JP2011186341A - Active ray-sensitive or radiation-sensitive resin composition, resist film formed by use of the composition, and pattern forming method using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active ray-sensitive or radiation-sensitive resin composition having excellent sensitivity while maintaining storage stability in a level suitable for practical use, and in particular, to provide a positive resist composition for electron beams, X-rays or EUV light, and a resist film formed of the composition and a pattern forming method using the composition. <P>SOLUTION: The active ray-sensitive or radiation-sensitive resin composition contains a resin (P) having a repeating unit expressed by general formula (I). In the formula, R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>each independently represent a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group or alkoxycarbonyl group; L<SB>1</SB>represents a single bond or a divalent linking group; L<SB>2</SB>represents an alkylene group or an arylene group having an electron withdrawing groups; and Ar represents an aromatic group, wherein L<SB>1</SB>or L<SB>2</SB>may be bonded to R<SB>3</SB>to form a five- or six-membered ring. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon reaction with actinic rays or radiation, a resist film using the composition, and a pattern forming method using the composition. . More specifically, the present invention relates to a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, a mold structure for imprinting, a further photofabrication process, a lithographic printing plate, an acid curing property. Actinic ray-sensitive or radiation-sensitive resin composition used in the composition, in particular, positive resist composition for electron beam, X-ray or EUV light, resist film using these compositions, and these compositions The present invention relates to a pattern forming method using

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line, and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is also being developed.

  In particular, electron beam lithography is positioned as a next-generation or next-generation pattern forming technique, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is an extremely important issue for shortening the wafer processing time. However, in positive resists for electron beams, when trying to increase sensitivity, not only the resolution is lowered, but also the line edge. Roughness deteriorates, and development of a resist that satisfies these characteristics at the same time is strongly desired. Here, the line edge roughness means that when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered. Particularly in the ultrafine region of 0.25 μm or less, the line edge roughness is an extremely important improvement issue. High sensitivity, high resolution, good pattern shape, and good line edge roughness are in a trade-off relationship, and it is very important how to satisfy them simultaneously.

  Further, microfabrication with a resist composition is not only directly used for the production of integrated circuits, but also recently applied to the production of so-called imprint mold structures (for example, Patent Documents 1 and 2 and (Refer nonpatent literature 1). Therefore, even when X-rays, soft X-rays, and electron beams are used as exposure light sources, it is important to satisfy high sensitivity, high resolution, good pattern shape, and good roughness characteristics at the same time. These solutions are necessary.

As one method for solving these problems, use of a resin having an ionic photoacid generator in the main chain or side chain has been studied (Patent Documents 3 to 5, Non-Patent Document 2). These resins are synthesized by radical polymerization of an ionic monomer and a nonionic monomer. At this time, since the residual monomer greatly affects the resist performance, it is necessary to remove and purify the residual monomer by reprecipitation or the like. As a purification method, a method of repeating a reprecipitation operation, a gel filtration chromatography method, and the like can be considered, but all have problems in producing economically.
As one means for solving the above problem, the use of a resin having a nonionic photoacid generating group in the main chain or side chain has been studied. For example, as a nonionic photoacid generating group, a positive resist composition using a resin having a disulfonyl group in Patent Document 6 and a resin containing an oxime sulfonate structure in Patent Documents 7 to 9 Reference 10 discloses positive resist compositions using a resin containing an aryl sulfonate structure, but each resist has reached a practical level that can be satisfied in terms of sensitivity and storage stability. There is no current situation.
Furthermore, although a specific aryl triflate compound is known as a nonionic photoacid generator (Patent Document 11), there is room for improvement in terms of acid generation ability, and it has these partial structures. The resin has not been known so far.

JP 2004-158287 A JP 2008-162101 A JP 2006-178317 A International Publication No. 06/121096 JP 2008-248063 A JP 2002-72483 A JP-A-4-25847 JP 2008-111120 A JP 2008-163218 A JP-A-10-221852 JP-A-5-181265

Nanoimprint Basics and Technology Development / Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Editing: Yoshihiko Hirai Frontier Publishing (issued in June 2006) Proc. of SPIE Vol. 6923, 692312, 2008

  In view of the above problems, the object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent sensitivity without impairing the practical level of storage stability, particularly an electron beam, X-ray or An object is to provide a positive resist composition for EUV light, a resist film using the composition, and a pattern forming method using the composition.

The above problems have been achieved by the following means.
That is, the present invention
[1]
An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (P) containing a repeating unit represented by the following general formula (I).

In the general formula (I),
R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
L ₁ represents a single bond or a divalent linking group,
L ₂ represents an alkylene group or an arylene group having an electron withdrawing group,
L ₁ or L ₂ may be bonded to R ₃ to form a 5-membered or 6-membered ring.
Ar represents an aromatic group.
[2]
In the general formula (I), actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the L ₂ is a fluorine-containing alkylene group or a fluorine-containing arylene group.
[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein in the general formula (I), L ₂ is a perfluoroalkylene group.
[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin (P) further contains a repeating unit having an acid-decomposable group. .
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin (P) further contains a repeating unit having a hydroxyl group.

[6]
The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein the repeating unit containing a hydroxyl group is a repeating unit derived from hydroxystyrene.
[7]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin (P) further contains a repeating unit having a lactone structure.
[8]
[1] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [7].
[9]
The pattern formation method characterized by including the process of exposing the resist film as described in [8], and the process of developing the exposed film | membrane.

[10]
The pattern forming method according to [9], wherein the exposure is performed using X-rays, electron beams, or extreme ultraviolet rays.
[11]
A resin comprising a repeating unit represented by the following general formula (II):

In the general formula (II),
R ₁ ′ represents a hydrogen atom or an alkyl group,
L ₁ represents a single bond or a divalent linking group,
Rf represents a perfluoroalkylene group,
Ar represents an aromatic group.

The present invention preferably further has the following configuration.
[12]
In the above general formula (I), L ₁ is —O—, —CO—, —S—, —SO—, —SO ₂ —, —NR′— (R ′ is a hydrogen atom or an alkyl group), an alkylene group. , A cycloalkylene group, an alkenylene group, an arylene group, a divalent group formed by combining a plurality of these, or a single bond, the actinic ray according to any one of [1] to [7] Or radiation sensitive resin composition.
[13]
[1] to [7] and [12], wherein Ar is a benzene ring group, a naphthalene ring group or an anthracene ring group in the general formula (I). A light-sensitive or radiation-sensitive resin composition.
[14]
Any of [4] to [7], [12] and [13], wherein the repeating unit having an acid-decomposable group is represented by the following general formula (AI) or (A-II): 2. The actinic ray-sensitive or radiation-sensitive resin composition according to item 1.

