufficient and uneven coating tends to occur.

  On the other hand, in order to solve the problems in the conventional antireflection film as described above, the present applicant has already disclosed in Patent Document 4 (a) an acrylamide compound such as 2-acrylamido-2-methylpropanesulfonic acid. A copolymer of a monomer in which a sulfonic acid group is bonded to a nitrogen atom of an amide group via an organic group and a fluoroalkyl acrylate compound such as 2,2,3,3,3-pentafluoropropyl acrylate, and (b) A base-blocking antireflection film containing a fluoroalkylsulfonic acid having a fluoroalkyl group having 5 to 15 carbon atoms and / or a fluoroalkylcarboxylic acid having a fluoroalkyl group having 5 to 15 carbon atoms and a resist pattern using the same A forming method is proposed. However, this antireflection film can effectively reduce the influence of the basic substance in the atmosphere and the standing wave effect, but there is a problem in the applicability of the composition used for forming the antireflection film on the resist film. In addition, there is a problem that microbubbles having a size on the order of μm are easily generated in the formed coating film.

JP 7-234514 A

  An object of the present invention is to provide an antireflection film-forming composition that has excellent coating properties, the formed antireflection film can sufficiently reduce the standing wave effect, and can remarkably suppress the generation of fine microbubbles. An object of the present invention is to provide a laminate in which an antireflection film formed from a composition for forming an antireflection film is formed on a resist film, and a method for forming a resist pattern using the composition for forming a base-blocking antireflection film.

The present invention, first,
(A) a water-soluble resin comprising a copolymer having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) and / or a salt thereof, and (B) the following formula ( 3) The composition for anti-reflective film formation characterized by including the compound represented by 3).

〔式（１）において、Ｒ¹ は水素原子または１価の有機基を示し、Ｒ² は２価の有機基を示す。〕

[In the formula (1), R ¹ represents a hydrogen atom or a monovalent organic group, and R ² represents a divalent organic group. ]

〔式（２）において、Ｒ³ は水素原子または１価の有機基を示し、Ｒf はフルオロアルキル基を示し、Ｘは直接結合、アルキレン基またはフルオロアルキレン基を示す。〕

[In the formula (2), R ³ represents a hydrogen atom or a monovalent organic group, R f represents a fluoroalkyl group, and X represents a direct bond, an alkylene group or a fluoroalkylene group. ]

〔式（３）において、各Ｒ⁴ は相互に独立に炭素数１〜５のアルキル基を示し、ｍおよびｎはそれぞれ０〜２５の整数で、（ｍ＋ｎ）＝０〜４０を満たす。〕

[In the formula (3), each R ⁴ represents an alkyl group having 1 to 5 carbon atoms independently of one another, an integer from respective m and n are 0 to 25, satisfying the (m + n) = 0 to 40. ]

The present invention secondly,
It consists of a laminate formed by forming an antireflective film made of the composition for forming an antireflective film on a resist film.

Third, the present invention
In forming a resist pattern by forming a resist film on a substrate, irradiating the resist film with radiation, and then developing the resist film, the antireflection film is formed on the resist film in advance from the antireflection film forming composition. After the formation of the resist pattern, the resist pattern is formed by irradiating a predetermined pattern shape with radiation, and then developing to remove the antireflection film.

Hereinafter, the present invention will be described in detail.
Antireflective film forming composition- component (A)-
The component (A) in the present invention includes a repeating unit represented by the formula (1) (hereinafter referred to as “repeating unit (1)”) and a repeating unit represented by the formula (2) (hereinafter referred to as “repeating”). Unit (2) ”) (hereinafter referred to as“ copolymer (α) ”) and / or a salt thereof (hereinafter referred to as“ copolymer (α) and its salt ”. A) Copolymer (salt) ").
In the copolymer (α), the repeating unit (1) and the repeating unit (2) may be present alone or in combination of two or more.
The copolymer (α) comprises a sulfonic acid group-containing acrylamide derivative corresponding to the repeating unit (1) (hereinafter referred to as “acrylamide derivative (i)”) and a fluoroalkyl group-containing acrylic acid corresponding to the repeating unit (2). It can be produced by copolymerizing a monomer mixture containing an ester derivative (hereinafter referred to as “acrylic ester derivative (ii)”).

In the formula (1), divalent organic groups, monovalent organic radicals and R ² R ¹ may be linear, branched or cyclic.
The monovalent organic group for R ¹ is preferably a group having 1 to 12 carbon atoms.
Carboxyl group; cyano group; methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl A C1-C12 alkyl group such as a group; carboxymethyl group, 2-carboxyethyl group, 2-carboxypropyl group, 3-carboxypropyl group, 2-carboxybutyl group, 3-carboxybutyl group, 4-carboxybutyl group A carboxyalkyl group having 2 to 12 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl, etc. Alkoxycarbonyl group; acetyloxy group, propionyloxy group, butanoyloxy, benzoyl An acyloxy group having 2 to 12 carbon atoms such as alkoxy groups;

Aryl groups having 6 to 12 carbon atoms such as phenyl group and cumenyl group; aralkyl groups having 7 to 12 carbon atoms such as benzyl group and α-methylbenzyl group; methoxy group, ethoxy group, n-propoxy group and i-propoxy group Alkoxy groups having 1 to 12 carbon atoms such as n-butoxy group and t-butoxy group; methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-methoxypropyl group, 3-methoxy C2-C12 alkoxyalkyl group such as propyl group, 2-methoxybutyl group, 3-methoxybutyl group, 4-methoxybutyl group, etc .; C3 such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. -12 cycloalkyl groups and substituted derivatives of these groups.

In formula (1), R ¹ is preferably a hydrogen atom, a methyl group, or the like.

The divalent organic group represented by R ² is preferably a group having 1 to 12 carbon atoms. Examples thereof include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, 1,1. -Dimethylethylene group, 1-methyl-1,3-propylene group, 1,4-butylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group, 1,5-pentylene Group, 1,1-dimethyl-1,4-butylene group, 2,2-dimethyl-1,4-butylene group, 1,2-dimethyl-1,4-butylene group, 1,6-hexylene group, 1, A 3-cyclopentylene group, a 1,4-cyclohexylene group, etc. can be mentioned.
Of these divalent organic groups, a 1,1-dimethylethylene group is particularly preferable.

Specific examples of the acrylamide derivative (i) include
2- (meth) acrylamide-2-methylpropanesulfonic acid, 2-α-carboxyacrylamide-2-methylpropanesulfonic acid, 2-α-carboxymethylacrylamide-2-methylpropanesulfonic acid, 2-α-methoxycarbonylacrylamide 2-methylpropanesulfonic acid, 2-α-acetyloxyacrylamide-2-methylpropanesulfonic acid, 2-α-phenylacrylamide-2-methylpropanesulfonic acid, 2-α-benzylacrylamide-2-methylpropanesulfonic acid 2-α-methoxyacrylamide-2-methylpropanesulfonic acid, 2-α- (2-methoxyethyl) acrylamide-2-methylpropanesulfonic acid, 2-α-cyclohexylacrylamide-2-methylpropanesulfonic acid, 2- α-shi And the like Bruno acrylamido-2-methylpropanesulfonic acid.
In the present invention, the acrylamide derivative (i) is particularly preferably 2- (meth) acrylamide-2-methylpropanesulfonic acid.

Next, in the formula (2), the monovalent organic group represented by R ³ can be linear, branched or cyclic.
The fluoroalkyl group of Rf can be linear, branched or cyclic and can be a hydrofluoroalkyl group or a perfluoroalkyl group.
Furthermore, the fluoroalkylene group of X can be linear, branched or cyclic, and may be a hydrofluoroalkylene group or a perfluoroalkylene group.

The monovalent organic group for R ³ is preferably a group having 1 to 12 carbon atoms. Examples thereof are the same as those exemplified for the monovalent organic group having 1 to 12 carbon atoms for R ¹ in formula (1). Can be mentioned.

In formula (2), R ³ is preferably a hydrogen atom, a methyl group or the like.

