KR20170113055A - Resist composition and method of forming resist pattern - Google Patents

Abstract

식 (1)
[식 중,
R₁ 및 R₂ 는, 각각 독립적으로 수산기로 치환될 수 있는 탄소수 1~10 의 탄화수소기이고, 상기 탄화수소기 중 1개의 -CH₂- 또는 인접하고 있지 않은 2개 이상의 -CH₂- 는, -O-, -S-, -NH-, -NR₃-, -C(O)-, -OC(O)-, -OC(O)O-, -SO-, -SO₂-, -CONH-, -CONR₃-, -OC(O)NH- 또는 -OC(O)NR₃- 로 대체될 수 있고, 이 때 R₃ 은 탄소수 1~10 의 탄화수소기이다.
n1, n2, m1 및 m2 는, 각각 독립적으로 0~5 의 정수이고, n1 + m1 과 n2 + m2 는, 둘 다 5 를 초과하지 않는다.] The present invention relates to a resin composition comprising a resin component (A) whose solubility in a developer is changed by the action of an acid, an acid generator component (B) which generates an acid by exposure, and a radiation absorbing compound (C). ≪ / RTI >

Equation (1)
[Wherein,
R ₁ and R ₂ are each independently a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a hydroxyl group, and one -CH ₂ - of the hydrocarbon groups or two or more non-adjacent -CH ₂ - _{O-, -S-, -NH-, -NR 3} -, -C (O) -, -OC (O) -, -OC (O) O-, -SO-, -SO 2 -, -CONH- , -CONR ₃ -, -OC (O) NH- or -OC (O) NR ₃ -, wherein R ₃ is a hydrocarbon group of 1 to 10 carbon atoms.
n1, n2, m1 and m2 are each independently an integer of 0 to 5, and n1 + m1 and n2 + m2 do not both exceed 5.]

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resist composition,

The present invention relates to a resist composition and a method for forming a resist pattern.

In the photolithography technique, for example, a resist film made of a resist composition is formed on a substrate, and the resist film is selectively exposed with radiation such as light, electron beam or the like through a photomask having a predetermined pattern formed thereon, Thereby forming a resist pattern of a predetermined shape on the resist film. A resist composition in which the exposed portion is changed to a property of dissolving in a developing solution is referred to as a positive type and a resist composition in which the exposed portion is changed into a property of not dissolving in a developing solution is referred to as a negative type.

BACKGROUND ART [0002] In recent years, in the production of semiconductor devices and liquid crystal display devices, miniaturization has progressed rapidly according to the progress of lithography technology. Conventionally, ultraviolet rays represented by g-line and i-line have been used. However, KrF excimer laser (248 nm) is now introduced, and ArF An excimer laser (193 nm) is beginning to be introduced. F ₂ excimer lasers (157 nm) having a shorter wavelength, EUV (extreme ultraviolet rays), electron beams, X-rays and the like have also been studied.

On the other hand, in the production of semiconductor elements and liquid crystal display elements, an impurity diffusion layer is formed on the surface of a substrate. The formation of the impurity diffusion layer is usually carried out in two steps of introduction and diffusion of impurities. As one of the introduction methods, impurities such as phosphorus and boron are ionized in a vacuum and accelerated in a high electric field to be injected into the substrate surface (Hereinafter referred to as implantation).

However, in an inclined implantation process using a thin film resist pattern (hereinafter referred to as a thin film implantation process), in consideration of the influence on subsequent ion implantation, generally, an antireflection film (BARC) is not used . In this case, particularly when a resin having high transparency to exposure light is used, defective shape of the resist pattern tends to occur due to the influence of incident light upon exposure or reflection light from the substrate. Particularly, in manufacturing a semiconductor device or a liquid crystal display device, it is difficult to form a resist film having a uniform film thickness on the substrate on which the electrodes and the like are formed because of the thin film deposition process. Therefore, there is a problem of the phenomenon that the dimension of the resist pattern increases or decreases as the resist film thickness changes, that is, a so-called standing wave (hereinafter abbreviated as SW). The change of the pattern dimension by the SW tends to increase as the resist film becomes thinner and as the resist film becomes more transparent, particularly in the case of a thin film having a film thickness of 500 nm or less. Further, the problem of dimensional change becomes a serious problem as the resist pattern becomes finer.

In addition, while the structure of the device becomes more advanced and complicated as the semiconductor device becomes three-dimensional, a resist pattern may be formed on the stepped substrate at the time of manufacturing an integrated circuit device having a three-dimensional structure. In such a case, the defective shape (SW) of the resist pattern tends to be caused by the influence of the incident light upon exposure and the reflected light from the substrate.

In order to solve this problem, a resist containing a compound containing an anthracene skeleton or a benzophenone skeleton, a so-called compound having a radiation absorbing ability (dye) in a resist and absorbing reflected light from the substrate, Compositions and the like have been used (see, for example, Patent Documents 1 and 2).

Patent Document 1: JP-A-2006-215163

Patent Document 2: JP-A-2011-113065

However, such a compound containing an anthracene skeleton or a benzophenone skeleton has a problem of toxicity (high risk in the human body), so that there is a problem that it is difficult to use it as a present dye.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a resist composition capable of effectively suppressing the pattern dimension change by SW while maintaining the resolution and high absorption ratio with respect to exposure light with a small addition amount, And a method for forming a resist pattern.

As a result of intensive studies, the inventors of the present invention have found that a photosensitive resin composition comprising a resin component (A) whose solubility in a developer varies by the action of an acid, an acid generator component (B) The present inventors have found that the above problems can be solved by combining a compound (C) having an absorption ability with respect to radiation (e.g., radiation).

That is, in the first aspect of the present invention,

[1] A resin composition comprising a resin component (A) whose solubility in a developer is changed by the action of an acid, an acid generator component (B) which generates an acid by exposure, and a radiation absorbing compound (C).

[Chemical Formula 1]

식 (1)

Equation (1)

[Wherein,

R ₁ and R ₂ are each independently a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a hydroxyl group, and one -CH ₂ - of the hydrocarbon groups or two or more non-adjacent -CH ₂ - _{O-, -S-, -NH-, -NR 3} -, -C (O) -, -OC (O) -, -OC (O) O-, -SO-, -SO 2 -, -CONH- , -CONR ₃ -, -OC (O) NH- or -OC (O) NR ₃ -, wherein R ₃ is a hydrocarbon group of 1 to 10 carbon atoms.

n1, n2, m1 and m2 are each independently an integer of 0 to 5, and n1 + m1 and n2 + m2 do not both exceed 5.]

[2] In the compound (C) having a radiation absorbing ability represented by the formula (1), m1 = m2 = 1.

[3] In the compound (C) having radiation-absorbing ability represented by the formula (1), R ₁ and R ₂ are each independently a hydrocarbon group of 1 to 5 carbon atoms substituted with a hydroxyl group, CH ₂ - or two or more non-adjacent -CH ₂ - may be replaced by -O-, -S- or -NH-.

[4] The resin component (A) may contain a structural unit (a1) derived from hydroxystyrene represented by the following formula (a1-1):

[Wherein,

R is a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen atom.