In the above general formula (AI),
R < _1a > -R < _3a > is synonymous with R < ₁ > -R < ₃ > mentioned above about general formula (I). R _3a may combine with L ₁₁ to form a 5-membered or 6-membered ring.
L ₁₁ represents a single bond or a divalent linking group (provided that it forms a 5-membered or 6-membered ring by binding to R _3a ). R ₁₁ represents an alkyl group, and R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ₁₂ and R ₁₃ may combine with each other to form a ring.
In the general formula (A-II),
R _<1b > -R < _3b > is synonymous with R < ₁ > -R < ₃ > mentioned above about general formula (I). R _3b may combine with L ₂₁ to form a 5-membered or 6-membered ring.
L ₂₁ is synonymous with L ₁₁ .
Ar ₂₁ represents an arylene group.
R ₂₁ and R ₂₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, an alicyclic group which may contain a hetero atom, an aromatic group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
Any two of Q, M, and R ₂₁ may combine to form a 5-membered or 6-membered ring.
[15]
The actinic ray-sensitive or radiation-sensitive resin composition according to [7], wherein the repeating unit having a lactone structure is represented by the following general formula (AII).

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group formed by combining these. .
V represents a group having a lactone structure.
[16]
In general formula (II), L ₁ is —O—, —CO—, —S—, —SO—, —SO ₂ —, —NR—, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or the like. The resin according to [11], wherein the resin is a divalent group formed by combining a plurality of groups or a single bond.
[17]
In general formula (II), Ar is a benzene ring group, a naphthalene ring group, or an anthracene ring group, The resin as described in [11] or [16] characterized by the above-mentioned.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can provide excellent sensitivity without impairing the practical level of storage stability.
In particular, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is suitable as a positive resist composition for electron beam, X-ray or EUV light.
Since the resist film and the pattern forming method of the present invention are formed using the resin composition, they are suitable for use with electron beams, X-rays, or EUV light.

Hereinafter, the present invention will be described in detail.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. In addition, the term “exposure” in the present specification is not limited to exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in exposure.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the resin composition of the present invention”) contains a resin (P).
<Resin (P)>
The resin (P) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin containing a repeating unit (I) represented by the following general formula (I).

In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
The alkyl group for R _{1 to} R ₃ may have a substituent, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or an n-butyl group, which may have a substituent. , Sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, and an alkyl group having 20 or less carbon atoms can be mentioned, and an alkyl group having 8 or less carbon atoms is preferable.
Specific examples of the substituent that the alkyl group for R _{1 to} R ₃ may have include a halogen atom (fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, a nitro group, a cyano group, an amide group, and a sulfonamide. Group, alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), alkoxy group (methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, etc.), alkoxycarbonyl group (Methoxycarbonyl group, ethoxycarbonyl group etc.), formyl group, acyl group (acetyl group, benzoyl group etc.), acyloxy group (acetoxy group, butyryloxy group etc.), carboxy group etc. are mentioned, and the carbon number of the substituent is 8 The following is preferred.
As the alkyl group contained in the alkoxycarbonyl group for R ₁ to R _3, the same alkyl groups represented by _R 1 to R ₃ are preferred.

The cycloalkyl group for R _{1 to} R ₃ may be a cycloalkyl group which may have a substituent and may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent. Specific examples of the substituent that the cycloalkyl group for R _{1 to} R ₃ may have include specific examples similar to the specific examples given as the substituent that the alkyl group may have. Can do.
As a halogen atom about R < ₁ > -R < ₃ >, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A fluorine atom is more preferable.
R ₁ is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and more preferably a hydrogen atom or a methyl group. R ₂ and R ₃ are preferably hydrogen atoms.

L ₁ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ₁ include —O—, —CO—, —S—, —SO—, —SO ₂ —, —NR′— (R ′ represents a hydrogen atom or an alkyl group). ) Divalent nitrogen-containing non-aromatic heterocyclic group, alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, specifically methylene group, ethylene group, propylene group, butylene group, etc.), A cycloalkylene group (preferably a cycloalkylene group having 3 to 8 carbon atoms, specifically 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group; Etc.), an alkenylene group (preferably an alkenylene group having 2 to 8 carbon atoms, specifically, a cis-2,3-butenylene group, trans-2,3-butenylene group, etc.), an arylene group (carbon number) Be an arylene group of 6 to 10 It is preferable. Specifically, 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene, 2,6-naphthylene group), and includes groups are combined. The divalent linking group represented by L ₁ preferably has 20 or less carbon atoms.
In —NR′— for L ₁ , the alkyl group represented by R ′ is a linear or branched alkyl group which may have a substituent, and preferably has a substituent. Preferred examples include methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, hexyl groups, 2-ethylhexyl groups, octyl groups, and dodecyl groups, and more preferred are alkyl groups having 20 or less carbon atoms. Is an alkyl group having 8 or less carbon atoms, particularly preferably an alkyl group having 3 or less carbon atoms. R ′ is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.
In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members, specifically, for example, Examples thereof include a divalent linking group having a structure.

As the divalent linking group represented by L ₁ , among them, —O—, —CO—, —SO ₂ —, a divalent nitrogen-containing non-aromatic heterocyclic group, an alkylene group, an arylene group (particularly preferably 1,4-phenylene) and a group obtained by combining a plurality of these are preferable.
Although the preferable example of the coupling group which combined multiple said coupling groups is shown below, this invention is not limited to these.

In the above formula, * represents a linking site with the polymer main chain, and ** represents a linking site with L ₂ .
In addition, these coupling groups may be further substituted with the above-described substituents and the like as the substituents that the alkyl group for R _{1 to} R ₃ may have.
L ₂ represents an electron withdrawing group (for example, fluorine atom, chlorine atom, nitro group, cyano group, acyl group, alkoxycarbonyl group, acyl group, carboxyl group, sulfo group, fluorinated alkyl group, alkylsulfone group, aryl An alkylene group or an arylene group having a sulfone group and the like.
The alkylene group having an electron withdrawing group represented by L ₂ is preferably a linear or branched, electron withdrawing group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. It is an alkylene group having a group, and may have a substituent other than the electron withdrawing group. Specific examples of the alkylene group having an electron withdrawing group for L ₂ include those having an electron withdrawing group as a substituent on the same alkylene group as the alkylene group described above for L ₁ .
The arylene group having an electron-withdrawing group represented by L ₂ is preferably an arylene group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms having an electron-withdrawing group, and the electron-withdrawing group. You may have substituents other than group. Specific examples of the arylene group having an electron-withdrawing group for L ₂ include those having an electron-withdrawing group as a substituent on the same arylene group as the arylene group described above for L ₁ .
Examples of the preferred substituent other than the electron-withdrawing group for L ₂ include the substituents described above as the substituent that the alkyl group for R _{1 to} R ₃ may have.
L ₂ is preferably an alkylene group or arylene group substituted with at least one fluorine atom (fluorine-containing alkylene group or fluorine-containing arylene group), more preferably an alkylene group in which all hydrogen atoms are substituted with fluorine atoms. Or an arylene group, particularly preferably an alkylene group (perfluoroalkylene group) in which all hydrogen atoms are substituted with fluorine atoms.
Preferred examples of L ₂ is the present invention is not limited to the following.