Further, the fluoroalkyl group of Rf is preferably a group having 1 to 15 carbon atoms.
Difluoromethyl group, trifluoromethyl group;
2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group;
1- (trifluoromethyl) ethyl group, 2- (trifluoromethyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, (pentafluoroethyl) methyl group, di (trifluoromethyl) methyl group, Heptafluoropropyl group;
1-methyl-2,2,3,3-tetrafluoropropyl group, 1- (pentafluoroethyl) ethyl group, 2- (pentafluoroethyl) ethyl group, 2,2,3,3,4,4-hexa Fluoro-n-butyl group, 2,2,3,4,4,4-hexafluoro-n-butyl group, (heptafluoro-n-propyl) methyl group, nonafluoro-n-butyl group;

1,1-dimethyl-2,2,3,3-tetrafluoropropyl group, 1,1-dimethyl-2,2,3,3,3-pentafluoropropyl group, 1-methyl-2,2,3, 3,4,4-hexafluorobutyl group, 1- (heptafluoro-n-propyl) ethyl group, 2- (heptafluoro-n-propyl) ethyl group, 2,2,3,3,4,4,5 , 5-octafluoro-n-pentyl group, (nonafluoro-n-butyl) methyl group, perfluoro-n-pentyl group;
1,1-dimethyl-2,2,3,3,4,4-hexafluorobutyl group, 1,1-dimethyl-2,2,3,3,4,4,4-heptafluorobutyl group, Methyl-2,2,3,3,4,4,5,5-octafluoropentyl group, 1- (nonafluoro-n-butyl) ethyl group, 2- (nonafluoro-n-butyl) ethyl group, 2,2 , 3,3,4,4,5,5,6,6-decafluoro-n-hexyl group, (perfluoro-n-pentyl) methyl group, perfluoro-n-hexyl group; 1,1-dimethyl- 2,2,3,3,4,4,5,5-octafluoropentyl group, 1,1-dimethyl-2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 1-methyl-2,2,3,3,4,4,5,5,6,6-decafluorohexyl group, 1- ( -Fluoro-n-pentyl) ethyl group, 2- (perfluoro-n-pentyl) ethyl group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-n -Heptyl group, (perfluoro-n-hexyl) methyl group, perfluoro-n-heptyl group;

1- (perfluoro-n-hexyl) ethyl group, 2- (perfluoro-n-hexyl) ethyl group, 2,2,3,3,4,4,5,5,6,6,7,7, 8,8-tetradecafluoro-n-octyl group, (perfluoro-n-heptyl) methyl group, perfluoro-n-octyl group;
1- (perfluoro-n-heptyl) ethyl group, 2- (perfluoro-n-heptyl) ethyl group, 2,2,3,3,4,4,5,5,6,6,7,7, 8,8,9,9-hexadecafluoro-n-nonyl group, (perfluoro-n-octyl) methyl group, perfluoro-n-nonyl group;
1- (perfluoro-n-octyl) ethyl group, 2- (perfluoro-n-octyl) ethyl group, 2,2,3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10,10-octadecafluoro-n-decyl group, (perfluoro-n-nonyl) methyl group, perfluoro-n-decyl group and the like can be mentioned.

  In the formula (2), Rf is preferably 2,2,2-trifluoroethyl group, (pentafluoroethyl) methyl group, 2- (perfluoro-n-octyl) ethyl group or the like.

Further, the alkylene group of X is preferably a group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, and a 1,1-dimethylethylene group. 1-methyl-1,3-propylene group, 1,4-butylene group and the like.
The fluoroalkylene group represented by X is preferably a group having 1 to 5 carbon atoms. Examples thereof include a difluoromethylene group, a 1,1-difluoroethylene group, a tetrafluoroethylene group, and a 1,1-difluoro-1,2-propylene. Group, 2,2,3,3-tetrafluoro-1,3-propylene group, hexafluoro-1,3-propylene group, 1,1-dimethyl-2,2-difluoroethylene group, 1-methyl-2, 2,3,3-tetrafluoro-1,3-propylene group, 2,2,3,3,4,4-hexafluoro-1,4-butylene group, octafluoro-1,4-butylene group, etc. be able to.

  In formula (2), X is particularly preferably a direct bond.

Specific examples of the acrylate derivative (ii) include
Difluoromethyl (meth) acrylate, trifluoromethyl (meth) acrylate;
2,2-difluoroethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate;
1- (trifluoromethyl) ethyl (meth) acrylate, 2- (trifluoromethyl) ethyl (meth) acrylate, 2,2,3,3-tetrafluoro-n-propyl (meth) acrylate, (pentafluoroethyl) Methyl (meth) acrylate, di (trifluoromethyl) methyl (meth) acrylate, heptafluoro-n-propyl (meth) acrylate;

1-methyl-2,2,3,3-tetrafluoropropyl (meth) acrylate, 1- (pentafluoroethyl) ethyl (meth) acrylate, 2- (pentafluoroethyl) ethyl (meth) acrylate, 2,2, 3,3,4,4-hexafluoro-n-butyl (meth) acrylate, (heptafluoro-n-propyl) methyl (meth) acrylate, nonafluoro-n-butyl (meth) acrylate;
1,1-dimethyl-2,2,3,3-tetrafluoropropyl (meth) acrylate, 1,1-dimethyl-2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (hepta Fluoro-n-propyl) ethyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoro-n-pentyl (meth) acrylate group, (nonafluoro-n-butyl) methyl (meth) ) Acrylate, perfluoro-n-pentyl (meth) acrylate;

1,1-dimethyl-2,2,3,3,4,4-hexafluorobutyl (meth) acrylate, 1,1-dimethyl-2,2,3,3,4,4,4-heptafluorobutyl ( (Meth) acrylate, 2- (nonafluoro-n-butyl) ethyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6-decafluoro-n-hexyl (meth) acrylate, (Perfluoro-n-pentyl) methyl (meth) acrylate, perfluoro-n-hexyl (meth) acrylate;
1,1-dimethyl-2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 1,1-dimethyl-2,2,3,3,4,4,5 5,5-nonafluoropentyl (meth) acrylate, 2- (perfluoro-n-pentyl) ethyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluoro-n-heptyl (meth) acrylate, (perfluoro-n-hexyl) methyl (meth) acrylate, perfluoro-n-heptyl (meth) acrylate;

2- (Perfluoro-n-hexyl) ethyl (meth) acrylate, 2,2,3,3,4,5,5,6,6,7,7,8,8-tetradecafluoro-n- Octyl (meth) acrylate, (perfluoro-n-heptyl) methyl (meth) acrylate, perfluoro-n-octyl (meth) acrylate;
2- (Perfluoro-n-heptyl) ethyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadeca Fluoro-n-nonyl (meth) acrylate, (perfluoro-n-octyl) methyl (meth) acrylate, perfluoro-n-nonyl (meth) acrylate;
2- (perfluoro-n-octyl) ethyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, Carbon number of fluoroalkyl groups, such as 10-octadecafluoro-n-decyl (meth) acrylate, (perfluoro-n-nonyl) methyl (meth) acrylate, perfluoro-n-decyl (meth) acrylate, is 1-10. In addition to the fluoroalkyl (meth) acrylates,

2,2,2-trifluoroethyl-α-carboxyacrylate, (pentafluoroethyl) methyl-α-carboxyacrylate;
2,2,2-trifluoroethyl-α- (carboxymethyl) acrylate, (pentafluoroethyl) methyl-α- (carboxymethyl) acrylate;
2,2,2-trifluoroethyl-α- (methoxycarbonyl) acrylate, (pentafluoroethyl) methyl-α- (methoxycarbonyl) acrylate;
2,2,2-trifluoroethyl-α- (acetyloxy) acrylate, (pentafluoroethyl) methyl-α- (acetyloxy) acrylate;
2,2,2-trifluoroethyl-α-phenyl acrylate, (pentafluoroethyl) methyl-α-phenyl acrylate;

2,2,2-trifluoroethyl-α-benzyl acrylate, (pentafluoroethyl) methyl-α-benzyl acrylate;
2,2,2-trifluoroethyl-α-ethoxy acrylate, (pentafluoroethyl) methyl-α-ethoxy acrylate;
2,2,2-trifluoroethyl-α- (2-methoxyethyl) acrylate, (pentafluoroethyl) methyl-α- (2-methoxyethyl) acrylate;
2,2,2-trifluoroethyl-α-cyclohexyl acrylate, (pentafluoroethyl) methyl-α-cyclohexyl acrylate;
Examples include 2,2,2-trifluoroethyl-α-cyanoacrylate and (pentafluoroethyl) methyl-α-cyanoacrylate.

  In the present invention, the acrylic ester derivative (ii) is preferably a fluoroalkyl (meth) acrylate having a fluoroalkyl group having 1 to 10 carbon atoms, and particularly having a perfluoroalkyl group having 1 to 10 carbon atoms. Perfluoroalkyl (meth) acrylates, fluoroalkyl (meth) acrylates in which a perfluoroalkyl group having 1 to 9 carbon atoms is bonded to an ester oxygen atom via a methylene group, and perfluoroalkyl groups having 1 to 8 carbon atoms are ethylene Fluoroalkyl (meth) acrylates bonded to an ester oxygen atom via a group are preferred.

  In the copolymer (α), the copolymerization ratio of the acrylamide derivative (i) and the acrylate derivative (ii) is usually 1 to 99 wt.% Based on the total amount of both compounds. %, Preferably 3 to 50% by weight, particularly preferably 5 to 30% by weight, and the acrylate derivative (ii) is usually 99 to 1% by weight, preferably 97 to 50% by weight, particularly preferably 95%. ~ 70 wt%. In this case, when the copolymerization ratio of the acrylamide derivative (i) is less than 1% by weight and the acrylate derivative (ii) exceeds 99% by weight, the solubility of the resulting antireflection film in water or an alkaline developer is lowered. When the copolymerization ratio of the acrylamide derivative (i) exceeds 99% by weight and the copolymerization ratio of the acrylate derivative (ii) is less than 1% by weight, the antireflection film tends to be deteriorated. As a result, the standing wave effect tends to be insufficiently reduced and the film formability tends to be reduced.

  In the present invention, when producing the copolymer (α), together with the acrylamide derivative (i) and the acrylate derivative (ii), other unsaturated monomers copolymerizable therewith are copolymerized. Can do. The amount of other unsaturated monomers used in this case is usually 50% by weight or less, preferably 40% by weight or less, based on the total monomers.