R ⁶ is a hydrocarbon group of 1 to 10 carbon atoms.

p is an integer of 1 to 3;

q is an integer of 0 to 2.]

[5] The resin component (A) may contain a polymer compound (A-2) having a structural unit (a4) derived from an acrylate ester represented by the following formula (a4-1) or (a4-2) .

[Wherein,

R is a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen atom.

Va ¹ is a divalent hydrocarbon group of 1 to 30 carbon atoms which may have an ether bond, a urethane bond or an amide bond.

n _a1 is an integer of 0 to 2;

Ra ¹ is an acid dissociable group.

n _a2 is an integer of 1 to 3;

Wa ¹ is an n _a2 +1 -valent hydrocarbon group having 1 to 30 carbon atoms.]

[6] The resin component (A) may be a resin whose alkaline solubility is increased by the action of an acid.

[7] The resin component (A) is an alkali-soluble resin and may further comprise a crosslinking component (D).

[8] The resist composition may further contain a nitrogen-containing organic compound (E).

[9] The resist composition may be for a thin film implantation process.

[10] The resist composition may be used to form a resist pattern on a stepped substrate.

According to a second aspect of the present invention,

[11] A resist pattern forming method, comprising forming a resist film on a substrate using the resist composition of the first aspect, subjecting the resist film to selective exposure treatment, and then developing the resist film to form a resist pattern to be.

According to the present invention, it is possible to provide a resist composition and a resist pattern forming method which can reduce the problem of toxicity, have a high water absorption rate with respect to exposure light with a small addition amount, and can effectively suppress pattern size change by SW while maintaining resolution have.

In the present specification and claims, " hydrocarbon group " means a monovalent residue derived from an organic compound composed of carbon and hydrogen or a derivative thereof. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

The term " aliphatic " is defined as meaning a group, compound, or the like having no aromaticity as a relative concept to an aromatic group.

The term "aliphatic hydrocarbon group" means a hydrocarbon group having no aromaticity.

The "aromatic hydrocarbon group" is a hydrocarbon group having aromaticity.

The "aliphatic cyclic group" is intended to mean a monocyclic group or a polycyclic group having no aromaticity.

The " alkyl group " includes straight-chain, branched-chain and cyclic monovalent saturated hydrocarbon groups.

The " alkylene group " includes straight-chain, branched-chain and cyclic divalent saturated hydrocarbon groups.

The "halogenated alkyl group" is a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

"Constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).

&Quot; Exposure " is a concept including the entire irradiation of radiation.

< Resist  Composition>

The resist composition of the present invention (hereinafter sometimes simply referred to as &quot; resist composition &quot;) contains a resin component (A) (hereinafter, referred to as component (A)) in which solubility in a developer is changed by the action of an acid, A resist composition containing an acid generator component (B) (hereinafter referred to as a component (B)) which generates an acid upon exposure and a compound (C) having a radiation absorbing ability (hereinafter referred to as a component (C) .

When a resist film is formed using the resist composition of the present invention and selectively exposed to the resist film, an acid is generated in the exposed portion, and the solubility of the component (A) in the developer is changed by the action of the acid , And the solubility of the component (A) in the developer is not changed in the unexposed portion, so that a difference in solubility in the developer occurs between the exposed portion and the unexposed portion. Therefore, when the resist film is developed, when the resist composition is a positive type, the exposed portion is dissolved and removed to form a positive resist pattern. When the resist composition is negative, the unexposed portion is dissolved and removed to form a negative resist pattern .

The resist composition of the present invention may be a positive resist composition or a negative resist composition.

The resist composition of the present invention may also be used for an alkali development process using an alkali developer for development processing at the time of forming a resist pattern and may be used for a solvent development process using a developer (organic developer) .

The resist composition to be used for forming a resist pattern has an acid-generating ability to generate an acid upon exposure, and the component (A) is an acid generator which generates an acid by exposure, Base component in which the solubility is changed ". In this case, the component (A) is preferably a polymer compound. As such a polymer compound, a resin having a constituent unit capable of generating an acid upon exposure can be used. As the constituent unit for generating an acid upon exposure, known ones can be used.

&Lt; Component (A) >

The component (A) is not particularly limited as long as it is a resin component in which the solubility in a developer is changed by the action of an acid, and may be arbitrarily selected from those used as alkali-soluble resin components so far.

(A1) derived from hydroxystyrene, a structural unit (a2) in which the hydrogen atom of the hydroxyl group of the structural unit (a1) is substituted with an acid dissociable group, and / or a structural unit derived from styrene (hereinafter sometimes referred to as component (A-1)).

The component (A) is preferably a copolymer comprising a structural unit (a4) having an acid-decomposable group whose polarity is increased by the action of an acid, a -SO ₂ -containing cyclic group, a lactone containing cyclic group, a carbonate containing cyclic group, (A5) having a cyclic group and / or a structural unit (a6) containing a polar group-containing aliphatic hydrocarbon group (hereinafter sometimes referred to as a component (A-2)).

The component (A-1) will be specifically described below.

constituent unit  (a1)

The structural unit (a1) is a structural unit derived from hydroxystyrene.

The term "hydroxystyrene" refers to hydrostyrene and hydrostyrene in which hydrogen atoms at the α-position of the hydroxystyrene are substituted with other substituents such as a halogen atom, an alkyl group, a halogenated alkyl group, and derivatives thereof. The term "structural unit derived from hydroxystyrene" means a structural unit constituted by cleavage of an ethylenic double bond of hydroxystyrene. The &quot; position of the constituent unit derived from hydroxystyrene (the carbon atom at the position) &quot; means a carbon atom to which a benzene ring is bonded, unless otherwise specified.

As the structural unit (a1), a structural unit represented by the following formula (a1-1) can be exemplified.

(2)

[Wherein,

R is a hydrogen atom, a halogen atom, or a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a halogen atom.

R ⁶ is a hydrocarbon group of 1 to 10 carbon atoms.

p is an integer of 1 to 3;

q is an integer of 0 to 2.]

In formula (a1-1), R may be a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group.

The alkyl group represented by R may be an alkyl group having 1 to 5 carbon atoms and is preferably a linear or branched alkyl group and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Butyl group, pentyl group, isopentyl group, neopentyl group and the like. The methyl group is preferable industrially.

The halogen atom of R may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, of which a fluorine atom is preferable.

As the halogenated alkyl group of R, a part or all of hydrogen atoms of the above-mentioned alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. In this case, the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these, a fluorine atom is preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

As the fluorinated alkyl group for R, it is preferable that all of the hydrogen atoms are fluorinated. The fluorinated alkyl group is preferably a linear or branched fluorinated alkyl group, more preferably a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group or a nonafluorobutyl group, and more preferably a trifluoromethyl group (-CF ₃₎ it is most preferred.

As R, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

In formula (a1-1), R ⁶ may be an alkyl group having 1 to 5 carbon atoms.

Examples of the alkyl group for R ^{6 include} the same alkyl groups as those for R ⁶ .

In the formula (a1-1), q is preferably 0 or 1, particularly preferably 0 in the industrial scale. The substitution position of R ⁶ may be any of o-position, m-position and p-position when q is 1, and arbitrary substitution positions may be combined when q is 2.