In the above formula, * represents a linking site with an aryl sulfonic acid ester, and ** represents a linking site with L ₁ .
L ₁ or L ₂ may be bonded to R ₃ to form a 5-membered or 6-membered ring.
Ar represents an aromatic group which may have a substituent. As the aromatic group represented by Ar, an aromatic ring having 6 to 30 carbon atoms is preferable, and specifically, a benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, a heptalene ring. Group, indecene ring group, perylene ring group, pentacene ring group, acetaphthalene ring group, phenanthrene ring group, anthracene ring group, naphthacene ring group, pentacene ring group, chrysene ring group, triphenylene ring group, indene ring group, fluorene ring group, Triphenylene ring group, naphthacene ring group, biphenyl ring group, pyrrole ring group, furan ring group, thiophene ring group, imidazole ring group, oxazole ring group, thiazole ring group, pyridine ring group, pyrazine ring group, pyrimidine ring group, pyridazine ring Group, indolizine ring group, indole ring group, benzofuran ring group, benzothiophene ring group, isobenzofuran Group, quinolidine ring group, quinoline ring group, phthalazine ring group, naphthyridine ring group, quinoxaline ring group, quinoxazoline ring group, isoquinoline ring group, carbazole ring group, phenanthridine ring group, acridine ring group, phenanthroline ring group, thianthrene ring Group, chromene ring group, xanthene ring group, phenoxathiin ring group, phenothiazine ring group, phenazine ring group and the like. Of these, an aromatic hydrocarbon group is preferable and a benzene ring group, a naphthalene ring group, and an anthracene ring group are more preferable from the viewpoint of achieving both higher sensitivity and storage stability. As a preferable substituent of Ar, the substituent etc. which were mentioned above can be mentioned as the substituent which the alkyl group about R < ₁ > -R < ₃ > may have.
As a preferred embodiment of the repeating unit represented by the general formula (I), there can be mentioned the repeating unit (II) represented by the following general formula (II).
The present invention also relates to a resin containing a repeating unit (II) represented by the following general formula (II) (hereinafter sometimes simply referred to as “resin of the present invention”).

Where
R ₁ ′ represents a hydrogen atom or an alkyl group.
L ₁ and Ar are as defined above for general formula (I).
Rf preferably represents a perfluoroalkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. Specific examples of the perfluoroalkylene group for Rf include a perfluoromethylene group, a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group.
According to the resin of the present invention, an actinic ray-sensitive or radiation-sensitive resin composition exhibiting the above excellent sensitivity and storage stability can be prepared.

  Although the preferable example of the repeating unit (I) represented by general formula (I) or (II) in this invention is shown below, this invention is not limited to these.

  The content of the repeating unit (I) represented by the general formula (I) in the resin (P) is preferably in the range of 0.5 to 90 mol%, more preferably based on all repeating units. Is in the range of 1 to 75 mol%, more preferably in the range of 2 to 50 mol%. One type of repeating unit represented by the general formula (I) may be used, or two or more types may be used in combination.

The repeating units (I) and (II) contained in the resin (P) have been described above. Thus, the resin (P) is represented by the repeating unit (I) represented by the general formula (I) or (II). ) Or (II), having L ₂ (or Rf) having an electron withdrawing group, and Ar, without impairing the practical level of storage stability (low sensitivity fluctuation with time), Excellent sensitivity can be provided.
Although it is not certain that the present invention can provide excellent sensitivity, L ₂ (or Rf) having an electron withdrawing group is bonded to the sulfonate group in the repeating unit (I) or (II). It is estimated that sulfonic acid is more easily generated by exposure, and as a result, the sensitivity is improved.
In addition, since the resin (P) in this invention has the acid anion group which generate | occur | produces by irradiation of actinic light or a radiation connected with the polymer chain, it can suppress a spreading | diffusion of an acid significantly, and it improves resolution. Since the generated acid does not diffuse even at high temperature PEB (post-exposure bake: post-exposure heating), in addition to the effects described above, the line width variation (LER) is small and the exposure latitude (MEEF) is established at a high level. Is something that can be done.
In addition, since the resin (P) in the present invention generates an acid upon irradiation with actinic rays or radiation, the resin (P) is excellent in solubility in an alkaline developer in an exposed area even if it does not have an acid-decomposable group.

  The resin (P) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a repeating unit (A) having an acid-decomposable group.

The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.
Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.

Examples of the group leaving with an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 to} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  The repeating unit (A) having an acid-decomposable group is preferably one that is decomposed by the action of an acid to improve the solubility in an alkali developer. As a preferred embodiment of the repeating unit having an acid-decomposable group which is decomposed by the action of an acid and improves the solubility in an alkali developer, the following can be exemplified.

In the above general formula (AI),
R < _1a > -R < _3a > is synonymous with R < ₁ > -R < ₃ > mentioned above about general formula (I), respectively. R _3a may combine with L ₁₁ to form a 5-membered or 6-membered ring.
L ₁₁ represents a single bond or a divalent linking group (provided that it forms a 5-membered or 6-membered ring by binding to R _3a ). R ₁₁ represents an alkyl group, and R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ₁₂ and R ₁₃ may combine with each other to form a ring.

Examples of the divalent linking group represented by L _11, an alkylene group, an arylene group, aralkylene _{group, -COO-L 12 -, -} O-L 12 -, a group formed by combining two or more of these Is mentioned. The divalent linking group represented by L ₁₁ preferably has 20 or less carbon atoms. Here, L ₁₂ represents an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group. Specific examples of the alkylene group, cycloalkylene group and arylene group for L ₁₁ and L ₁₂ include the specific examples of the alkylene group, cycloalkylene group and arylene group described above for L _{1 in} formula (I). .
Specific examples of the aralkylene group for L ₁₁ and L ₁₂ include a benzylene group and a xylylene group.

L ₁₁ is preferably a single bond, a group represented by —COO-L ₁₂ — (L ₁₂ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group or a propylene group) or an arylene group.
The alkyl group for R _{11 to} R ₁₃ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n- Particularly preferred are those having 1 to 4 carbon atoms such as a butyl group, an isobutyl group and a t-butyl group.

The cycloalkyl group represented by R ₁₂ and R ₁₃ is preferably one having 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group or a tetracyclodecanyl group. Polycyclic such as tetracyclododecanyl group may be used, but monocyclic is more preferable from the viewpoint of solubility in a resist solvent.
The ring formed by combining R ₁₂ and R ₁₃ with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetra Polycyclic such as cyclodecanyl group and tetracyclododecanyl group may be used, but monocyclic is more preferable from the viewpoint of solubility in a resist solvent. When R ₁₂ and R ₁₃ are bonded to each other to form a ring, R ₁₁ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

The aryl group represented by R ₁₂ and R ₁₃ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. When one of R ₁₂ and R ₁₃ is a hydrogen atom, the other is preferably an aryl group.

In the general formula (A-II),
R _<1b > -R < _3b > is synonymous with R < ₁ > -R < ₃ > mentioned above about general formula (I), respectively. R _3b may combine with L ₂₁ to form a 5-membered or 6-membered ring.
L ₂₁ is synonymous with L ₁₁ .
Ar ₂₁ represents an arylene group.
R ₂₁ and R ₂₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and the alkyl group, cycloalkyl group, aryl group, or aralkyl group has a substituent. Also good.
M represents a single bond or a divalent linking group.
Q may have a substituted or unsubstituted alkyl group, a substituent, an alicyclic group that may contain a heteroatom, a substituent, or a heteroatom. It represents a good aromatic group, an amino group which may have a substituent, an ammonium group which may have a substituent, a mercapto group which may have a substituent, a cyano group or an aldehyde group.
Any two of Q, M, and R ₂₁ may combine to form a 5-membered or 6-membered ring.