As the other unsaturated monomer, for example,
(Meth) acrylic acid, crotonic acid, cinnamic acid, atropaic acid, 3-acetyloxy (meth) acrylic acid, 3-benzoyloxy (meth) acrylic acid, α-methoxyacrylic acid, 3-cyclohexyl (meth) acrylic acid Unsaturated monocarboxylic acid compounds such as
(Meth) acrylic acid alkyl ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, methyl crotonate, methyl cinnamate, etc. Other unsaturated monocarboxylic acid ester compounds;
Unsaturated polycarboxylic acids such as fumaric acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid and their anhydride compounds;
Mono- or di-ester compounds such as mono- or di-methyl esters, mono- or di-ethyl esters, mono- or di-n-propyl esters of the unsaturated polycarboxylic acids;

Esters of unsaturated alcohols such as vinyl acetate, vinyl propionate, vinyl caproate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-methylacrylonitrile, α-chloroacrylonitrile, α- (chloromethyl) acrylonitrile, α- (trifluoromethyl) acrylonitrile, vinylidene cyanide;
Other aromatic monovinyl compounds such as styrene, α-methylstyrene, vinyltoluene and the like;
Halogenated olefin compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene;
Diene compounds such as butadiene, isoprene, chloroprene, piperylene, 2,3-dimethylbutadiene, methylpentadiene, cyclopentadiene, vinylcyclohexene, ethylidene norbornene, divinylbenzene, dimethylvinylstyrylsilane;

Unsaturated ether compounds such as methyl vinyl ether, ethyl vinyl ether, methyl allyl ether;
Epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether;
Halogen-containing unsaturated compounds other than the above, such as 2-chloroethyl vinyl ether, vinyl chloroacetate, allyl chloroacetate, p- (chloromethyl) styrene;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, N-methylol (meth) acrylamide, 2-propenyl alcohol, 2-methyl- Hydroxyl group-containing unsaturated compounds such as 2-propenyl alcohol;
Amide group-containing unsaturated compounds other than the above, such as (meth) acrylamide, crotonic acid amide, cinnamic acid amide;

Succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], hexahydrophthalic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- And (meth) acryloyloxyethyl] and compounds represented by the following formula (4) (hereinafter referred to as “acrylamide derivative (iii)”) and other carboxyl group-containing unsaturated compounds.

〔式（４）において、Ｒ⁵ は水素原子または１価の有機基を示し、Ｒ⁶ は２価の有機基を示す。〕

[In Formula (4), R ⁵ represents a hydrogen atom or a monovalent organic group, and R ⁶ represents a divalent organic group. ]

In the formula (4), examples of the monovalent organic group of R ⁵ include the same groups as those exemplified for the monovalent organic group having 1 to 12 carbon atoms of R ¹ in the formula (1). In addition, examples of the divalent organic group represented by R ⁶ include the same groups as those exemplified for the divalent organic group having 1 to 12 carbon atoms represented by R ² in the formula (1). .

  Specific examples of the acrylamide derivative (iii) include 2- (meth) acrylamide-2-methylpropanecarboxylic acid, 2-α-carboxyacrylamide-2-methylpropanecarboxylic acid, 2-α- (carboxymethyl) acrylamide-2. -Methylpropanecarboxylic acid, 2-α- (methoxycarbonyl) acrylamide-2-methylpropanecarboxylic acid, 2-α- (acetyloxy) acrylamide-2-methylpropanecarboxylic acid, 2-α-phenylacrylamide-2-methyl Propanecarboxylic acid, 2-α-benzylacrylamide-2-methylpropanecarboxylic acid, 2-α-methoxyacrylamide-2-methylpropanecarboxylic acid, 2-α- (2-methoxyethyl) acrylamide-2-methylpropanecarboxylic acid , 2-α-cyclohexyla Examples include chloramido-2-methylpropanecarboxylic acid, 2-α-cyanoacrylamide-2-methylpropanecarboxylic acid, and the like.

In the present invention, the other unsaturated monomer is preferably a (meth) acrylic acid alkyl ester compound, particularly preferably methyl (meth) acrylate, ethyl (meth) acrylate, acrylamide derivative (iii), etc. As the acrylamide derivative (iii), 2- (meth) acrylamide-2-methylpropanecarboxylic acid is particularly preferable.
In this invention, another unsaturated monomer can be used individually or in mixture of 2 or more types.

Copolymerization for producing the copolymer (α) is performed by appropriate methods such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization, for example, bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsification. It can be carried out in various polymerization forms such as polymerization, solution polymerization and precipitation polymerization. In the copolymerization, the reaction components such as the monomers and the polymerization initiator can be added all at once, or dividedly or continuously.
The copolymer (α) can also be produced by chemical post-treatment of a suitable precursor copolymer in some cases.

Next, the salt of the copolymer (α) is obtained by neutralizing at least a part of the sulfonic acid group in the repeating unit (1).
The salt of the copolymer (α) is, for example,
(A) A method of neutralizing at least part of the sulfonic acid group in the repeating unit (1) of the copolymer (α) with an alkaline compound;
(B) After neutralizing at least part of the sulfonic acid group in the acrylamide derivative (i) with an alkaline compound in advance, copolymerization with the acrylate derivative (ii) and other unsaturated monomers used in some cases It can manufacture by the method to do.
In the method (a), when an acidic group other than the sulfonic acid group in the repeating unit (1) is present, at least a part of the acidic group may be neutralized. In the method (b), when other unsaturated monomer also has an acidic group, at least a part of the acidic group can be neutralized.
In the present invention, the salt of the copolymer (α) is preferably produced by, for example, adding the copolymer (α) to an aqueous solution of an alkaline compound and mixing them by the method (a).

In the present invention, it is preferable to use ammonia and / or an organic amine as the alkaline compound used when the salt of the copolymer (α) is produced.
Examples of the organic amine include methylamine, ethylamine, n-propylamine, n-butylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, trimethylamine, triethylamine, tri-n-propylamine, Primary to tertiary 1 such as tri-n-butylamine, ethanolamine, aminomethylpropanol, 2-dimethylethanolamine, diethanolamine, triethanolamine, cyclohexylamine, pyrrole, pyrrolidine, oxazole, pyridine, piperidine, morpholine Divalent amines;
Examples include primary to tertiary polyvalent amines such as ethylenediamine, diethylenediamine, tetraethylenediamine, diethylenetriamine, tetraethylenetriamine, imidazole, imidazolidine, oxazole, pyrazine, piperazine, and s-triazine.
Of these organic amines, monovalent or polyvalent tertiary organic amines are preferred.
The said organic amine can be used individually or in mixture of 2 or more types.
In the present invention, as the alkaline compound, ammonia and monovalent tertiary amines are particularly preferable.
In the present invention, the degree of neutralization of the salt of the copolymer (α) is usually 5 to 100 mol%, preferably 30 to 90 mol% with respect to the sulfonic acid group in the repeating unit (1).

  (A) A copolymer (salt) can take various structures, such as a random copolymer, a block copolymer, and a graft copolymer. In the case of a block copolymer, the repeating unit (1) and the repeating unit (2) may coexist in the same polymer block or may exist in different polymer blocks, and the graft copolymer. In this case, both the repeating unit (1) and the repeating unit (2) can coexist in the trunk polymer and / or the branch polymer, and the repeating unit (1) is formed of the trunk polymer or the branch polymer. Present in either one, the repeat unit (2) can be present in either the other branch polymer or the trunk polymer.

As the preferred (A) copolymer (salt) in the present invention, for example,
A copolymer (salt) of 2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one fluoroalkyl (meth) acrylate having a fluoroalkyl group having 1 to 10 carbon atoms;
2- (meth) acrylamido-2-methylpropanesulfonic acid, at least one fluoroalkyl (meth) acrylate having 1 to 10 carbon atoms in the fluoroalkyl group, and other unsaturated monomers ( Copolymer (salt) with at least one of (meth) acrylic acid alkyl ester compounds and / or at least one of acrylamide derivative (iii)
Etc.

As the more preferable (A) copolymer (salt) in the present invention, for example,
2- (meth) acrylamido-2-methylpropanesulfonic acid, perfluoroalkyl (meth) acrylates having 1 to 10 carbon atoms in the perfluoroalkyl group, and perfluoroalkyl groups having 1 to 9 carbon atoms in the methylene group Selected from the group of fluoroalkyl (meth) acrylates bonded to an ester oxygen atom via an alkyl group and fluoroalkyl (meth) acrylates having a C 1-8 perfluoroalkyl group bonded to an ester oxygen atom via an ethylene group A copolymer (salt) with at least one selected from
2- (meth) acrylamido-2-methylpropanesulfonic acid, perfluoroalkyl (meth) acrylates having 1 to 10 carbon atoms in the perfluoroalkyl group, and perfluoroalkyl groups having 1 to 9 carbon atoms in the methylene group Selected from the group of fluoroalkyl (meth) acrylates bonded to an ester oxygen atom via an alkyl group and fluoroalkyl (meth) acrylates having a C 1-8 perfluoroalkyl group bonded to an ester oxygen atom via an ethylene group A copolymer (salt) of at least one selected from the above-mentioned (meth) acrylic acid alkyl ester compounds and / or at least one acrylamide derivative (iii)
Etc.