In the formula (a1-1), p is preferably 1. When p is 1, the substitution position of the hydroxyl group may be any of o-position, m-position and p-position, and the p-position is preferable because it is readily available and inexpensive. When p is 2 or 3, arbitrary substitution positions can be combined.

The structural unit (a1) may be used alone or in combination of two or more.

When the component (A-1) contains the structural unit (a1), the proportion of the structural unit (a1) is preferably from 50 to 95 mol% based on the total structural units constituting the component (A-1) , And more preferably 60 to 80 mol%. Within this range, solubility in a suitable developing solution is obtained and the balance with other constituent units is good.

constituent unit  (a2)

The structural unit (a2) is a structural unit in which the hydrogen atom of the hydroxyl group of the structural unit (a1) is substituted with an acid dissociable group.

As the acid dissociable group, it is preferable to contain an acid dissociable group (II) represented by the following formula (II) as a main component.

(3)

[Wherein,

X and R ¹ are each independently a hydrocarbon group having 1 to 16 carbon atoms, or X and R ¹ are each independently an alkylene group having 1 to 16 carbon atoms, and even when the terminal of X and the terminal of R ¹ are bonded to form a ring do.

R ² is a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms.]

Means that the acid dissociable group contained in the component (A-1) is contained in an amount of not less than 50 mol%, preferably not less than 70 mol%, more preferably not less than 80 mol% % Or more, and most preferably 100 mol%.

In the formula (II), X may be an aliphatic cyclic hydrocarbon group or an aromatic cyclic hydrocarbon group.

The aliphatic cyclic hydrocarbon group in X is a monovalent aliphatic group. The aliphatic cyclic hydrocarbon group can be appropriately selected from among many proposed ones in conventional KrF resists and ArF resists, for example. Specific examples of the aliphatic cyclic hydrocarbon group represented by X include, for example, an aliphatic monocyclic group having 5 to 10 carbon atoms and an aliphatic polycyclic group having 7 to 16 carbon atoms. Examples of the aliphatic monocyclic group having 5 to 10 carbon atoms include groups in which one hydrogen atom has been removed from the monocycloalkane. Specific examples thereof include groups in which one hydrogen atom has been removed from cyclopentane, cyclohexane, cyclooctane, etc. . Examples of the aliphatic polycyclic group having 7 to 16 carbon atoms include groups in which one hydrogen atom has been removed from a bicycloalkane, a tricycloalkane, a tetracycloalkane or the like. Specific examples thereof include adamantane, norbornane, And a group in which one hydrogen atom has been removed from a polycycloalkane such as isobornane, tricyclodecane or tetracyclododecane. Of these, an adamantyl group, a norbornyl group and a tetracyclododecanyl group are industrially preferable, and an adamantyl group is particularly preferable.

Examples of the aromatic cyclic hydrocarbon group of X include an aromatic polycyclic group having 10 to 16 carbon atoms. Specific examples thereof include groups in which one hydrogen atom has been removed from naphthalene, anthracene, phenanthrene, pyrene, and the like. Specific examples thereof include a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, And 2-naphthyl group is particularly preferable in industry.

X may be a linear, branched, or cyclic hydrocarbon group.

The linear hydrocarbon group is preferably a linear alkyl group and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- T-butyl, neopentyl and the like. The linear aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms.

As the branched aliphatic hydrocarbon group, a branched alkyl group is preferable, and specifically, -CH (CH ₃ ) CH ₃ , -C (CH ₃ ) ₂ CH ₃ , -CH (CH ₂ CH ₃ ) CH ₃ ; -CH (CH ₃ ) CH ₂ CH ₃ , and -CH ₂ CH (CH ₃ ) CH ₃ ; And an alkylbutyl group such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₃ and -CH ₂ CH (CH ₃ ) CH ₂ CH ₃ . The branched-chain aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms.

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group, but a monocyclic group is preferred. Examples of the monocyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic group include isobonyl, norbornyl, tricyclodecanyl, and the like. The cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 5 to 10 carbon atoms.

The aromatic hydrocarbon group of R ₁ and R ₂ is a concept including an aralkyl group and an alkylaryl group, and specifically includes a phenyl group, a phenylethyl group, a phenylpropyl group, a benzyl group and a naphthalene group.

The hydrocarbon group of X is preferably an alkyl group. The alkyl group represented by X may be the same as the alkyl group represented by R in the formula (a1-1), wherein the alkyl group is preferably a methyl group or an ethyl group, and more preferably an ethyl group.

In the formula (II), R ¹ may be an alkyl group having 1 to 5 carbon atoms.

The alkyl group represented by R ^{1 includes} the same groups as those represented by R in the formula (a1-1). Industrially, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

In the formula (II), R ² may be a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Examples of the alkyl group for R ^{2 include} the same alkyl groups as those for R ¹ . R ² is preferably a hydrogen atom industrially.

In the formula (II), X and R ¹ are each independently an alkylene group having 1 to 5 carbon atoms, and the terminal of X and the terminal of R ¹ may be bonded to form a ring. In this case, in the formula (II), a cyclic group is formed by an oxygen atom to which R ¹ , X and X are bonded, and an oxygen atom and a carbon atom to which R ¹ is bonded. The cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group, and the like.

As the acid dissociable group (II), a group in which R ² is a hydrogen atom is particularly preferable because the effect of the present invention is excellent. Specific examples thereof include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-iso-propoxyethyl group, a 1-n-butoxyethyl group , 1-tert-butoxyethyl group, methoxymethyl group, ethoxymethyl group, iso-propoxymethyl group, n-butoxymethyl group and tert-butoxymethyl group. Of these, 1-ethoxyethyl group is particularly preferable Do. Examples of the group in which X is an aliphatic cyclic group include 1-cyclohexyloxyethyl group, 1- (2-adamantyl) oxymethyl group, 1- (1-adamantyl) oxy Ethyl group and the like. Examples of the group in which X is an aromatic cyclic hydrocarbon group include a 1- (2-naphthyl) oxyethyl group represented by the following formula (II-b).

 [Chemical Formula 4]

In the present invention, the acid dissociable group may have an acid dissociable group other than the acid dissociable group (II) represented by the formula (II) within the range not to impair the effect of the present invention.

As such an acid dissociable group, a resin for a resist composition such as a KrF excimer laser or an ArF excimer laser, for example, can be appropriately selected from among many proposed ones.

Such an acid dissociable group includes at least one acid dissociable group (II) selected from the group consisting of a chain type tertiary alkoxycarbonyl group, a chain type or cyclic tertiary alkyl group, and a chain type tertiary alkoxycarbonyl alkyl group ) Can be exemplified. By including the acid dissociable group (II), the heat resistance is improved.

The carbon number of the chain type tertiary alkoxycarbonyl group is preferably 4 to 10, more preferably 4 to 8. Specific examples of the chain-type tertiary alkoxycarbonyl group include a tert-butoxycarbonyl group and a tert-amyloxycarbonyl group.

The number of carbon atoms of the chain type tertiary alkyl group is preferably 4 to 10, more preferably 4 to 8. As the chain type tertiary alkyl group, more specific examples include a tert-butyl group and a tert-amyl group.