The arylene group represented by Ar ₂₁ is preferably an arylene group having 6 to 14 carbon atoms which may have a substituent, and specific examples include a phenylene group, a methylphenylene group, a benzylene group, and a naphthylene group. . Preferable substituents for Ar ₂₁ include the substituents as described above for R _{1 to} R ₃ .
The alkyl group represented by R ₂₁ and R ₂₂ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group. , A hexyl group, and an octyl group can be preferably exemplified.
The cycloalkyl group represented by R ₂₁ and R ₂₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group are preferably exemplified. it can.
The aryl group represented by R ₂₁ and R ₂₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a tolyl group, a naphthyl group, an anthryl group, and the like. .
The aralkyl group represented by R ₂₁ and R ₂₂ has, for example, 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

Examples of the divalent linking group represented by M include an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group), a cycloalkylene group (for example, a cyclopentylene group). , Cyclohexylene group, etc.), alkenylene group (eg, vinylene group, propenylene group, butenylene group, etc.), arylene group (eg, phenylene group, tolylene group, naphthylene group, etc.), -S-, -O-, -CO- , —SO ₂ —, —N (R ₀ ) —, and a divalent linking group in which a plurality of these are combined. The divalent linking group represented by M preferably has 20 or less carbon atoms. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group). Octyl group, etc.).

The alkyl group represented by Q is the same as the alkyl group as R ₂₁ and R ₂₂ described above.
The in alicyclic and aromatic groups in the aromatic group which may also contain a good alicyclic group and hetero atom contain a hetero atom as Q, described above as R ₂₁ and R ₂₂ of the above cyclo An alkyl group, an aryl group, etc. are mentioned, Preferably it is C3-C15.
Examples of the alicyclic group containing a hetero atom and the aromatic group containing a hetero atom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. And groups having a heterocyclic structure such as pyrrolidone, but are not limited to these as long as the structure is generally called a heterocyclic ring (a ring formed of carbon and a heteroatom, or a ring formed of a heteroatom). .

As the 5-membered or 6-membered ring that may be formed by bonding any two of Q, M, and R ₂₁ , any two of Q, M, and R ₂₁ are bonded to each other, for example, propylene group, butylene group To form a 5-membered or 6-membered ring containing an oxygen atom.
Each group represented by R ₂₁ , R ₂₂ , M, and Q may further have a substituent. Specific examples of such a substituent include an alkyl group for R _{1 to} R _3. Specific examples of the substituent described above are given as the substituent that may be included.

The group represented by -MQ is preferably a group composed of 1 to 30 carbon atoms, more preferably a group composed of 5 to 20 carbon atoms.
Specific examples of the repeating unit (A) having an acid-decomposable group are shown below, but the present invention is not limited thereto.

One type of repeating unit (A) having an acid-decomposable group may be used, or two or more types may be used in combination.
The resin (P) in the present invention may or may not contain the repeating unit (A) having an acid-decomposable group, but when the repeating unit (A) is contained in the resin (P), The content of the repeating unit (A) having an acid-decomposable group in the resin (P) is preferably in the range of 0.1 to 90 mol% with respect to all repeating units, and is preferably 5 to 80 mol%. It is more preferable that it be in the range, and it is particularly preferable that it be contained in the range of 7 to 70 mol%.
Ratio of repeating unit (I) represented by general formula (I) in resin (P) to repeating unit (A) having an acid-decomposable group [number of moles of repeating unit (I) / repeating unit (A) The number of moles] is preferably 0.04 to 1.0, more preferably 0.05 to 0.9, and particularly preferably 0.06 to 0.8.

  The resin (P) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is further used from the viewpoint of assisting the improvement in solubility in an alkali developer and the adhesion with the substrate. It preferably contains a repeating unit (B) having a hydroxyl group. Preferable embodiments of the repeating unit (B) having a hydroxyl group include those shown below.

In formula (B),
R _<1c > -R <_3c> is synonymous with R < ₁ > -R < ₃ > mentioned above about general formula (I), respectively, Z represents the organic group containing a hydroxyl group.
The organic group represented by Z is preferably an organic group having 1 to 30 carbon atoms, and more preferably 6 to 15 carbon atoms. Although the preferable example of the organic group Z containing a hydroxyl group is shown below, this invention is not limited to these. * Represents a linking site to the carbon atom to which R _1c is bonded.

In the formula, p represents an integer of 1 to 3.
The organic group represented by Z is more preferably represented by the following formula.

One type of repeating unit (B) having a hydroxyl group may be used, or two or more types may be used in combination. The repeating unit (B) having a hydroxyl group is particularly preferably a repeating unit derived from hydroxystyrene (hydroxystyrene unit), and most preferably a p-hydroxystyrene unit.
The resin (P) in the present invention may or may not contain the repeating unit (B) having a hydroxyl group. However, when the resin (P) contains the repeating unit (B) having a hydroxyl group, the resin (P ) The content of the repeating unit (B) having a hydroxyl group is preferably in the range of 0.1 to 90 mol%, more preferably in the range of 2 to 80 mol%, based on all repeating units. A range of 3 to 70 mol% is particularly preferable.

  The resin (P) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a repeating unit (C) having a lactone structure. As the repeating unit (C) having a lactone structure, those represented by the following general formula (AII) are preferred.

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).
Preferable substituents that the alkyl group for Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these. The divalent linking group represented by Ab preferably has 20 or less carbon atoms. Preferably a single _bond, -Ab 1 -CO ₂ - is a divalent linking group represented by.
Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
V represents a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer. A group having an ester bond is preferable, and a group having a lactone structure is more preferable.

  As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. It is preferable that the other ring structure is condensed in the form to be formed. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures include (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17), (LC1-4) is more preferable.

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 2 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

  The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

Although the specific example of the repeating unit represented by general formula (AII) in resin (P) is shown below, this invention is not limited to this. In the formula, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

One type of repeating unit represented by formula (AII) may be used, or two or more types may be used in combination.
The resin (P) in the present invention may or may not contain the repeating unit (C) having a lactone structure. When the repeating unit (C) is contained in the resin (P), the content of the repeating unit (C) having a lactone structure in the resin (P) is 0.1 to 80 mol% with respect to all repeating units. It is preferable that it is the range of this, More preferably, it is the range of 1-60 mol%, More preferably, it is the range of 2-40 mol%. Since the resin (P) in the present invention contains a specific lactone structure, the solubility in an alkali developer is improved, and the line edge roughness and the like are improved.

The form of the resin (P) in the present invention may be any of random type, block type, comb type, and star type.
The resin (P) in the present invention can be produced, for example, by a polymerization method such as radical, cation, or anion polymerization of an unsaturated monomer corresponding to each repeating unit. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each repeating unit.
In the present invention, the unsaturated monomer corresponding to the precursor of the repeating unit represented by the general formula (II) is preferably a polymerizable compound represented by the following general formula (III).

Where
R ₁ ′, L ₁ , Ar and Rf have the same meaning as described above for the general formula (II).

  The polymerizable compound represented by the general formula (III) can be used for producing a resin contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention that exhibits excellent sensitivity and storage stability. .