As a particularly preferred (A) copolymer (salt) in the present invention, for example,
A copolymer (salt) of 2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one perfluoroalkyl (meth) acrylate having a perfluoroalkyl group having 1 to 10 carbon atoms;
2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one fluoroalkyl (meth) acrylate having a C1-C9 perfluoroalkyl group bonded to an ester oxygen atom via a methylene group Copolymer (salt);
2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one fluoroalkyl (meth) acrylate in which a perfluoroalkyl group having 1 to 8 carbon atoms is bonded to an ester oxygen atom via an ethylene group Copolymer (salt);

2- (meth) acrylamido-2-methylpropanesulfonic acid, at least one perfluoroalkyl (meth) acrylate having a C 1-10 perfluoroalkyl group, and C 1-9 perfluoro A copolymer (salt) with at least one fluoroalkyl (meth) acrylate in which an alkyl group is bonded to an ester oxygen atom via a methylene group;
2- (meth) acrylamido-2-methylpropanesulfonic acid, at least one perfluoroalkyl (meth) acrylate having a C 1-10 perfluoroalkyl group, and C 1-8 perfluoro A copolymer (salt) with at least one fluoroalkyl (meth) acrylate in which an alkyl group is bonded to an ester oxygen atom via an ethylene group;

2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one fluoroalkyl (meth) acrylate in which a C1-C9 perfluoroalkyl group is bonded to an ester oxygen atom via a methylene group; A copolymer (salt) with at least one fluoroalkyl (meth) acrylate in which a C 1-8 perfluoroalkyl group is bonded to an ester oxygen atom via an ethylene group;
2- (meth) acrylamido-2-methylpropanesulfonic acid, at least one perfluoroalkyl (meth) acrylate having a C 1-10 perfluoroalkyl group, and C 1-9 perfluoro At least one fluoroalkyl (meth) acrylate in which an alkyl group is bonded to an ester oxygen atom through a methylene group, and a fluoro in which a perfluoroalkyl group having 1 to 8 carbon atoms is bonded to an ester oxygen atom through an ethylene group A copolymer (salt) with at least one alkyl (meth) acrylate;

2- (meth) acrylamide-2-methylpropanesulfonic acid, at least one perfluoroalkyl (meth) acrylate having a perfluoroalkyl group having 1 to 10 carbon atoms, and the (meth) acrylic acid alkyl ester A copolymer (salt) with at least one type of compound and / or at least one type of acrylamide derivative (iii);
2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one fluoroalkyl (meth) acrylate in which a C1-C9 perfluoroalkyl group is bonded to an ester oxygen atom via a methylene group; A copolymer (salt) with at least one of the (meth) acrylic acid alkyl ester compounds and / or at least one of the acrylamide derivatives (iii);

2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one fluoroalkyl (meth) acrylate in which a C 1-8 perfluoroalkyl group is bonded to an ester oxygen atom via an ethylene group; A copolymer (salt) with at least one of the (meth) acrylic acid alkyl ester compounds and / or at least one of the acrylamide derivatives (iii);
2- (meth) acrylamido-2-methylpropanesulfonic acid, at least one perfluoroalkyl (meth) acrylate having a C 1-10 perfluoroalkyl group, and C 1-9 perfluoro At least one fluoroalkyl (meth) acrylate having an alkyl group bonded to an ester oxygen atom via a methylene group, at least one of the above (meth) acrylic acid alkyl ester compounds and / or an acrylamide derivative (iii) A copolymer (salt) with at least one;

2- (meth) acrylamido-2-methylpropanesulfonic acid, at least one perfluoroalkyl (meth) acrylate having a C 1-10 perfluoroalkyl group, and C 1-8 perfluoro At least one fluoroalkyl (meth) acrylate in which an alkyl group is bonded to an ester oxygen atom via an ethylene group, at least one of the above (meth) acrylic acid alkyl ester compounds and / or an acrylamide derivative (iii) A copolymer (salt) with at least one;
2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one fluoroalkyl (meth) acrylate in which a C1-C9 perfluoroalkyl group is bonded to an ester oxygen atom via a methylene group; At least one fluoroalkyl (meth) acrylate in which a perfluoroalkyl group having 1 to 8 carbon atoms is bonded to an ester oxygen atom via an ethylene group, at least one of the above (meth) acrylic acid alkyl ester compounds, and A copolymer (salt) with at least one of the acrylamide derivatives (iii);

2- (meth) acrylamido-2-methylpropanesulfonic acid, at least one perfluoroalkyl (meth) acrylate having a C 1-10 perfluoroalkyl group, and C 1-9 perfluoro At least one fluoroalkyl (meth) acrylate in which an alkyl group is bonded to an ester oxygen atom through a methylene group, and a fluoro in which a perfluoroalkyl group having 1 to 8 carbon atoms is bonded to an ester oxygen atom through an ethylene group Copolymer (salt) of at least one of alkyl (meth) acrylates and at least one of (meth) acrylic acid alkyl ester compounds and / or at least one of acrylamide derivatives (iii)
Etc.

  (A) The copolymer (salt) can be used after hydrogenation when a carbon-carbon unsaturated bond is present. The hydrogenation rate in this case is usually 90% or less, preferably 70% or less, particularly preferably 50% or less.

  The solubility of (A) copolymer (salt) in water at 25 ° C. is preferably 0.1% by weight or more, particularly preferably 0.1 to 50% by weight. (A) Since the copolymer (salt) has such solubility in water, it can have sufficient releasability to water and developer after exposure.

(A) The polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer (salt) is usually 1,000 to 1,000,000, preferably 1,500 to 500,000, particularly preferably. Is 2,000-100,000. In this case, if the Mw of the copolymer (salt) is less than 1,000, there is a tendency that the coating property, film forming property, etc. when forming the antireflection film are lowered, while 1,000,000 is selected. When it exceeds, there exists a tendency for the solubility with respect to water or a developing solution, applicability | paintability, etc. to fall.
In the present invention, the (A) copolymer (salt) can be used alone or in admixture of two or more.

-(B) component-
(B) component in this invention consists of a compound (henceforth "(B) additive") represented by the said Formula (3).

In the formula (3), the alkyl group having 1 to 5 carbon atoms of R ⁴ can be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, i- A propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like can be mentioned. Of these, a methyl group, an ethyl group, and the like are preferable.
M and n are each an integer of 0 to 20, and preferably satisfy (m + n) = 0 to 10.

  Specific examples of the additive (B) that satisfies (m + n) = 0 in the formula (3) include 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, 5,8-dimethyl- 6-dodecin-5,8-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 4,7-dimethyl-5-decyne-4,7-diol, 8-hexadecine -7,10-diol, 7-tetradecine-6,9-diol, 2,3,6,7-tetramethyl-4-octyne-3,6-diol, 3,6-diethyl-4-octyne-3, Examples include 6-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 2,5-dimethyl-3-hexyne-2,5-diol.

Moreover, as a specific example of the (B) additive satisfying (m + n) = 1 to 40 in the formula (3), an ethylene oxide addition derivative of a diol compound exemplified for the (B) additive satisfying the above (m + n) = 0 Can be mentioned.
In this invention, (B) additive can be used individually or in mixture of 2 or more types.

  (B) As an additive, for example, Surfinol 104, 104E, 420, 440, 465, SE, SE-F, 61, 82, 504, 2502, DF58, DF110D, DF110L, DF37, DF75, DF210, CT111, CT121, CT131, CT136, GA, TG, TGE, E104, PD-001, PD-002W, PD-004, EXP4001, EXP4051, Dynol 604, Olphine B, P, Y, A, STG, SPC, E1004, E1010, AK-02 (above, manufactured by Air Products) What is marketed with brand names, such as these, can also be used.

  In this invention, the usage-amount of (B) additive is 0.01-20 weight part normally per 100 weight part of (A) copolymer (salt), Preferably it is 0.1-5 weight part. In this case, if the amount of the compound (3) used is less than 0.01 parts by weight, it may be difficult to ensure sufficient antifoaming properties. On the other hand, if it exceeds 20 parts by weight, the solubility in the solvent decreases. Thus, there is a possibility that aggregates are formed when the solution is used, and it is difficult to sufficiently reduce the surface tension.

-Other additives-
<(C) Additive>
In the composition for forming an antireflection film of the present invention, the surface tension (hereinafter referred to as “surface tension [25 / 0.1]” in an aqueous solution of 25 ° C. and a concentration of 0.1% by weight is used unless the desired effect of the present invention is impaired. ")" Is 45 mN / m or less, preferably 10 to 45 mN / m, and particularly preferably 15 to 43 mN / m, a surfactant (hereinafter referred to as "(C) additive").
(C) The additive is not particularly limited as long as the surface tension satisfies the above conditions, and may be an anionic surfactant, a nonionic surfactant, a cationic surfactant or an amphoteric surfactant. In particular, a fluorosurfactant is preferable.