The cyclic tertiary alkyl group is a monocyclic or polycyclic monovalent saturated hydrocarbon group containing a tertiary carbon atom on the ring. Specific examples of the cyclic tertiary alkyl group include a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group, 2-ethyl-2-adamantyl group and the like.

The number of carbon atoms in the chain type tertiary alkoxycarbonylalkyl group is preferably from 4 to 10, more preferably from 4 to 8. Specific examples of the chain-type tertiary alkoxycarbonylalkyl group include a tert-butoxycarbonylmethyl group and a tert-amyloxycarbonylmethyl group.

As the acid dissociable group (II), in view of resolution, a chain type tertiary alkyl group is particularly preferable, and tert-butyl group is particularly preferable.

The structural unit (a2) may be used alone or in combination of two or more.

When the component (A-1) contains the structural unit (a2), the proportion of the structural unit (a2) is preferably 5 to 40 mol% based on the total structural units constituting the component (A-1) And more preferably 10 to 35 mol%. When the amount is not less than the lower limit value, a pattern can be obtained when the resist composition is used, and when it is not more than the upper limit value, the balance with other constituent units is good.

constituent unit  (a3)

The structural unit (a3) is a structural unit derived from styrene.

Here, the term &quot; styrene &quot; means that styrene, styrene, hydrogen atoms at the alpha -position of styrene are substituted with other substituents such as halogen atoms, alkyl groups, halogenated alkyl groups and the like, and derivatives thereof (excluding hydroxystyrene) . The term "constitutional unit derived from styrene" means a constitutional unit constituted by cleavage of an ethylenic double bond of styrene. In the styrene, the hydrogen atom of the phenyl group may be substituted with a substituent such as an alkyl group.

As the structural unit (a3), a structural unit represented by the following formula (a3-1) can be exemplified.

[Chemical Formula 5]

[Wherein,

R is a hydrogen atom, a halogen atom, or a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a halogen atom.

R ⁷ is a hydrocarbon group of 1 to 10 carbon atoms.

and r represents an integer of 0 to 3.]

In the formula (a3-1), examples of R and R ⁷ include the same ones as R and R ⁶ in the formula (a1-1).

In formula (a3-1), r is preferably 0 or 1, and particularly preferably 0 in industrial terms.

In the formula (a3-1), the substitution position of R ⁷ may be any of o-, m- and p-positions when r is 1 to 3, and when r is 2 or 3, The substitution positions can be combined.

As the structural unit (a3), one type may be used alone, or two or more types may be used in combination.

When the component (A-1) contains the structural unit (a3), the proportion of the structural unit (a3) is preferably from 1 to 20 mol% based on the total structural units constituting the component (A- And more preferably 5 to 10 mol%. Within this range, the effect of having the constituent unit (a3) is high, and the balance with other constituent units is good.

 The component (A-1) may contain other constitutional units than the above-mentioned constitutional units (a1) to (a3) within the range not to impair the effect of the present invention. Such a constituent unit is not particularly limited as long as it is other constituent units not classified as the above-mentioned constituent units (a1) to (a3), and is used for resist resins for KrF excimer laser and ArF excimer laser, A number of conventionally known ones can be used.

As the component (A-1), a copolymer having one or more structural units (a1), structural units (a2) and / or (a3) and optionally other structural units may be used. May be used as a mixture of polymers having at least one polymer.

 The component (A-1) can be obtained by polymerizing monomers which derive each constituent unit by a known method, for example, by radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) .

The weight average molecular weight of the component (A-1) (converted in terms of polystyrene by gel permeation chromatography (GPC), the same shall apply hereinafter) is preferably 5,000 to 30,000, more preferably 15,000 to 25,000. When the mass average molecular weight is 30,000 or less, resolution is high and it is particularly preferable for thin film implantation. If it is 5,000 or more, heat resistance is high and it is particularly preferable for thin film implantation.

The smaller the dispersion degree (Mw / Mn (number average molecular weight)) of the resin component (A-1) is (more preferably, closer to dispersion), the better the resolution. The dispersion degree is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

The component (A-2) will be specifically described below.

constituent unit  (a4)

The structural unit (a4) is a structural unit containing an acid-decomposable group whose polarity increases due to the action of an acid.

The "acid-decomposable group" is an acid-decomposable group capable of cleaving at least part of the bonds in the acid decomposable group structure by the action of an acid. Examples of the acid decomposable group whose polarity is increased by the action of an acid include a group which is decomposed by the action of an acid to generate a polar group. Examples of the polar group at this time include a carboxyl group, a hydroxyl group, an amino group, and a sulfo group (-SO ₃ H). Of these, a sulfo group or a polar group containing -OH (a polar group containing OH) is preferable in the structure, and a sulfo group or a carboxyl group or a hydroxyl group is preferable, and a carboxyl group or a hydroxyl group is particularly preferable.

More specifically, the acid decomposable group in which the polar group is protected by an acid dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid dissociable group) have. The acid-dissociable group constituting the acid-decomposable group needs to be a group having a lower polarity than the polar group generated by dissociation of the acid-dissociable group, whereby when the acid-dissociable group is dissociated by the action of an acid, Polarity with higher polarity than genitalia is generated and polarity increases. As a result, the polarity of the entire component (A-2) increases. As the polarity increases, the solubility in the developer changes relatively, and when the developer is an organic developer, the solubility decreases. The acid dissociable group is not particularly limited, and the acid dissociable group of the base resin for the chemically amplified resist can be used.

As the structural unit (a4), a structural unit derived from an acrylate ester in which a hydrogen atom bonded to the carbon atom at the? -Position may be substituted with a substituent is preferable.

The term "structural unit derived from an acrylate ester" means a structural unit constituted by cleavage of an ethylenic double bond of an acrylate ester.

"Acrylic acid ester" is a compound in which a hydrogen atom at the terminal of a carboxyl group of acrylic acid (CH ₂ ═CH-COOH) is substituted with an organic group.

The acrylic acid ester may have a hydrogen atom bonded to the carbon atom at the? -Position thereof substituted with a substituent. The substituent (R ^? ) For substituting a hydrogen atom bonded to the carbon atom at the ^{? -Position} is an atom or a group other than a hydrogen atom, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, . The carbon atom at the? -Position of the acrylate ester refers to a carbon atom to which a carbonyl group is bonded, unless otherwise specified.

Hereinafter, an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the? -Position is substituted with a substituent is sometimes referred to as an? -Substituted acrylate ester. In some cases, an acrylic acid ester and an alpha-substituted acrylic acid ester are collectively referred to as &quot; (alpha-substituted) acrylic ester &quot;.

As the structural unit (a4), a structural unit represented by the following formula (a4-1) or (a4-2) can be exemplified.

[Chemical Formula 6]

[Wherein,

R is a hydrogen atom, a halogen atom, or a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a halogen atom.

Va ¹ is a divalent hydrocarbon group which may have an ether bond, a urethane bond or an amide bond.

n _a1 is 0 to 2;

Ra ¹ is an acid dissociable group represented by the following formula (a4-r-1) or (a4-r-2).