As a polymerization method for producing the resin (P) in the present invention, for example, a batch polymerization method in which an unsaturated monomer and an initiator corresponding to a precursor of each repeating unit are dissolved in a solvent and polymerization is performed by heating. And a dropping polymerization method in which the solution of the unsaturated monomer and the initiator is added dropwise to the heating solvent over 1 to 10 hours, and the dropping polymerization method is preferable.
Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the below-mentioned solvent (For example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone etc.) contained in the resin composition of this invention is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent described later contained in the resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

For the detailed polymerization method and purification method, the methods described in Chapter 2 “Polymer Synthesis” of “5th edition Experimental Chemistry Course 26 Polymer Chemistry” published by Maruzen Co., Ltd. can be used.
The resin (P) in the present invention has a main chain or a side chain because the repeating unit (I) or (II) represented by the general formula (I) or (II) is nonionic near neutrality. The resin is more suitable for production than a resin having an ionic photoacid generating group. For example, when a resin having an ionic photoacid generating group in the main chain or side chain is purified, it is necessary to repeat the reprecipitation operation a plurality of times in order to remove the residual monomer. Exchange resin cannot be used. In contrast, the resin (P) in the present invention does not cause such a problem.

The molecular weight of the resin (P) in the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 20000, and in the range of 2000 to 10,000. It is particularly preferred. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).
The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50.

Further, for the purpose of improving the performance of the resin (P) in the present invention, it may further have a repeating unit derived from another polymerizable monomer as long as the dry etching resistance is not significantly impaired.
The content of repeating units derived from other polymerizable monomers in the resin is generally 50 mol% or less, preferably 30 mol% or less, based on all repeating units. Other polymerizable monomers that can be used include those shown below. For example, (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, dialkyl itaconates, dialkyl esters of maleic acid or fumaric acid, etc. It is a compound having one selected addition polymerizable unsaturated bond.
Specifically, (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Amyl acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid-t-octyl, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid 2 -Hydroxyethyl, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate and the like.
(Meth) acrylamides include, for example, (meth) acrylamide, N-alkyl (meth) acrylamide, (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl Group, t-butyl group, heptyl group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-aryl (meth) acrylamide (as aryl groups, for example, phenyl group, tolyl group , Nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl group, carboxyphenyl group, etc.), N, N-dialkyl (meth) acrylamide (the alkyl group has 1 to 10 carbon atoms, for example, , Methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Hexyl group, etc.), N, N-aryl (meth) acrylamide (aryl groups include, for example, phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide. N-2-acetamidoethyl-N-acetylacrylamide and the like.

Examples of allyl compounds include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyl Examples include oxyethanol.
Examples of vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl aryl ethers (eg vinyl phenyl ether, vinyl tolyl ether, vinyl chloride) Phenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether) and the like.
Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Examples thereof include vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.
Examples of styrenes include styrene and alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene). , Trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg, methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), alkylcarbonyloxy styrene (eg, 4-acetoxy styrene, 4-cyclohexylcarbonyloxystyrene), arylcarbonyloxystyrene (for example, 4-phenylcarbonyloxystyrene) ), Halogen styrene (for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro) Rumethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), cyanostyrene, carboxystyrene and the like.
Examples of the crotonic acid esters include alkyl crotonic acid (for example, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.).
Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
Examples of the dialkyl esters of maleic acid or fumaric acid include dimethyl maleate and dibutyl fumarate.
In addition, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilonitrile, and the like can be given. In general, any addition-polymerizable unsaturated compound copolymerizable with the repeating unit according to the present invention can be used without any particular limitation.

  Resin (P) in this invention can be used individually by 1 type or in combination of 2 or more types. The content of the resin (P) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. 70-100 mass% is especially preferable.

Specific examples of the resin (P) include, for example, specific examples of the repeating unit (A) having one or more repeating units selected from the specific examples of the general formula (I) as essential components and having the acid-decomposable group. Examples include a resin further having one or more types of repeating units selected from the specific examples of the repeating unit (B) having a hydroxyl group and the specific examples of the repeating unit (C) having a lactone structure.
Although the preferable specific example of resin (P) is shown below, this invention is not limited to these.

〔solvent〕
The solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably an organic solvent, and examples thereof include the following.
Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA; alias: 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether Preferred are acetate and ethylene glycol monoethyl ether acetate.
Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME; alias: 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, Preferred is ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.
Examples of cyclic lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Preferred examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and 1-methoxy-2-propyl acetate.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. However, there is a problem of outgassing (irradiating high energy rays such as EUV light under high vacuum) In this case, the compound in the resist film is destroyed by fragmentation and volatilizes as a low molecular component during exposure to contaminate the environment in the exposure apparatus). Glycol monomethyl ether acetate, propylene glycol monomethyl ether, boiling point are particularly preferred 0.99 ° C. or less of the solvent at atmospheric pressure. These solvents may be used alone or in combination of two or more. The content of the solvent in the total amount of the resin composition of the present invention can be appropriately adjusted according to the desired film thickness and the like, but generally the total solid content concentration of the composition is 0.5 to 30% by mass, Preferably it is prepared so that it may become 1.0-20 mass%, More preferably, it will be 1.5-10 mass%.

[Other ingredients]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is further decomposed by the action of a basic compound and an acid in addition to the resin (P) and the solvent described above, and is soluble in alkali water. Resins that increase the dissolution rate in water, conventional photoacid generators, surfactants, acid-decomposable dissolution-inhibiting compounds, dyes, plasticizers, photosensitizers, and dissolution-promoting compounds in developer solutions, proton acceptor properties A compound having a functional group or the like can be contained.

<Basic compound>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound.
The basic compound is preferably a nitrogen-containing organic basic compound.

  Although the compound which can be used as the said basic compound is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.

(1) Compound represented by the following general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom, an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, or an aralkyl group. However, not all three Rs are hydrogen atoms.
Although carbon number of the alkyl group as R is not specifically limited, Usually, 1-20, Preferably it is 1-12. Specific examples include the alkyl groups described above for R _{1 to} R ₃ in the general formula (I).
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, 3-20, Preferably it is 5-15. Specific examples include the cycloalkyl groups described above for R _{1 to} R ₃ in the general formula (I).
Although carbon number of the aryl group as R is not specifically limited, Usually, 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, 7-20, Preferably it is 7-11. Specific examples include a benzyl group.
In the alkyl group, cycloalkyl group, aryl group or aralkyl group as R, a hydrogen atom may be substituted with a substituent. Specific examples of the substituent include arbitrary substituents such as the substituents described above as the substituent that the alkyl group for R _{1 to} R ₃ may have.
In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are not hydrogen atoms.

Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, and dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline and the like.
In addition, a compound in which at least one R in the general formula (BS-1) is an alkyl group substituted with a hydroxyl group can be mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

The alkyl group as R may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 and thereafter of US Pat. No. 6,040,112.

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, a compound having an imidazole structure (such as 2-phenylbenzimidazole), a compound having a piperidine structure (such as N-hydroxyethylpiperidine), a compound having a pyridine structure (such as 4-dimethylaminopyridine), an antipyrine structure Compounds having antipyrine and the like.
A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. Preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.
Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007/0224539. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt Ammonium salts are also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

  In addition, compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in paragraph 0108 of JP-A No. 2007-298869, and the like can also be used.