  (C) Among the additives, as the fluorine-based anionic surfactant, for example, Surflon S-111 (surface tension [25 / 0.1] = 17 mN / m), S-112 (surface tension [25 / 0.1] = 37.4 mN / m), S-113 (surface tension [25 / 0.1] = 15.8 mN / m) S-121 (surface tension [25 / 0.1] = 16.2 mN / m), S- 131 (surface tension [25 / 0.1] = 15.5 mN / m), S-132 (surface tension [25 / 0.1] = 17 mN / m), S-141 (surface tension [25 / 0.1] = 15.5 mN / m) m) S-145 (surface tension [25 / 0.1] = 15.5 mN / m) (above, manufactured by Seimi Chemical Co., Ltd.); footage 100 (surface tension [25 / 0.1] = 21 mN / m), 100C (Surface tension [25 / 0.1] = 33 mN / m), 150 (Surface tension [25 / 0.1] = 20 mN / m), 150 CH ( Surface tension [25 / 0.1] = 22 mN / m), AK (surface tension [25 / 0.1] = 30 mN / m), 501 (surface tension [25 / 0.1] = 20 mN / m), 250 ( Surface tension [25 / 0.1] = 26 mN / m), 251 (surface tension [25 / 0.1] = 21 mN / m), 222 F (surface tension [25 / 0.1] = 36 mN / m), 300 (surface tension) [25 / 0.1] = 19 mN / m), 222F (surface tension [25 / 0.1] = 36 mN / m) (above, manufactured by Neos Co., Ltd.); F-top EF-103 (surface tension [25 / 0.1] = 26 mN / m), EF-112 (surface tension [25 / 0.1] = 12 mN / m), EF-121 (surface tension [25 / 0.1] = 18 mN / m), EF-122A (surface tension [ 25 / 0.1] = 26 mN / m), EF-122B (surface tension [25 / 0.1] = 23 mN / m), EF-122C (surface tension [25 / 0.1 = 16 mN / m), EF-123A (surface tension [25 / 0.1] = 15 mN / m), EF-123B (surface tension [25 / 0.1] = 17 mN / m), EF-352 (surface tension [ 25 / 0.1] = 25 mN / m), EF-802 (surface tension [25 / 0.1] = 21.7 mN / m), (above, manufactured by Gemco Co., Ltd.) and the like.

  As the fluorine-based nonionic surfactant, for example, Surflon S-141 (surface tension [25 / 0.1] = 15.5 mN / m), S-145 (surface tension [25 / 0.1] = 15.5 mN / m), S-381 (surface tension [25 / 0.1] = 17.5 mN / m), S-393 (surface tension [25 / 0.1] = 32.3 mN / m) (above, Seimi Chemical Co., Ltd.); Footage 250 (surface tension [25 / 0.1] = 26 mN / m), 251 (surface tension [25 / 0.1] = 21.0 mN / m), 222 F (surface tension [25 / 0.1] = 36.0 mN / m), FTX-212M (surface tension [25 / 0.1] = 21 mN / m), FTX-209F (surface tension [25 / 0.1] = 26 mN / m), FTX-213F (Surface tension [25 / 0.1] = 27 mN / m), FTX-233F (Surface tension [25 / 0.1] = 24 N / m), FTX-245F (surface tension [25 / 0.1] = 28 mN / m) (above, manufactured by Neos Co., Ltd.); F-top EF-121 (surface tension [25 / 0.1] = 18 mN / m) EF-122A (surface tension [25 / 0.1] = 26 mN / m), EF-122B (surface tension [25 / 0.1] = 23 mN / m), EF-122C (surface tension [25 / 0.1] = 16 mN / m), EF-352 (surface tension [25 / 0.1] = 25.0 mN / m), EF-802 (surface tension [25 / 0.1] = 21.7 mN / m) (above GEMCO Corporation) Manufactured) and the like.

  In addition, as the fluorine-based cationic surfactant, for example, Surflon S-121 (surface tension [25 / 0.1] = 16.2 mN / m) (manufactured by Seimi Chemical Co., Ltd.); Tension [25 / 0.1] = 19.0 mN / m) and 310 (surface tension [25 / 0.1] = 18.0 mN / m) (above, manufactured by Neos Co., Ltd.).

  Further, as the fluorinated amphoteric surfactant, for example, Surflon S-131 (surface tension [25 / 0.1] = 15.5 mN / m), S-132 (surface tension [25 / 0.1] = 17 mN / m) (above, manufactured by Seimi Chemical Co., Ltd.); Footage 400S (surface tension [25 / 0.1] = 21 mN / m) (manufactured by Neos Co., Ltd.); Ftop EF-132 (surface tension [25 / 0.1] = 10 mN / m) (manufactured by Gemco).

  Furthermore, as surfactants other than the fluorine-based surfactant, for example, Fluorard FC-4430 (Sumitomo 3M Co., Ltd.) and the like can be given under the trade name.

Said (C) additive can be used individually or in mixture of 2 or more types.
The blending amount of (C) additive is usually 50 parts by weight or less, preferably 0.01 to 40 parts by weight, particularly preferably 0.1 to 30 parts by weight per 100 parts by weight of (A) copolymer (salt). Part. In this case, if the amount of the additive (C) used exceeds 50 parts by weight, the resist film may be dissolved when the antireflection film-forming composition is applied as a solution on the resist film.

<(D) Additive>
In the composition for forming an antireflection film of the present invention, a fluoroalkylsulfonic acid having 4 to 12 carbon atoms or a salt thereof and / or a fluoroalkylcarboxylic acid having 4 to 12 carbon atoms is used unless the desired effect of the present invention is impaired. An acid or a salt thereof (hereinafter, these compounds are collectively referred to as “(D) additive”) can be blended. (D) An additive is a component which has the effect | action which improves the reduction effect of the standing wave effect of an anti-reflective film more, and mix | blends (C) additive with the composition for anti-reflective film formation of this invention. Furthermore, it is preferable to further use (D) an additive in combination.
Each of the fluoroalkylsulfonic acid and the fluoroalkylcarboxylic acid can be linear or branched, and each of these fluoroalkyl groups can be a hydrofluoroalkyl group or a perfluoroalkyl group.

Examples of each fluoroalkyl group in the fluoroalkylsulfonic acid and the fluoroalkylcarboxylic acid include those similar to the fluoroalkyl group having 4 to 10 carbon atoms among the groups exemplified for Rf in the formula (2),
1,1,2,2,3,3,4,4,5,5-decafluoro-n-pentyl group;
1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-n-hexyl group; 1,1,2,2,3,3,4,4,5 5,6,6,7,7-tetradecafluoro-n-heptyl group;
1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-n-octyl group;
1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-octadecafluoro-n-nonyl group;
1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-eicosafluoro-n-decyl group;

2- (perfluoro-n-nonyl) ethyl group, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,11 , 11-eicosafluoro-n-undecyl group, (perfluoro-n-decyl) methyl group, 1,1,2,2,3,3,4,4,5,5,6,6,7,7 , 8, 8, 9, 9, 10, 10, 11, 11-docosafluoro-n-undecyl group, perfluoro-n-undecyl group;
2- (perfluoro-n-decyl) ethyl group, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,11 , 11,12,12-docosafluoro-n-dodecyl group, (perfluoro-n-undecyl) methyl group, 1,1,2,2,3,3,4,4,5,5,6,6 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12-tetracosafluoro-n-dodecyl group, perfluoro-n-dodecyl group, and the like.

Specific examples of fluoroalkylsulfonic acid include
2- (Heptafluoro-n-propyl) ethanesulfonic acid, 1,1,2,2,3,3,4,4,5,5-decafluoro-n-pentanesulfonic acid, perfluoro-n-pentanesulfone acid;
2- (Nonafluoro-n-butyl) ethanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-n-hexanesulfonic acid, perfluoro-n -Hexanesulfonic acid;
2- (Perfluoro-n-pentyl) ethanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7-tetradecafluoro-n-heptanesulfone Acid, perfluoro-n-heptanesulfonic acid;

2- (perfluoro-n-hexyl) ethanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro- n-octane sulfonic acid, perfluoro-n-octane sulfonic acid;
2- (Perfluoro-n-heptyl) ethanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Octadecafluoro-n-nonanesulfonic acid, perfluoro-n-nonanesulfonic acid;
2- (perfluoro-n-octyl) ethanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 10,10-eicosafluoro-n-decanesulfonic acid, perfluoro-n-decanesulfonic acid;

2- (perfluoro-n-nonyl) ethanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 10,10,11,11-docosafluoro-n-undecanesulfonic acid, perfluoro-n-undecanesulfonic acid;
2- (perfluoro-n-decyl) ethanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, Examples include 10, 10, 11, 11, 12, 12-tetracosafluoro-n-dodecane sulfonic acid, perfluoro-n-dodecane sulfonic acid, and the like.

As specific examples of fluoroalkylcarboxylic acids,
2- (Heptafluoro-n-propyl) ethanecarboxylic acid, 1,1,2,2,3,3,4,4,5,5-decafluoro-n-pentanecarboxylic acid, perfluoro-n-pentanecarboxylic acid acid;
2- (Nonafluoro-n-butyl) ethanecarboxylic acid, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-n-hexanecarboxylic acid, perfluoro-n -Hexanecarboxylic acid;
2- (Perfluoro-n-pentyl) ethanecarboxylic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7-tetradecafluoro-n-heptanecarboxylic Acid, perfluoro-n-heptanecarboxylic acid;

2- (Perfluoro-n-hexyl) ethanecarboxylic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro- n-octane carboxylic acid, perfluoro-n-octane carboxylic acid;
2- (Perfluoro-n-heptyl) ethanecarboxylic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Octadecafluoro-n-nonanecarboxylic acid, perfluoro-n-nonanecarboxylic acid;
2- (perfluoro-n-octyl) ethanecarboxylic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, Examples thereof include 10,10-eicosafluoro-n-decane carboxylic acid and perfluoro-n-decane carboxylic acid.