Wa ¹ is a hydrocarbon group of n _a2 +1.

n _a2 is 1 to 3;

Ra ² is an acid dissociable group represented by the following formula (a4-r-1) or (a4-r-3)

In formula (a4-1), R may be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.

The alkyl group having 1 to 5 carbon atoms represented by R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.

The halogenated alkyl group having 1 to 5 carbon atoms of R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom at this time include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

As R, a hydrogen atom or a methyl group is most preferable in view of industrial availability.

In the formula (a4-1), Va ¹ includes the case where the divalent hydrocarbon group is bonded via an ether bond, a urethane bond or an amide bond.

The hydrocarbon group of Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually saturated. More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in the structure.

The linear or branched aliphatic hydrocarbon preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

The aliphatic hydrocarbon group is preferably a linear alkylene group of a linear, in particular a methylene group [-CH ₂ -], an ethylene group _{[- (CH 2) 2 -} ], a trimethylene group [- (CH ₂ ) ₃ -], tetramethylene group [- (CH ₂ ) ₄ -], pentamethylene group [- (CH ₂ ) ₅ -] and the like.

Aliphatic hydrocarbon group of the branched alkylene group is preferably a branched, and specifically _{-CH (CH 3) -, -CH} (CH 2 CH 3) -, -C (CH 3) 2 -, -C (CH ₃ ) (CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, and -C (CH ₂ CH ₃ ) ₂ -; _{-CH (CH 3) CH 2 -} , -CH (CH 3) CH (CH 3) -, -C (CH 3) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 -, -C (CH ₂ CH _{3) 2} -CH ₂ - alkyl group such as ethylene; _{-CH (CH 3) CH 2 CH} 2 -, -CH 2 CH (CH 3) CH 2 - alkyl trimethylene group and the like; And alkyl alkylene groups such as alkyltetramethylene groups such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ - and the like. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include alicyclic hydrocarbon groups (groups in which two hydrogen atoms have been removed from the aliphatic hydrocarbon ring), groups in which alicyclic hydrocarbon groups are bonded to the ends of a linear or branched aliphatic hydrocarbon group , And groups in which an alicyclic hydrocarbon group is interposed in a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as described above.

The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

The alicyclic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane. The polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, iso Borane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, ~ 10 is most preferred. Provided that the number of carbon atoms does not include the number of carbon atoms in the substituent.

Specific examples of aromatic rings of aromatic hydrocarbon groups include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene and phenanthrene; An aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom; And the like. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring (arylene group); A group in which one hydrogen atom of a group (aryl group) from which one hydrogen atom is removed from the aromatic hydrocarbon ring is substituted with an alkylene group (e.g., a benzyl group, a phenethyl group, a 1-naphthylmethyl group, , A 1-naphthylethyl group, a 2-naphthylethyl group, or the like; or a group obtained by removing one additional hydrogen atom from an aryl group in an arylalkyl group such as a 2-naphthylethyl group); And the like. The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the formula (a4-1), Ra ¹ An acid dissociable group represented by the following formula (a4-r-1) (hereinafter occasionally referred to as &quot; acetal type acid dissociable group &quot;

(7)

[Wherein,

Ra ' ¹ and Ra' ² are a hydrogen atom or an alkyl group.

Ra ' ³ is a hydrocarbon group, or may be bonded to any of Ra' ¹ and Ra ' ² to form a ring.

* Means a combined hand.]

Examples of the alkyl group represented by Ra ' ¹ and Ra' ^{2 in} the formula (a4-r-1) include the same alkyl groups exemplified as substituent groups which may be bonded to the carbon atom at the α- , And a methyl group or an ethyl group is preferable, and a methyl group is most preferable.

In the formula (a4-r-1), the hydrocarbon group of Ra ' ³ is preferably an alkyl group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 10 carbon atoms; The alkyl group is preferably a linear or branched alkyl group, and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, Butyl group, 1,1-dimethylethyl group, 1,1-diethylpropyl group, 2,2-dimethylpropyl group, 2,2-dimethylbutyl group and the like.

When Ra ' ³ is a cyclic hydrocarbon group, it may be aliphatic or aromatic, and may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane preferably has 3 to 8 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and cyclooctane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from the polycycloalkane. The polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, iso Borane, tricyclodecane, tetracyclododecane and the like.

When Ra ' ³ is an aromatic hydrocarbon group, specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene and phenanthrene; An aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom; And the like. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom and a nitrogen atom. Specific examples of the aromatic hydrocarbon group include groups in which one hydrogen atom is removed from the aromatic hydrocarbon ring (aryl group); A group in which one of the hydrogen atoms of the aryl group is substituted with an alkylene group (e.g., a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, Lt; / RTI &gt; And the like. The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

When Ra ' ³ is bonded to any of Ra' ¹ and Ra ' ² to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group, and the like.

In the formula (a4-1), examples of the acid dissociable groups of Ra ¹ include acid dissociable groups represented by the following formula (a4-r-2).

[Chemical Formula 8]

[Wherein,

Ra ' ⁴ to Ra' ⁶ are hydrocarbon groups.

Ra ' ⁵ and Ra' ⁶ may combine with each other to form a ring.

* Means a combined hand.]

Examples of the hydrocarbon group of Ra ' ⁴ to Ra' ⁶ include the same groups as those of Ra ' ³ above. Ra ' ⁴ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. When Ra ' ⁵ and Ra' ⁶ are bonded to each other to form a ring, there can be mentioned a group represented by the following formula (a4-r2-1).

On the other hand, when Ra ' ⁴ to Ra' ⁶ are not bonded to each other and are independent hydrocarbon groups, there may be mentioned groups represented by the following formula (a4-r2-2).

[Chemical Formula 9]

[Wherein,

Ra ^'10 is an alkyl group having 1 to 10 carbon atoms.

Ra is a group that forms an aliphatic cyclic group with ^'11 is Ra, the carbon atom ¹⁰ is bonded.

Ra ^'12 to Ra' ¹⁴ each independently represent a hydrocarbon group.

* Means a combined hand.]

Formula (r2-1-a4) of, Ra 'group having a carbon number of alkyl group of from 1 to 10 of ¹⁰ the formula (a4-r-1) Ra of the "exemplified as ³ linear or branched alkyl group of Group is preferable.

Formula (r2-1-a4) of, Ra 'aliphatic cyclic group for Ra is ^11, the configuration of the formula (a4-r-1)' is preferably an alkyl group exemplified as the cyclic ^3.

Formula (r2-2-a4) of, Ra ', and Ra ^{12' 14} are each independently preferably an alkyl group of 1 to 10 carbon atoms, and the alkyl group of the formula (a4-r-1) of the Ra 'in the ^three More preferably a linear or branched alkyl group, more preferably a linear alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group or an ethyl group.

In the formula (a4-r2-2), Ra is the ^"13 formula (a4-r-1) Ra of the" a linear, branched or cyclic alkyl group exemplified as the hydrocarbon ^group which are preferable . Among them, it is more preferable that R &lt; ³ &gt; is a group exemplified as a cyclic alkyl group.