These basic compounds are used alone or in combination of two or more.
The usage-amount of the said basic compound is 0.001-10 mass% normally based on the total solid of actinic-ray-sensitive or radiation-sensitive resin composition, Preferably it is 0.01-5 mass%.

<Resin that is decomposed by the action of an acid to increase the dissolution rate with respect to alkaline water solubility>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain, in addition to the resin (P), a resin that decomposes by the action of an acid to increase the dissolution rate with respect to alkali water solubility.

  Resins that decompose due to the action of an acid and increase the dissolution rate in an alkaline aqueous solution (hereinafter also referred to as “acid-decomposable resins”) are not included in the main chain or side chain of the resin, or both of the main chain and side chain. It is a resin having a group (acid-decomposable group) that decomposes by the action of and produces an alkali-soluble group. Among these, a resin having an acid-decomposable group in the side chain is more preferable.

The acid-decomposable resin is decomposed with an acid into an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It can be obtained by reacting a precursor of a group capable of being reacted or copolymerizing an alkali-soluble resin monomer having an acid-decomposable group bonded thereto with various monomers.
As the acid-decomposable group, for example, in a resin having an alkali-soluble group such as —COOH group and —OH group, a group in which the hydrogen atom of the alkali-soluble group shown on the left is substituted with a group capable of leaving by the action of an acid is preferable.
Specific examples of the acid-decomposable group include the same groups as the acid-decomposable groups described above for the repeating unit (A) in the resin (P) in the present invention.

  The resin having an alkali-soluble group is not particularly limited. For example, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene) and copolymers thereof, hydrogenated poly (Hydroxystyrene), poly (hydroxystyrene) s having a substituent represented by the following structure, and resins having phenolic hydroxyl groups, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers, hydrogen An alkali-soluble resin having a hydroxystyrene structural unit such as a modified novolak resin, and an alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

  The alkali dissolution rate of these alkali-soluble resins is preferably at least 170 kg / second as measured with 2.38 mass% tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 Å / second or more.

  The content of the group capable of decomposing with an acid is determined by the number of repeating units (X) having a group decomposable with an acid in the resin and the number of repeating units having an alkali-soluble group not protected by a group capable of leaving with an acid ( Y) and represented by X / (X + Y). The content is preferably 0.01 to 0.70, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

The weight average molecular weight of the acid-decomposable resin is preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000 as a polystyrene conversion value by the GPC method.
The dispersity (Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.1 to 1.7.
Two or more acid-decomposable resins may be used in combination.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain an acid-decomposable resin in addition to the resin (P). When the composition contains an acid-decomposable resin other than the resin (P), the content of the acid-decomposable resin other than the resin (P) in the resin composition is 0.00 in the total solid content of the resin composition. 0001-60 mass% is preferable, More preferably, it is 0.0001-50 mass%.

<Acid generator>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”).
Examples of such an acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or an actinic ray or radiation used for a microresist. A known compound that generates an acid by irradiation and a mixture thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Specific examples thereof include those described in [0164] to [0248] of US Patent Application Publication No. 2008 / 0241737A1. These acid generators may be used in combination of two or more.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, when an acid generator is used in addition to the repeating unit (I) in the resin (P), the acid generator is used singly or in combination. More than one species can be used in combination. The content of the acid generator other than the repeating unit (I) in the resin (P) in the resin composition is preferably 0 to 10% by mass, more preferably 0 to 5%, based on the total solid content of the resin composition. % By mass. The acid generator other than the repeating unit (I) in the resin (P) is not an essential component in the present invention, but is usually used in an amount of 0.01% by mass or more in order to obtain the effect of being contained.

<Surfactant>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a surfactant.
As the surfactant, fluorine-based and / or silicon-based surfactants are preferable. Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include those described in [0273] et seq. Of US Patent Application Publication No. 2008/0248425.

Surfactants may be used alone or in combination of two or more.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but when it contains a surfactant, the content of the surfactant is Preferably it is 0.001-2 mass% with respect to the total solid of a light sensitive or radiation sensitive resin composition, More preferably, it is 0.001-1 mass%.

<Acid-decomposable dissolution inhibiting compound>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter referred to as “dissolution inhibiting compound”) that decomposes by the action of an acid and increases the dissolution rate in an alkali developer. May also be included).
The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996). . Examples of the acid-decomposable group include the same acid-decomposable groups as described above for the acid-decomposable resin. As an alicyclic structure which comprises an alicyclic compound, the thing similar to the alicyclic group mentioned above about Q in the said repeating unit (A) is mentioned.
When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with an electron beam or EUV light, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. The phenol compound is preferably a phenol compound containing 1 to 9 phenol skeletons, more preferably 2 to 6 phenol compounds.

  The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

<Dye>
Examples of the dye suitably used in the present invention include oil dyes and basic dyes.

<Photosensitizer>
In this invention, in order to improve the acid generation efficiency by exposure, arbitrary photosensitizers can be contained.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable. Examples of such phenolic compounds having a molecular weight of 1000 or less include those described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent 219294. Can do.

  In addition, compounds having a proton acceptor functional group described in JP-A No. 2006-208781 and JP-A No. 2007-286574 can be suitably used for the resin composition of the present invention.

<Resist film and pattern formation method>
The resist film of the present invention is formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. More specifically, it is preferably formed by coating on a support such as a substrate.
As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
The film thickness of the resist film of the present invention is preferably 0.02 to 0.2 μm.
The pattern forming method of the present invention includes a step of exposing the obtained resist film and a step of developing the exposed resist film.

More specifically, the pattern forming method of the present invention can be applied, for example, by using an actinic ray-sensitive or radiation-sensitive resin composition on a substrate such as a spinner, a coater or the like on a substrate used for manufacturing a precision integrated circuit element. A resist film is formed by coating and drying by a coating method. In addition, a known antireflection film can be applied in advance. There are no particular restrictions on the said _{substrate, Si, Si / SiO 2,} SiN, TiN, such as a quartz substrate having a Cr layer.
In the pattern forming method of the present invention, the resist film is irradiated with an electron beam (EB), X-rays, EUV light or the like through a mask as necessary, and is preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
In addition, when the resin composition of the present invention is applied to the production of an information recording medium (more specifically, the production of a mold structure and a stamper used in the production of an information recording medium) described in the background art, the substrate is rotated. In other words, exposure / drawing can be performed while controlling the substrate in the r-θ direction. For details of this method and the manufacture of the mold structure by this method, refer to, for example, Japanese Patent No. 4109085 and Japanese Patent Application Laid-Open No. 2008-162101.

The development step in the pattern forming method of the present invention can be performed using an alkaline developer. Examples of the alkali developer used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, etc. Alkaline aqueous solutions of cyclic amines such as quaternary ammonium salts, pyrrole and pihelidine can be used, and TMAH is preferred.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

  By using the pattern formed as described above as a mask, etching, ion implantation, and the like can be performed to produce a semiconductor microcircuit, an imprint mold structure, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.
(Synthesis example)
Synthesis of (P-1) (P-1) was synthesized according to the following scheme.