  Of these fluoroalkylsulfonic acids and fluoroalkylcarboxylic acids, compounds having 6 to 12 carbon atoms in the fluoroalkyl group are preferred, and compounds having 7 to 12 carbon atoms in the fluoroalkyl group are particularly preferred.

Examples of the salt of fluoroalkylsulfonic acid and the salt of fluoroalkylcarboxylic acid include sodium salt, potassium salt, ammonium salt, and lithium salt, respectively.
Of these salts, sodium salts, potassium salts, ammonium salts and the like are preferable.

Said (D) additive can be used individually or in mixture of 2 or more types.
(D) The compounding quantity of an additive becomes like this. Preferably it is 0.001 to 100 weight% with respect to (C) additive, Most preferably, it is 0.01 to 80 weight%. In this case, when the blending amount of the additive (D) is less than 0.001% by weight, the effect of improving the standing wave effect tends to be reduced, whereas when it exceeds 100% by weight, the surface tension due to the additive (C) is increased. The lowering effect may be impaired.

Furthermore, in the composition for forming an antireflection film of the present invention, for example, other water-soluble resins, other alkali-soluble resins, acid generators, and the like may be blended unless the intended effect of the present invention is impaired. it can.
Examples of the other water-soluble resins and other alkali-soluble polymers include polyvinyl alcohol, polymethyl vinyl ether, polyethyl vinyl ether, polyethylene glycol, ammonium polyacrylate, sodium polyacrylate, polyhydroxystyrene or a derivative thereof, and styrene. -Maleic anhydride copolymer or a hydrolyzate thereof, polyvinyl hydroxybenzoate, carboxyl group-containing (meth) acrylic resin, and the like.
These other water-soluble polymers or other alkali-soluble polymers can be used alone or in admixture of two or more.
The amount of the other water-soluble polymer and / or other alkali-soluble polymer is usually 200 parts by weight or less, preferably 100 parts by weight or less, per 100 parts by weight of the copolymer (salt).

The acid generator is a component having an action of improving the resist pattern shape, resolution, developability, and the like.
Examples of such an acid generator include onium salts, haloalkyl group-containing compounds, o-quinonediazide compounds, nitrobenzyl compounds, sulfonic acid ester compounds, and sulfone compounds.

Examples of the onium salt include compounds represented by the following formula (5), formula (6), or formula (7) .

[In the formulas (5) to (7), each R ⁷ , each R ⁸ and each R ⁹ independently represent a hydrogen atom, an amino group, a nitro group, a cyano group, an alkyl group or an alkoxyl group, and Y ¹ , Y ² and Y ³ are independently of each other SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , ClO ₄ , CF ₃ CO ₂ , CF ₃ SO ₃ ,

（ここで、Ｒ¹⁰は水素原子、アミノ基、ニトロ基、シアノ基、アルキル基もしくはアルコキシル基である。）、

(Wherein R ¹⁰ is a hydrogen atom, amino group, nitro group, cyano group, alkyl group or alkoxyl group),

（ここで、各Ｒ¹¹は相互に独立にアルコキシル基である。）、

(Wherein each R ¹¹ is independently an alkoxyl group),

（ここで、Ｒ¹²は水素原子、アミノ基、アニリノ基、アルキル基もしくはアルコキシル基である。）または

(Wherein R ¹² represents a hydrogen atom, an amino group, an anilino group, an alkyl group or an alkoxyl group) or

を示す。〕

Indicates. ]

  Examples of the haloalkyl group-containing compound include compounds represented by the following formula (8) or formula (9).

〔式（８）において、Ｒ¹³はトリクロロメチル基、フェニル基、メトキシフェニル基、ナフチル基またはメトキシナフチル基を示す。〕

[In the formula (8), R ¹³ represents a trichloromethyl group, a phenyl group, a methoxyphenyl group, a naphthyl group or a methoxynaphthyl group. ]

〔式（９）において、各Ｒ¹⁴は相互に独立に水素原子、ハロゲン原子、メチル基、メトキシ基または水酸基を示す。〕

[In Formula (9), each R < ¹⁴ > shows a hydrogen atom, a halogen atom, a methyl group, a methoxy group, or a hydroxyl group mutually independently. ]

  Examples of the o-quinonediazide compound include compounds represented by the following formula (10) or formula (11).

〔式（１０）において、Ａｒ¹ は

[In the formula (10), Ar ¹ is

または

Or

{Wherein D ¹ and D ² are each independently a hydrogen atom or a 1,2-naphthoquinonediazide-4-sulfonyl group, and a and b are each an integer of 0 to 3 (provided that a and b are simultaneously 0 The plurality of D ¹ or D ² may be the same or different from each other. }
Indicates. ]

〔式（１１）において、Ａｒ² は

[In the formula (11), Ar ² represents

または

Or

（ここで、Ｄ³ は水素原子もしくは１，２−ナフトキノンジアジド−４−スルホニル基である。）
を示す。〕

(Here, D ³ is a hydrogen atom or a 1,2-naphthoquinonediazide-4-sulfonyl group.)
Indicates. ]

  Examples of the nitrobenzyl compound include a compound represented by the following formula (12).

〔式（１２）において、p は１〜３の整数であり、Ｒ¹⁵はアルキル基を示し、Ｒ¹⁶は水素原子またはアルキル基を示し、Ｒ¹⁷は

In [Equation (12), p is an integer from 1 to 3, R ¹⁵ represents an alkyl group, R ¹⁶ represents a hydrogen atom or an alkyl group, R ¹⁷ is

（ここで、Ｒ¹⁸は水素原子もしくはアルキル基である。）、

(Wherein R ¹⁸ is a hydrogen atom or an alkyl group),

（ここで、各Ｒ¹⁹は相互に独立にアルコキシル基である。）または

(Wherein each R ¹⁹ is independently an alkoxyl group) or

を示す。〕

Indicates. ]

  Examples of the sulfonic acid ester compound include compounds represented by the following formula (13), formula (14), formula (15), or formula (16).

〔式（１３）において、各Ｒ²⁰は相互に独立に水素原子またはアルキル基を示し、各Ｒ²¹は相互に独立に水素原子、アルキル基またはアリール基を示す。〕

[In the formula (13), each R ²⁰ independently represents a hydrogen atom or an alkyl group, and each R ²¹ independently represents a hydrogen atom, an alkyl group or an aryl group. ]

〔式（１４）において、Ｒ²²は水素原子またはアルキル基を示し、各Ｒ²³は相互に独立にアルキル基もしくはアリール基を示すか、または２つのＲ²³が相互に結合して形成した環の構成単位を示す。〕

[In the formula (14), R ²² represents a hydrogen atom or an alkyl group, and each R ²³ independently represents an alkyl group or an aryl group, or a ring formed by bonding two R ²³ to each other. Indicates the structural unit. ]

〔式（１５）において、各Ｒ²⁴は相互に独立にメチル基、トリフルオロメチル基、トリクロロメチル基、フェニル基、トリル基、シアノフェニル基、トリクロロフェニル基または（トリフルオロメチル）フェニル基を示す。〕

In [Equation (15), each R ²⁴ represents independently of one another methyl group, a trifluoromethyl group, a trichloromethyl group, a phenyl group, a tolyl group, a cyanophenyl group, a trichlorophenyl group or a (trifluoromethyl) phenyl group . ]

〔式（１６）において、Ｚ¹ 、Ｚ² およびＺ³ は相互に独立にフッ素原子、塩素原子、水素原子、アルキル基またはアリール基を示し、各３個存在するＺ¹ 、Ｚ² あるいはＺ³ はそれぞれ相互に同一でも異なってもよい。〕

[In the formula (16), Z ¹ , Z ² and Z ³ each independently represent a fluorine atom, a chlorine atom, a hydrogen atom, an alkyl group or an aryl group, and three each of Z ¹ , Z ² or Z ³ are present. May be the same as or different from each other. ]

  As said sulfone compound, the compound etc. which are represented by following formula (17) can be mentioned, for example.

〔式（１７）において、Ｗは−ＣＯ−または−ＳＯ₂ −を示し、各Ｒ²⁵は相互に独立にハロゲン原子またはアルキル基を示し、Ｒ²⁶はハロゲン原子またはアルキル基を示し、ｑは０〜３の整数であり、複数存在するＲ²⁶は相互に同一でも異なってもよい。〕

[In the formula (17), W represents —CO— or —SO ₂ —, each R ²⁵ independently represents a halogen atom or an alkyl group, R ²⁶ represents a halogen atom or an alkyl group, and q represents 0 And a plurality of R ²⁶ may be the same or different from each other. ]

Of these acid generators, onium salts are particularly preferred.
The acid generators can be used alone or in admixture of two or more.
The compounding amount of the acid generator is usually 20 parts by weight or less, preferably 10 parts by weight or less per 100 parts by weight of the total polymer components in the composition for forming an antireflection film. In this case, when the usage-amount of an acid generator exceeds 20 weight part, there exists a tendency for developability to fall.
Examples of additives other than those described above include light absorbers, storage stabilizers, antifoaming agents, adhesion assistants, preservatives, and dyes and pigments.