Formula (a4-2) wherein n valent group _a2 +1 hydrocarbon Wa ¹ may be either an aliphatic hydrocarbon, it may be an aromatic hydrocarbon. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, a ring-containing aliphatic hydrocarbon group, or a combination of a linear or branched aliphatic hydrocarbon group and a ring-containing aliphatic hydrocarbon group And specifically a group the same as Va ¹ in the above-mentioned formula (a4-1) can be mentioned.

In the formula (a4-2), Ra ² may seonggiil dissociation represented by the formula (a4-r-1) as defined in the Ra ^1.

Alternatively, Ra ² in the formula (a4-2) may be an acid dissociable group represented by the following formula (a4-r-3) (hereinafter occasionally referred to as "tertiary alkyloxycarbonyl acid dissociable group" for convenience) .

[Chemical formula 10]

[Wherein,

Ra ' ⁷ to Ra' ⁹ represent an alkyl group.

* Means a combined hand.]

In the formula (a4-r-3), Ra ' ⁷ to Ra' ⁹ are preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The total carbon number of each alkyl group is preferably from 3 to 7, more preferably from 3 to 5, and most preferably from 3 to 4.

Specific examples of the formulas (a4-1) and (a4-2) are shown in the following formulas (11) and (12). In the following formulas, R ⁰ represents a hydrogen atom, a methyl group or a trifluoromethyl group.

 (11)

[Chemical Formula 12]

When the component (A-2) contains the structural unit (a4), the proportion of the structural unit (a4) is preferably 20 to 80 mol% , More preferably 75 mol%, and still more preferably 25 mol% to 70 mol%. By setting it to the lower limit value or more, lithography characteristics such as sensitivity, resolution, and LWR are improved. In addition, by setting it to be not more than the upper limit value, balance with other constituent units can be obtained.

constituent unit  (a5)

The structural unit (a5) may contain a structural unit (a5) having a -SO ₂ -containing cyclic group, a lactone-containing cyclic group, a carbonate-containing cyclic group or a heterocyclic group other than these.

When the component (A-2) is used for forming a resist film, the -SO ₂ -containing cyclic group, the lactone-containing cyclic group, the carbonate-containing cyclic group, or the other heterocyclic group other than those of the constituent unit (a5) Which is effective in improving the adhesion to the substrate.

When the above-mentioned structural unit (a4) has a -SO ₂ -containing cyclic group, a lactone-containing cyclic group, a carbonate-containing cyclic group or a heterocyclic group other than these, a5). However, such a structural unit corresponds to the structural unit (a4) and does not correspond to the structural unit (a5).

The constituent unit (a5) is preferably a constituent unit represented by the following formula (a5-1).

[Chemical Formula 13]

[Wherein,

R is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms, or a halogenated hydrocarbon group of 1 to 10 carbon atoms.

Ya ²¹ is a single bond or a divalent linking group.

La ²¹ represents -O-, -COO-, -CON (R ') -, -OCO-, -CONHCO- or -CONHCS-, and R' represents a hydrogen atom or a methyl group. However, when La ²¹ is -O-, Ya ²¹ is not -CO-.

Ra ²¹ is a -SO ₂ -containing cyclic group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a heterocyclic group other than these.

In the formula (a5-1), Ra ²¹ Of "-SO ₂ - containing cyclic group" means, -SO ₂ during the ring backbone - represents a cyclic group containing a ring containing, specifically, -SO ₂ - a cyclic sulfur atom (S) in the Is a cyclic group that forms part of the ring skeleton of &lt; RTI ID = 0.0 &gt; A ring containing -SO ₂ - in the ring skeleton is counted as the first ring, and in the case of only the ring, a monocyclic ring and, in the case of having another ring structure, it is called a polycyclic ring regardless of its structure. The -SO ₂ -containing cyclic group may be monocyclic or polycyclic.

Ra ²¹ Refers to a cyclic group containing a ring (lactone ring) containing -OC (= O) - in its ring skeleton. The lactone ring is counted as the first ring, and when it is only a lactone ring, it is called a monocyclic ring, and when it has another ring structure, it is called a ring ring regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. The lactone-containing cyclic group is not particularly limited and any cyclic group may be used. Specific examples thereof include groups represented by the following formulas (a5-r-1) to (a5-r-7).

[Chemical Formula 14]

[Wherein,

Ra ^'21 are each independently hydrogen atom, alkyl group, alkoxy group, halogen atom, halogenated alkyl group, a hydroxyl group, -COOR ", -OC (= O ) R", hydroxy alkyl, or cyano group.

R "is a hydrogen atom, or an alkyl group.

A "is an alkylene group, an oxygen atom, or a sulfur atom of 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom.

n 'is an integer of 0 to 2.

m 'is 0 or 1.

* Means a combined hand.]

Ra ²¹ Includes a cyclic group containing a ring (carbonate ring) containing -OC (= O) -O- in the cyclic skeleton of the "carbonate-containing cyclic group". When the carbonate ring is counted as the first ring, only the carbon ring is monocyclic, and when it has another ring structure, it is called the polycyclic ring regardless of its structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.

Ra ²¹ Refers to a cyclic group containing at least one atom other than carbon in addition to carbon, and examples thereof include a heterocyclic group and a nitrogen-containing heterocyclic ring. The term &quot; heterocyclic group &quot; Examples of the nitrogen-containing heterocyclic group include a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with one or two oxo groups. As the cycloalkyl group, for example, 2,5-dioxopyrrolidine and 2,6-dioxopiperidine are preferable.

When the component (A-2) contains the structural unit (a5), the proportion of the structural unit (a5) is preferably 1 to 80% by mole relative to the total of all the structural units constituting the component (A-2) , More preferably from 5 to 70 mol%, even more preferably from 10 to 65 mol%, and particularly preferably from 10 to 60 mol%. The effect of incorporating the constituent unit (a5) can be sufficiently obtained by setting the amount to not less than the lower limit value, and if it is not more than the upper limit value, balance with other constituent units can be obtained, and various lithographic characteristics and pattern shapes are improved.

constituent unit  (a6)

The structural unit (a6) is a structural unit containing a polar group-containing aliphatic hydrocarbon group (except those corresponding to the above-mentioned structural units (a4) and (a5)). It is considered that the component (A-2) has the hydrophilic property of the component (A-2) by having the constituent unit (a6), thereby contributing to the improvement of the resolution.

Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, a fluorinated hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom, and particularly, a hydroxyl group is preferable.

Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) or a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be either a monocyclic group or a polycyclic group. For example, in the resin for a resist composition for an ArF excimer laser, a large number of proposed ones can be appropriately selected and used. The cyclic group is preferably a polycyclic group and more preferably 7 to 30 carbon atoms.

Among them, a structural unit derived from an acrylate ester containing a hydroxyl group, a cyano group, a carboxyl group, or an aliphatic polycyclic group containing a fluorinated hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from a bicycloalkane, a tricycloalkane, a tetracycloalkane, and the like. Specific examples thereof include groups obtained by removing two or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isoborane, tricyclodecane and tetracyclododecane. Among these polycyclic groups, groups in which two or more hydrogen atoms have been removed from adamantane, groups in which two or more hydrogen atoms have been removed from norbornane, and groups in which two or more hydrogen atoms have been removed from tetracyclododecane are industrially preferable.