Synthesis of Compound 2 N, N-dimethylformamide (15 ml) at 25 ° C. in a mixture of Compound 1 (33.6 g) synthesized by the method described in Journal of Materials Chemistry, 2006, 16, 3701 and thionyl chloride (150 ml) Was added dropwise over 1 hour, and the reaction solution was further stirred for 4 hours. The reaction solution was slowly poured into 2 L of ice water, and the solid was filtered off. The solid was dissolved in chloroform (400 ml), washed with 400 ml of distilled water three times, and dried over magnesium sulfate. Chloroform was concentrated under reduced pressure to obtain Compound 2 (28 g).

Synthesis of Compound 3 Triethylamine (30 ml) was added dropwise at 10 ° C. to a mixture of Compound 2 (28 g, 84.2 mmol), 1-naphthol (12.1 g) and dichloromethane (500 ml), and the reaction solution was further cooled at 25 ° C. Stir for 12 hours. The reaction mixture was washed once with 1N aqueous hydrochloric acid (500 ml), water (500 ml), aqueous sodium bicarbonate (500 ml), water (500 ml) and saturated brine (500 ml), and dried over magnesium sulfate. Dichloromethane was concentrated under reduced pressure, and the residue was purified by column chromatography to give compound 3 (26 g).

Synthesis of p-hydroxystyrene 47.60 g of sodium methoxide (28% methanol solution) was added dropwise to a solution of p-acetoxystyrene (100.0 g) in ethyl acetate (400 g) at 0 ° C. over 30 minutes, and then the reaction solution. Was stirred at 25 ° C. for 5 hours. The reaction solution was washed 3 times with distilled water (300 ml) and then dried over anhydrous sodium sulfate. The reaction solution was concentrated under reduced pressure, and methyl ethyl ketone was added to obtain 131.70 g of p-hydroxystyrene (54% methyl ethyl ketone solution).

Synthesis of (P-1) Compound 3 (13.2 g, 30 mmol), t-butyl methacrylate (4.3 g, 30 mmol), 54% methyl ethyl ketone solution of p-hydroxystyrene (9.0 g, 40 mmol) and polymerization initiator V A methyl ethyl ketone (50 ml) solution of -601 (manufactured by Wako Pure Chemical Industries, Ltd.) (2.8 g) was prepared. Methyl ethyl ketone (20 ml) was placed in a reaction vessel, and the solution prepared above was added dropwise at 70 ° C. in a nitrogen gas atmosphere over 4 hours, and further stirred at that temperature for 2 hours. The reaction liquid was cooled to 25 ° C., and then slowly dropped into 1 L of methanol while stirring. The obtained solid was filtered and dried to obtain 12.5 g of (P-1).

Synthesis of (P-2) In the synthesis of (P-1), the method described in the following compound 4 (14.0 g, Solid State Ionics, 1999, 123, 233) instead of compound 3 (13.2 g), and the above 12.0 g of (P-2) was obtained in the same manner except that (synthesized in the same manner as in the synthesis of compounds 2 and 3) was used.

Synthesis of (P-4) (P-4) was synthesized according to the following scheme.

Synthesis of Compound 5 1,2,2,2,3,3-Hexafluoropropane-1,3-in a 54% methyl ethyl ketone solution (18.52 g) of p-hydroxystyrene in ethyl acetate (56 g) at 0 ° C. Disulfonyldifluoride (31.6 g) was added, and a solution of 12.63 g of triethylamine (12.6 g) in ethyl acetate (25 g) was added dropwise over 30 minutes, and the mixture was stirred at that temperature for 4 hours. Phenol (10 g) and triethylamine (12.6 g) were slowly added to the reaction solution, and the mixture was further stirred for 10 hours. The reaction mixture was slowly poured into ethyl acetate (300 ml) / 1N aqueous hydrochloric acid (300 ml), and the mixture was separated after shaking. The organic layer was washed once each with water (300 ml), aqueous sodium bicarbonate (300 ml), water (300 ml) and saturated brine (300 ml), and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography to obtain Compound 5 (35 g).

Synthesis of (P-4) Compound 5 (14.7 g, 30 mmol), 2-cyclohexyl-2-propyl methacrylate (6.3 g, 30 mmol), p-hydroxystyrene in 54% methyl ethyl ketone (9.0 g, 40 mmol) and A methyl ethyl ketone (50 ml) solution of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) (2.8 g) was prepared. Methyl ethyl ketone (20 ml) was placed in a reaction vessel, and the solution prepared above was added dropwise at 70 ° C. in a nitrogen gas atmosphere over 4 hours, and further stirred at that temperature for 2 hours. The reaction liquid was cooled to 25 ° C., and then slowly dropped into 1 L of methanol while stirring. The obtained solid was filtered and dried to obtain 13.0 g of (P-4).

Synthesis of (P-6) In the synthesis of (P-4), Compound 5 (14.7 g, 30 mmol) and 2-cyclohexyl-2-propyl methacrylate (6.3 g, 30 mmol) were respectively added to the following compound 6 (16. 4P, 30 mmol), and 13.8 g of (P-6) was obtained in the same manner except that it was changed to 1-ethylcyclopentyl methacrylate (5.5 g, 30 mmol).

Synthesis of (P-7) In the synthesis of (P-4), Compound 5 (14.7 g, 30 mmol) and 2-cyclohexyl-2-propyl methacrylate (6.3 g, 30 mmol) were respectively added to the following compound 7 (17.17. (0-7, 25 mmol) and 13.5 g of (P-7) were obtained in the same manner except that 1-methylcyclohexyl methacrylate (6.4 g, 35 mmol) was used.

Synthesis of (P-9) In the synthesis of (P-4), Compound 5 (14.7 g, 30 mmol) and 2-cyclohexyl-2-propyl methacrylate (6.3 g, 30 mmol) were respectively added to the following compound 8 (18. (3 g, 25 mmol), 15.1 g of (P-9) was obtained in the same manner except that it was changed to 2-methyl-2-butoxycarbonylmethyl methacrylate (7.5 g, 35 mmol).

Synthesis of (P-10) In the synthesis of (P-4), Compound 5 (14.7 g, 30 mmol), 2-cyclohexyl-2-propyl methacrylate (6.3 g, 30 mmol), 54% methyl ethyl ketone of p-hydroxystyrene The solution (9.0 g, 40 mmol) was added to the following compound 9 (16.2 g, 30 mmol), 1-ethylcyclopentyloxycarbonylmethyl methacrylate (8.4 g, 35 mmol), and 54% methyl ethyl ketone solution of p-hydroxystyrene (7. 14.5 g of (P-10) was obtained in the same manner except that the amount was changed to 8 g, 35 mmol).

Synthesis of (P-11) In the synthesis of (P-4), Compound 5 (14.7 g, 30 mmol), 2-cyclohexyl-2-propyl methacrylate (6.3 g, 30 mmol), 54% methyl ethyl ketone of p-hydroxystyrene The solution (9.0 g, 40 mmol) was added to the following compound 10 (16.7 g, 30 mmol), 2-methyl-2-adamantyl methacrylate (8.2 g, 35 mmol), and 54% methyl ethyl ketone solution of p-hydroxystyrene (7. (P-11) 14.8g was obtained similarly except having changed to 8g, 35 mmol).