Preferred composition of antireflection film-forming composition As described above in detail, the antireflection film-forming composition of the present invention comprises (A) a copolymer (salt) and (B) an additive. It is contained as a component, and is formed by blending various other additives as described above, if necessary. Here, a more preferable composition of the composition is shown as follows:
[I] From a copolymer (salt) of 2- (meth) acrylamido-2-methylpropanesulfonic acid and at least one fluoroalkyl (meth) acrylate having a fluoroalkyl group having 1 to 10 carbon atoms (A) at least one copolymer (salt), Surfinol 104, 104E, 420, 440, 465, SE, SE-F, 61, 82, 504, 2502, DF58, DF110D, DF110L, DF37, DF75, DF210, CT111, CT121, CT131, CT136, GA and TG (B) at least one additive selected from the group An antireflective film-forming composition containing a seed; and

[II] 2- (meth) acrylamido-2-methylpropanesulfonic acid, at least one fluoroalkyl (meth) acrylate having 1 to 10 carbon atoms in the fluoroalkyl group, and other unsaturated monomers At least one of (meth) acrylic acid alkyl ester compounds and / or a copolymer (salt) with at least one acrylamide derivative (iii) (A) at least one copolymer (salt) Surfinol 104, 104E, 420, 440, 465, SE, SE-F, 61, 82, 504, 2502, DF58, DF110D, DF110L, DF37, DF75, DF210, CT111, CT121, CT131, CT136, GA and TG (B) Antireflection film-forming composition comprising at least one vulcanizing agents may include,

As a more preferable combination,
[I-1] 2- (Meth) acrylamido-2-methylpropanesulfonic acid, perfluoroalkyl (meth) acrylates having 1 to 10 carbon atoms in the perfluoroalkyl group, and perfluorocarbons having 1 to 9 carbon atoms Fluoroalkyl (meth) acrylates in which an alkyl group is bonded to an ester oxygen atom through a methylene group and fluoroalkyl (meth) acrylates in which a C 1-8 perfluoroalkyl group is bonded to an ester oxygen atom through an ethylene group (A) at least one copolymer (salt) consisting of a copolymer (salt) with at least one selected from the group of groups, and selected from the group of Surfynol 104, 420, 440 and 465 And (B) an antireflective film-forming composition containing at least one additive;

[II-1] 2- (meth) acrylamido-2-methylpropanesulfonic acid, perfluoroalkyl (meth) acrylates having a perfluoroalkyl group having 1 to 10 carbon atoms, and perfluorocarbons having 1 to 9 carbon atoms Fluoroalkyl (meth) acrylates in which an alkyl group is bonded to an ester oxygen atom through a methylene group and fluoroalkyl (meth) acrylates in which a C 1-8 perfluoroalkyl group is bonded to an ester oxygen atom through an ethylene group (A) comprising a copolymer (salt) of at least one selected from the group of at least one and at least one of the (meth) acrylic acid alkyl ester compounds and / or at least one of the acrylamide derivatives (iii) At least one copolymer (salt), Surfynol 104, 420, 440 and Selected from 465 the group of (B) anti-reflective coating forming composition containing at least one additive can be exemplified.

The composition for forming an antireflection film of the present invention has a foaming degree of “10 or less” with respect to the defoaming property represented by “foaming degree” and “foaming stability” defined in JIS K2518. Is preferably “5 or less”, in particular the foaming degree is “1 or less”, and the foam stability is preferably “0”.
Here, the “foaming degree” means the volume of the foam (unit: milliliters) 5 minutes after the start of blowing when air is blown under the prescribed conditions, and the “foam stability” is 5% from the start of blowing. It means the volume of foam (unit: milliliter) after stopping blowing after a minute and then leaving it for another 10 minutes.

Solvent In the present invention, when forming an antireflection film from the composition for forming an antireflection film, after dissolving a predetermined amount of the composition in a solvent at a solid content concentration of, for example, 2 to 10% by weight, A solution (hereinafter referred to as “antireflection film forming composition solution”) is prepared by filtering with a filter of about 0.2 μm, and this antireflection film forming composition solution is spin coated, cast coated, roll It is applied on the resist film by an appropriate application method such as application.
As a solvent used for the preparation of the composition solution for forming an antireflection film, a solvent capable of dissolving each component constituting the composition, for example, water, monohydric alcohols such as methanol, ethanol, isopropanol, etc. , Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl ethyl ketone, cyclohexanone, 2 -Methyl hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl lupropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl -3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, ethyl pyruvate, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, Caproic acid, caprylic acid, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate and the like can be used.
These solvents are used alone or in admixture of two or more.
Among the solvents, those containing 10% by weight or more of water and / or monohydric alcohols are preferable.

Laminated body The laminated body of this invention forms the antireflection film which consists of a composition for antireflection film formation of this invention on a resist film.
The laminate of the present invention can be produced, for example, by the procedure described in the resist pattern forming method described below.
In the laminate of the present invention, the thickness of the antireflection film varies depending on the wavelength of the radiation used for forming the resist pattern, the refractive index of the antireflection film, etc., but λ / 4n (λ is the wavelength of the radiation, It is desirable that n is an odd multiple of the refractive index of the antireflection film), preferably within a range of 1 to 3 times λ / 4n.

Method for Forming Resist Pattern In the method for forming a resist pattern of the present invention, a resist film is formed on a substrate, exposed to the resist film, and then developed to form a resist pattern. The antireflection film is formed from the composition for forming an antireflection film of the present invention, then exposed to a predetermined pattern shape, and then developed to remove the antireflection film.
Examples of the resist used in the method for forming a resist pattern of the present invention include a positive resist such as a novolak resist containing a quinonediazide compound, and a positive or negative chemically amplified resist.
When forming a resist film from such a resist, the resist is dissolved in an appropriate solvent as required at a solid content concentration of, for example, 5 to 50% by weight, and then, for example, a filter having a pore diameter of about 0.2 μm. The resist solution is prepared by filtration with a suitable coating method such as spin coating, cast coating, roll coating, etc., on a substrate such as a silicon wafer or a wafer coated with aluminum. The resist film is formed by pre-baking and volatilizing the solvent. In this case, when using a commercially available resist solution, it can be used for forming a resist pattern as it is.
Examples of the solvent used for preparing the resist solution include the same solvents as those exemplified for the composition solution for forming an antireflection film.

Next, an antireflection film is formed by applying a composition solution for forming an antireflection film onto the resist film and usually baking again. In this case, as the thickness of the antireflection film is closer to an odd multiple of λ / 4n (λ is the wavelength of radiation and n is the refractive index of the antireflection film), the antireflection effect at the upper interface of the resist film increases.
When the antireflection film forming composition solution is applied on the resist film, an appropriate application method such as spin coating, cast coating, roll coating or the like can be employed.
In the present invention, any of the pre-bake after applying the resist solution and the bake after applying the anti-reflective film forming composition solution may be omitted to simplify the process.
Then, it exposes partially so that it may become a predetermined pattern shape. The radiation used at this time is, for example, visible light; ultraviolet light such as g-line or i-line; ArF excimer laser, KrF excimer laser, etc., depending on the resist used or the combination of the resist and the base-blocking antireflection film. Various kinds of radiation such as deep ultraviolet rays; X-rays such as synchrotron radiation; and charged particle beams such as electron beams are selectively used. In this case, post-exposure baking is preferably performed in order to improve the resolution, pattern shape, developability, and the like of the resist. The post-exposure baking temperature is appropriately adjusted depending on the resist used, but is usually about 50 to 200 ° C.

Thereafter, the resist film is developed to form a desired resist pattern.
The developer used for development can be appropriately selected according to the resist used, but an alkaline developer is preferable. In the case of developing with an alkaline developer, washing is usually performed after development.
In the method for forming a resist pattern of the present invention, by using an alkaline developer as a developer, there is no need to provide a separate anti-reflection film peeling step. However, the antireflection film can be easily removed at the same time as the resist coating, and this is one of the important features of the present invention.

Examples of the alkali developer 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- [ An aqueous solution in which an alkaline compound such as 4,3,0] -5-nonene is dissolved can be given.
In addition, an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant can be added to these alkaline developers.
In the case where development is performed using the alkali developer, it is usually washed with water after development.
As described above, the components constituting the composition for forming an antireflection film of the present invention, the relationship between these components, and the method for forming a laminate and a resist pattern of the present invention have been described in detail. As long as the above is not exceeded, various modifications other than the above can be adopted.