As the structural unit (a6), a structural unit containing a polar group-containing aliphatic hydrocarbon group as a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the? -Position may be substituted with a substituent is preferable.

When the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the structural unit (a6) is preferably a structural unit derived from a hydroxyethyl ester of acrylic acid, When the hydrocarbon group is a polyglycolic group, the structural unit represented by the following formula (a6-1), the structural unit represented by the formula (a6-2), and the structural unit represented by the formula (a6-3) are preferred.

[Chemical Formula 15]

[Wherein,

R is a hydrogen atom, a halogen atom, or a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a halogen atom.

j is an integer of 1 to 3, k is an integer of 1 to 3, t 'is an integer of 1 to 3, 1 is an integer of 1 to 5, and s is an integer of 1 to 3.]

The constituent unit (a6) contained in the component (A-2) may be one kind or two or more kinds.

The proportion of the constituent unit (a6) in the component (A-2) is preferably 5 to 50 mol%, more preferably 5 to 40 mol% based on the total amount of all the constituent units constituting the resin component (A-2) , More preferably from 5 to 25 mol%. When the ratio of the constituent unit (a6) is set to the lower limit value or more, the effect of containing the constituent unit (a6) is sufficiently obtained, and when it is not more than the upper limit value, balance with other constituent units becomes easy.

 The component (A-2) is preferably a copolymer having (a4), more preferably a copolymer having (a4) and (a5), and a copolymer having (a4), (a5) and (a6) desirable.

The component (A-2) may be used alone or in combination of two or more. The proportion of the component (A-2) in the resin (A) is preferably 25% by mass or more, more preferably 50% by mass, further preferably 75% by mass, based on the total mass of the component (A- 100% by mass. When the ratio is 25 mass% or more, the lithography characteristics are further improved. In the present invention, the content of the component (A-2) may be adjusted in accordance with the thickness of the resist film to be formed.

&Lt; Component (B) >

The component (B) is not particularly limited, and any of those proposed as acid-generating agents for chemically amplified resists can be used.

Examples of such an acid generator include an onium salt acid generator such as an iodonium salt or a sulfonium salt, an oxime sulfonate acid generator, bisalkyl or bisaryl sulfonyl diazomethanes, a poly (bis-sulfonyl) diazo Diazomethane-based acid generators such as methanes, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators are known.

Examples of the onium salt-based acid generators include the compounds represented by the following formula (b-1) or (b-2).

[Chemical Formula 16]

[Wherein,

R ^{1 "} to R ^3" and R ^{5 "} to R ^6" are each independently an aryl group or an alkyl group.

R ^{4 "} is an alkyl group of a linear, branched, or cyclic type in which some or all of the hydrogen atoms of the alkyl group may be substituted with fluorine.

At least one of R ^{1 "} to R ^3" is an aryl group.

At least one of R ^" to R ^" is an aryl group.

In the formula (b-1), the aryl group of R ^{1 "} to R ^3" is not particularly limited and is, for example, an aryl group having 6 to 20 carbon atoms, , An alkoxy group, a halogen atom, or the like, or may be unsubstituted. The aryl group is preferably an aryl group having 6 to 10 carbon atoms in that it can be synthesized at low cost. Specific examples thereof include a phenyl group and a naphthyl group. The alkyl group in which the hydrogen atom of the aryl group may be substituted is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. The alkoxy group to which the hydrogen atom of the aryl group may be substituted is preferably an alkoxy group having 1 to 5 carbon atoms, and most preferably a methoxy group or an ethoxy group. The halogen atom to which the hydrogen atom of the aryl group may be substituted is preferably a fluorine atom.

The alkyl group of R ^{1 "} to R ^3" is not particularly limited and includes, for example, a linear, branched, or cyclic alkyl group of 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specific examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decanyl group, A methyl group is preferable in that it is excellent in resolution and can be synthesized at low cost.

R ^{1 "~} R ^3" wherein, among two or more aryl groups is preferred, in which all of R ^{1 "~} R ^3" is more preferably an aryl group, and of these, R ^{1 "~} R ^3" is that the whole group Most preferred.

In the formula (b-1), the linear alkyl group represented by R ^{4 "} preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.

The cyclic alkyl group of R ^{4 "} preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.

When at least one of the hydrogen atoms of the R ^{4 "} alkyl group is substituted with fluorine, that is, the fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms (The proportion of fluorine atoms in the alkyl group) of the fluorinated alkyl group is preferably from 10 to 100%, more preferably from 50 to 100%. In particular, the fluorinated alkyl group preferably has a fluorinated alkyl group substituted with a fluorine atom Is preferable because the strength of the acid becomes strong.

R ^{4 "} is most preferably a linear or cyclic alkyl group, or a fluorinated alkyl group.

In the formula (b-2), R ^{4 "} is the same as R ^1" in the above formula (b-1).

In the formula (b-2), the aryl group of R ^{5 "} to R ^{6" includes} the same aryl groups as R ^{1 "} to R ^3" . Examples of the alkyl group represented by R ^{5 "} to R ^{6" include} the same alkyl groups as those represented by R ^{1 "} to R ^3" .

R ^{5 "~} R ^6" wherein at least two aryl groups that are preferable, in which all of R ^{5 "~} R ^6" is more preferably an aryl group. Among them, it is most preferable that R ^{5 "} to R ^6" are all phenyl groups.

Specific examples of the onium salt-based acid generators include trifluoromethane sulfonate or nonafluorobutane sulfonate of diphenyl iodonium, trifluoromethane sulfonate of bis (4-tert-butylphenyl) iodonium, Trifluoromethanesulfonate of triphenylsulfonium, fluorobutanesulfonate thereof, trifluoromethanesulfonate of triphenylsulfonium, heptafluoropropanesulfonate, camphorsulfonate or nonafluorobutanesulfonate thereof, trifluosulfonate of tri (4-methylphenyl) sulfonium, Heptafluoropropanesulfonate, its camphorsulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of dimethyl (4-hydroxynaphthyl) sulfonium, its heptafluoropropane Sulfonate, its camphorsulfonate or its nonafluorobutanesulfonate, monophenyldimethylsulfonium trifluoromethanesulfonate, its heptafluorope &lt; RTI ID = 0.0 &gt; The camphorsulfonate or its nonafluorobutanesulfonate, the diphenylmonomethylsulfonium trifluoromethanesulfonate, the heptafluoropropanesulfonate, the camphorsulfonate or the nonafluorobutane sulfone (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate, its camphorsulfonate or its nonafluorobutanesulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, Heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of tri (4-tert-butyl) phenylsulfonium, heptafluoropropanesulfone thereof, trifluoromethanesulfonate of tri (Trifluoromethanesulfonate) of diphenyl (1- (4-methoxy) naphthyl) sulfonium, the heptafluro A plate-sulfonate, and camphor sulfonate or nonafluoro-rope and the like butane sulfonate. Onium salts in which the anion portion of the onium salt is substituted with methanesulfonate, n-propanesulfonate, n-butanesulfonate or n-octanesulfonate can also be used.

In the formula (b-1) or (b-2), the anion moiety may be substituted with an anion moiety represented by the following formula (b-3) or (b- 1) or (b-2).