Synthesis of (P-12) In the synthesis of (P-4), compound 5 (14.7 g, 30 mmol), 2-cyclohexyl-2-propyl methacrylate (6.3 g, 30 mmol), 54% methyl ethyl ketone of p-hydroxystyrene The solution (9.0 g, 40 mmol) was added to the following compound 11 (12.3 g, 40 mmol), 2-methyl-2-adamantyl methacrylate (7.0 g, 30 mmol), and 54% methyl ethyl ketone solution of p-hydroxystyrene (6. (P-12) 12.5 g was similarly obtained except having changed to 7 g and 30 mmol).

Synthesis of (P-18) In the synthesis of (P-4), Compound 5 (14.7 g, 30 mmol), 2-cyclohexyl-2-propyl methacrylate (6.3 g, 30 mmol), 54% methyl ethyl ketone of p-hydroxystyrene The solution (9.0 g, 40 mmol) was added to the following compound 12 (9.9 g, 30 mmol), t-butyl 3-vinylbenzoate (7.1 g, 35 mmol), 50% methyl ethyl ketone of 4-hydroxy-1-vinylnaphthalene, respectively. 13.3 g of (P-18) was obtained in the same manner except that the solution was changed to 11.9 g (35 mmol).

[Examples 1 to 18 and Comparative Examples 1 to 8]
<Resist evaluation (EB)>
The components shown in Table 1 below were dissolved in the mixed solvent shown in Table 1 to prepare a solution having a solid content concentration of 4.0% by mass. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution. The prepared positive resist solution is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist having a film thickness of 100 nm. A film was formed.
This resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage: 50 keV). Immediately after the irradiation, it was heated on a hot plate at 120 ° C. for 90 seconds. Furthermore, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern. Was evaluated by the following method.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).
[Resolution]
The resolving power was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the irradiation dose showing the above sensitivity.
[Line edge roughness (LER)]
The distance from the reference line where there should be an edge, using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) for any 30 points in the length direction 50 μm of the 100 nm line pattern at the irradiation amount showing the sensitivity described above. Was measured, the standard deviation was obtained, and 3σ was calculated.
[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and three-step evaluation was performed: rectangular, slightly tapered, and tapered.
[Storage stability]
After the resist composition is stored at room temperature (25 ° C.) for 1 month, sensitivity is obtained by the method described in [Sensitivity] above, and the degree of sensitivity fluctuation before and after 1 month storage is determined according to the following criteria. evaluated.
(Criteria)
○: Sensitivity fluctuation of <1 μC / cm ² observed.
△: 1μC / cm ² or more 3 .mu.C / cm ² or less in sensitivity fluctuation observed.
×: Sensitivity fluctuation of> 3 μC / cm ² observed.

  The structures of the materials (other resins, acid generators, basic compounds) used in the examples and comparative examples are shown below.

R-1 was synthesized by the method described in JP-A-5-181265.
R-2 and PR-2 were synthesized with reference to the method described in JP-A-2008-163218.
R-3 and PR-1 are compounds generally known in the art, and can be synthesized by a known synthesis method.
PR-3 was synthesized with reference to the method described in JP-A-2008-111120.
PR-4 was synthesized with reference to the method described in JP-A No. 2002-72483.
PR-5 to 7 were synthesized by a method similar to the synthesis of the resin (P-4) with reference to the methods described in JP-A-2-245756 and JP-A-10-221852.
The synthesis was carried out with reference to the method described in the Japanese Patent Publication.
Commercially available TBAH and TPI were used.

Surfactants and solvents used in Examples and Comparative Examples are shown below.
W-1: Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd., fluorine and silicon)
W-3: Polysiloxane polymer (Shin-Etsu Chemical Co., Ltd., silicon-based)
W-4: PolyFoxPF-6320 (manufactured by OMNOVA Solutions Inc., fluorine-based)
S1: Propylene glycol monomethyl ether acetate S2: Propylene glycol monomethyl ether S3: Ethyl lactate S4: Cyclohexanone

As is clear from Table 1, Comparative Examples 1 to 8 of the resin composition using the resin having no repeating unit represented by the general formula (I) are inferior in either sensitivity or storage stability. It was. In particular, Comparative Examples 1, 3, 4, and 6 were inferior in sensitivity, and Comparative Examples 2 to 5, 7, and 8 were all inferior in storage stability.
On the other hand, all of Examples 1 to 18 of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention having the repeating unit represented by the general formula (I) are excellent in sensitivity and storage stability, and It can be seen that image quality, pattern shape, line edge roughness, etc. are also good.

[Examples 19 to 21]
<Resist evaluation (EUV light)>
The components shown in Table 2 below were dissolved in the mixed solvent shown in Table 2 to prepare a solution having a solid content concentration of 4.0% by mass. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution. The symbols of the compounds described in Table 2 are the same as those in Table 1.
The prepared positive resist solution is uniformly coated on a silicon substrate that has been subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 90 seconds to form a resist having a film thickness of 100 nm. A film was formed.
The resist film was irradiated with an EUV exposure apparatus (wavelength 13 nm), and immediately after the irradiation, it was heated on a hot plate at 120 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern (line: space = 1: 1). ) And the obtained pattern was evaluated by the following method.
〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).
[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and three-step evaluation was performed: rectangular, slightly tapered, and tapered.
[Storage stability]
After storing the resist composition at room temperature (25 ° C.) for 1 month, the sensitivity is obtained by the method described in [Sensitivity] above, and the degree of sensitivity fluctuation before and after 1 month storage is determined according to the following criteria. evaluated.
(Criteria)
○: Sensitivity fluctuation of <1 mJ / cm ² observed.
△: 1mJ / cm ² or more 3 mJ / cm ² or less in sensitivity fluctuation observed.
X: Sensitivity fluctuation of> 3 mJ / cm ² observed.

  As is apparent from the results in Table 2, Examples 19 to 21 of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention having the repeating unit represented by the general formula (I) are all EUV exposed. It can be seen that both good sensitivity and storage stability are achieved.

Claims (11)

An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (P) containing a repeating unit represented by the following general formula (I).

In the general formula (I),
R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
L ₁ represents a single bond or a divalent linking group,
L ₂ represents an alkylene group or an arylene group having an electron withdrawing group,
L ₁ or L ₂ may be bonded to R ₃ to form a 5-membered or 6-membered ring.
Ar represents an aromatic group. In the general formula (I), actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, L ₂ is characterized in that it is a fluorine-containing alkylene group or a fluorine-containing arylene group. In the general formula (I), L ₂ is claim 1 or 2 actinic ray-sensitive or radiation-sensitive resin composition according to characterized in that it is a perfluoroalkylene group.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the resin (P) further contains a repeating unit having an acid-decomposable group.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the resin (P) further contains a repeating unit having a hydroxyl group.   6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, wherein the repeating unit containing a hydroxyl group is a repeating unit derived from hydroxystyrene.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the resin (P) further contains a repeating unit having a lactone structure.   The resist film formed using the actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-7.   A pattern forming method comprising: exposing the resist film according to claim 8; and developing the exposed film.   The pattern forming method according to claim 9, wherein the exposure is performed using X-rays, electron beams, or extreme ultraviolet rays. A resin comprising a repeating unit represented by the following general formula (II):

In the general formula (II),
R ₁ ′ represents a hydrogen atom or an alkyl group,
L ₁ represents a single bond or a divalent linking group,
Rf represents a perfluoroalkylene group,
Ar represents an aromatic group.