The composition for forming an antireflective film of the present invention has excellent coating properties, and remarkably suppresses reflection of radiation at the interface between the formed antireflective film and the resist film, thereby sufficiently reducing the standing wave effect. The pattern shape is excellent, and the generation of microbubbles can be remarkably suppressed, and the penetration of basic substances in the atmosphere into the resist film is effectively prevented to prevent resist pattern deterioration. It is also excellent in resolution and developability.
In addition, according to the resist pattern forming method of the present invention using the composition for forming an antireflection film, it is not affected by the basic substance in the atmosphere, even if the time from exposure to development changes. , Resist pattern dimensional variation can be suppressed to a very small level, and it is not affected by the standing wave effect, even if there are steps on the substrate surface, or the resist composition and viscosity, resist coating conditions, etc. Even if this changes, the dimensional variation of the resist pattern can be kept extremely small, and a highly accurate fine resist pattern can be stably formed. Furthermore, the resist pattern forming method of the present invention is excellent in resist resolution, developability, pattern shape, coatability, and the like.
Therefore, the present invention greatly contributes to the manufacture of highly integrated circuit elements.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. Here, parts and percentages are based on weight unless otherwise specified.
The resist used in each example and comparative example is AR1221J (trade name, manufactured by JSR Corporation) which is a chemically amplified positive resist for KrF excimer laser.
The formation of the resist pattern and the performance evaluation of the antireflection film were performed as follows.
Formation of resist pattern The resist was spin-coated on a silicon wafer having a diameter of 8 inches and then pre-baked on a hot plate at 140 ° C. for 90 seconds to form a resist film having a thickness of 0.6 μm. Thereafter, each antireflection film-forming composition solution was spin-coated on the resist film so that the thickness of each antireflection film to be formed was in the range of 35 to 50 nm. Thereafter, exposure was performed for a predetermined time using a stepper NSRS203B (wavelength 248 nm) manufactured by Nikon Corporation. Immediately after the exposure, a post-exposure bake was performed on a hot plate at 140 ° C. for 90 seconds, followed by tetramethylammonium hydroxide. Using a 2.38% aqueous solution, the resist pattern was developed at 25 ° C. for 1 minute, washed with water and dried.

Anti-reflection coating performance evaluation <br/>
In accordance with JIS K2518, when air is blown under the specified conditions, the volume of the foam after 5 minutes from the start of blowing (unit: milliliter (indicated as “ml” in Tables 3 and 4; the same shall apply hereinafter)). “Foam Stability (Ff)” and “Foam Stability (Fs)” defined by the volume of foam (unit: milliliters) after 5 minutes from the start of blowing and after standing for 10 minutes. The defoaming property was expressed as “Ff / Fs”.
resolution:
The line width of the resolved minimum resist pattern was measured with a scanning electron microscope to obtain the resolution.

Developability:
The antireflective film and the resist film were observed with a scanning electron microscope, and when no scum or development residue was observed, the developability was good.
Pattern shape and base blocking effect:
The cross-sectional shape of the resist pattern was observed with a scanning electron microscope, and when the cross-sectional shape shown in FIG. 1 was “A”, “B”, or “C”, the pattern shape was good. In addition, when no wrinkle as shown in “f” in FIG. 1 was observed on the upper part of the pattern, the blocking effect on the basic substance in the atmosphere (base blocking effect) was good.
Film loss:
The resist pattern was observed with a scanning electron microscope, and the difference between the initial film thickness of the resist film and the film thickness after formation of the resist pattern was defined as the amount of film reduction.

Micro bubble:
After forming a resist film on a silicon wafer, an antireflection film is formed as described above, and then the antireflection film is observed using a defect inspection apparatus KLA2351 manufactured by KLA Tencor, and the maximum dimension is 0.5 μm. The presence or absence of the above microbubbles was evaluated.
Defect after development:
After the resist pattern was formed on the silicon wafer as described above, the antireflection film was observed using a defect inspection apparatus KLA2351 manufactured by KLA Tencor and evaluated based on the presence or absence of defects due to microbubbles in the antireflection film.

The physical properties of the water-soluble resins obtained in Synthesis Example 1 and Synthesis Example 2 were measured as follows.
Mw:
Tosoh Corporation GPC column with using, Flow rate: 1.0 ml / min, eluent tetrahydrofuran, analytical conditions of column temperature 40 ° C., (G2000H _XL: 2 present, G3000H _XL: one: 1, G4000H _XL) The measurement was performed by gel permeation chromatography using monodisperse polystyrene as a standard.
Copolymerization ratio of each monomer:
Based on the absorption spectra by ¹ H-NMR and ¹³ C-NMR, the calculation was performed based on the area ratio of the peaks attributed to the side chain groups of each monomer.

Synthesis example 1
A stainless steel autoclave equipped with a stirrer, thermometer, heater, monomer addition pump and nitrogen gas introducing device was charged with 140 parts of ethylene glycol monobutyl ether, and the gas phase part was purged with nitrogen for 15 minutes. The temperature was raised to ° C. Thereafter, 10 parts 2-acrylamido-2-methylpropanesulfonic acid, 50 parts 2,2,3,3,3-pentafluoropropyl acrylate, 40 parts methyl methacrylate and benzoyl peroxide 2 while maintaining the internal temperature at 80 ° C. The mixture consisting of parts was continuously added over 3 hours. After the addition, the mixture was further reacted at 85 to 95 ° C. for 2 hours, and then cooled to 25 ° C. Thereafter, the reaction solution was vacuum dried to remove the solvent to obtain a water-soluble resin.
This water-soluble resin has an Mw of 3.0 × 10 ⁴ and a copolymerization ratio of 2-acrylamido-2-methylpropanesulfonic acid / 2,2,3,3,3-pentafluoropropyl acrylate / methyl methacrylate. It was 10/51/39 (%). This water-soluble resin is referred to as “water-soluble resin (A-1)”.

Synthesis example 2
A separable flask equipped with a stirrer, a thermometer, and a condenser tube was charged with 170 parts of methanol and bubbled with nitrogen gas for 15 minutes, and then 10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2,2,2-trimethyl 60 parts of fluoroethyl acrylate, 30 parts of ethyl acrylate and 4 parts of 2,2′-azobisisobutyronitrile were added, and the internal temperature was raised to 60 ° C. After 1 hour, the internal temperature was raised to 80 ° C., and the reaction was further continued for 4 hours, followed by cooling to 25 ° C. Thereafter, the reaction solution was vacuum dried to remove the solvent to obtain a water-soluble resin. The water-soluble resin, Mw is 1.5 × 10 ^4, 2-acrylamido-2-methylpropanesulfonic acid / 2,2,2-copolymerization ratio of trifluoroethyl acrylate / ethyl acrylate 10/59 / 31 (%). This water-soluble resin is referred to as “water-soluble resin (A-2)”.

Examples 1-12
After adding water to the water-soluble resin and the additive (B) shown in Table 1 to obtain a solid content concentration of 3%, the solution is filtered through a membrane filter having a pore size of 0.2 μm to obtain an antireflection film-forming composition solution. Obtained.
Next, a resist pattern was formed for each antireflection film-forming composition solution, and the performance of the antireflection film was evaluated. The evaluation results are shown in Table 3.

Comparative Examples 1-15
After adding water to the water-soluble resin and the additive (C) shown in Table 2 to obtain a solid content concentration of 3%, the mixture is filtered through a membrane filter having a pore size of 0.2 μm to obtain an antireflection film-forming composition solution. Obtained.
Next, a resist pattern was formed for each antireflection film-forming composition solution, and the performance of the antireflection film was evaluated. The evaluation results are shown in Table 4.

In Tables 1 and 2, components other than the water-soluble resin (A-1) and the water-soluble resin (A-2) are as follows.
Other water-soluble resins:
A-3: Poly (acrylic acid) (Mw = 3.0 × 10 ⁴ )
A-4: Poly (vinyl pyrrolidone) (Mw = 2.0 × 10 ⁴ )

(B) Additive:
B-1: Surfynol 104S (trade name, manufactured by Air Products)
B-2: Surfinol 465 (trade name, manufactured by Air Products)
B-3: Surfynol 440 (trade name, manufactured by Air Products)

(C) Additive:
C-1: F-top EF-112 (trade name, manufactured by Gemco)
C-2: Surflon S-141 (trade name, manufactured by Seimi Chemical Co., Ltd.)

It is a figure which shows the cross-sectional shape of a pattern, and the evaluation criteria of each pattern shape.

Claims (5)

(A) a water-soluble resin comprising a copolymer having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) and / or a salt thereof, and (B) the following formula ( 3. A composition for forming an antireflection film, comprising the compound represented by 3).

[In the formula (1), R ¹ represents a hydrogen atom or a monovalent organic group, and R ² represents a divalent organic group. ]

[In the formula (2), R ³ represents a hydrogen atom or a monovalent organic group, R f represents a fluoroalkyl group, and X represents a direct bond, an alkylene group or a fluoroalkylene group. ]

[In the formula (3), each R ⁴ represents an alkyl group having 1 to 5 carbon atoms independently of one another, an integer from respective m and n are 0 to 25, satisfying the (m + n) = 0 to 40. ]   The composition for forming an antireflection film according to claim 1, wherein the content of the component (B) is 0.01 to 20 parts by weight with respect to 100 parts by weight of the component (A).   A laminate obtained by forming an antireflection film comprising the composition for forming an antireflection film according to claim 1 or 2 on a resist film.   The antireflection according to claim 1 or 2, wherein a resist film is formed on the substrate, irradiated with radiation, and then developed to form a resist pattern on the resist film in advance. A method for forming a resist pattern, comprising: forming an antireflection film from a film-forming composition, irradiating a predetermined pattern shape with radiation, and then developing to remove the antireflection film.   5. The method for forming a resist pattern according to claim 4, wherein the development is carried out using an alkaline developer, whereby the antireflection film and the resist film are simultaneously removed during development.

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