[Chemical Formula 17]

[Wherein,

X "is an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

Y "and Z" each independently represent an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

In the formula (b-3), X "is preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms.

In the formula (b-3), the alkyl groups of Y "and Z" each independently have 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 3 carbon atoms.

The number of carbon atoms of the alkylene group of X "or Y &quot;,Z" The number of carbon atoms in the alkyl group of the alkyl group is preferably as small as possible within the range of the carbon number and good solubility in a resist solvent.

Further, X " The higher the number of hydrogen atoms substituted with fluorine atoms in the alkylene group or the alkyl group of Y "and Z &quot;, the higher the strength of the acid and the higher the transparency to high energy light or electron beam of wavelengths of 200 nm or less desirable. The proportion of the fluorine atom in the alkylene group or the alkyl group, that is, the fluorine atom, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, the perfluoroalkyl Or a perfluoroalkyl group.

In the present invention, the oxime sulfonate-based acid generator is a compound having at least one group represented by the following formula (b-5) and has a property of generating an acid upon irradiation with radiation. These oxime sulfonate-based acid generators may be arbitrarily selected from those proposed for the chemically amplified resist composition.

[Chemical Formula 18]

[Expression

R ²¹ and R ²² each independently represent an organic group]

In the present invention, the "organic group" is a group containing a carbon atom, and includes atoms other than carbon atoms (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, Or the like).

In the formula (b-5), the organic group of R ²¹ is preferably an alkyl group or aryl group of a linear, branched, or cyclic type. These alkyl group and aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and the like. Here, the term "having a substituent" means that a part or all of the hydrogen atoms of the alkyl group or the aryl group is substituted with a substituent.

The alkyl group represented by R ²¹ preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, most preferably 1 to 4 carbon atoms . As the alkyl group, particularly a partially or fully halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is preferable. The partially halogenated alkyl group means an alkyl group in which a part of the hydrogen atoms are substituted with halogen atoms and the fully halogenated alkyl group means an alkyl group in which all of the hydrogen atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

The aryl group of R ²¹ preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. The aryl group is preferably a partially or fully halogenated aryl group. The partially halogenated aryl group means an aryl group in which a part of the hydrogen atoms are substituted with a halogen atom, and the fully halogenated aryl group means an aryl group in which all of the hydrogen atoms are substituted with a halogen atom.

R ²¹ is preferably an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms, which has no substituent.

In the formula (b-5), the organic group of R ²² is preferably an alkyl group, an aryl group or a cyano group of a linear, branched or cyclic type. Examples of the alkyl group and aryl group for R ^{22 include} the same alkyl groups and aryl groups exemplified for R ²¹ above.

As R ²² , a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms is particularly preferable.

More preferable examples of the oxime sulfonate-based acid generator include compounds represented by the following formula (b-6) or (b-7).

[Chemical Formula 19]

[Wherein,

R ³¹ is a cyano group, an alkyl group having no substituent or a halogenated alkyl group.

R ³² is an aryl group.

R ³³ is an alkyl group having no substituent or a halogenated alkyl group.]

[Chemical Formula 20]

[Wherein,

R ³⁴ is a cyano group, an alkyl group having no substituent or a halogenated alkyl group.

R ³⁵ is a 2 or 3-valent aromatic hydrocarbon group.

R ³⁶ is an alkyl group having no substituent or a halogenated alkyl group.

p is 2 or 3.]

In the formula (b-6), the alkyl group or halogenated alkyl group having no substituent represented by R ³¹ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.

As R ³¹ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

The fluorinated alkyl group for R ³¹ preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more, and more preferably 90% or more.

Examples of the aryl group for R ^{32 in} the formula (b-6) include an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group and a phenanthryl group And a heteroaryl group in which a part of the carbon atoms constituting the ring of these groups is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Among them, a fluorenyl group is preferable.

The aryl group of R ³² may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.

In the formula (b-7), the alkyl group or halogenated alkyl group having no substituent represented by R ³³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.

As R ³³ , a halogenated alkyl group is preferable, a fluorinated alkyl group is more preferable, and a partially fluorinated alkyl group is most preferable.

The fluorinated alkyl group for R ³³ preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more, more preferably 90% or more of the fluorinated alkyl group, Therefore, it is preferable. Most preferably, it is a completely fluorinated alkyl group in which the hydrogen atom is 100% fluorine-substituted.

Examples of the alkyl group or halogenated alkyl group having no substituent group represented by R ^{34 in} the formula (b-7) include the same alkyl group or halogenated alkyl group having no substituent as the R ³¹ .

Examples of the bivalent or trivalent aromatic hydrocarbon group represented by R ^{35 in} the formula (b-7) include groups in which one or two hydrogen atoms have been further removed from the aryl group of R ³² .

Examples of the alkyl group having no substituent or the halogenated alkyl group for R ^{36 include} the same groups as the alkyl group or halogenated alkyl group having no substituent for R ³³ .

p is preferably 2.

Specific examples of the oxime sulfonate-based acid generators include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzenesulfonyloxyimino) -benzyl cyanide,? - (benzenesulfonyloxyimino) -4-nitrobenzenesulfonyloxyimino) -benzyl cyanide, (Benzenesulfonyloxyimino) -2,4-dichlorobenzyl cyanide,? - (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide,? - (benzenesulfonyloxyimino) (2-chlorobenzenesulfonyloxyimino) -4-methoxybenzyl cyanide,? - (benzenesulfonyloxyimino) -thien-2-yl acetonitrile, [alpha] - (4-dodecylbenzenesulfonyloxyimino) -benzyl cyanide, [alpha] - [(p- toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, alpha - [(dodecylbenzenesulfonyloxy Amino) -4-methoxyphenyl] acetonitrile , α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclopentenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenyl aceto Nitrile,? - (methylsulfonyloxyimino) -1-cycloheptenyl acetonitrile,? - (methylsulfonyloxyimino) -1-cyclooctenyl acetonitrile,? - (trifluoromethylsulfonyloxyimino) (Trifluoromethylsulfonyloxyimino) -cyclohexyl acetonitrile,? - (ethylsulfonyloxyimino) -ethylacetonitrile,? - (propylsulfonyloxyimino) -cyclopentenylsuccinonitrile, (Cyclohexylsulfonyloxyimino) -cyclopentyl acetonitrile,? - (cyclohexylsulfonyloxyimino) -cyclohexyl acetonitrile,? - (cyclohexylsulfonyloxyimino) -1- Cyclopentenyl acetonitrile,? - (ethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile,? - ( Propylsulfonyloxyimino) -1-cyclopentenyl acetonitrile,? - (n-butylsulfonyloxyimino) -1-cyclopentenyl acetonitrile,? - (ethylsulfonyloxyimino) -1-cyclohexenyl Acetonitrile,? - (isopropylsulfonyloxyimino) -1-cyclohexenyl acetonitrile,? - (n-butylsulfonyloxyimino) -1-cyclohexenyl acetonitrile,? - (methylsulfonyloxyimino ) -Phenylacetonitrile,? - (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile,? - (trifluoromethylsulfonyloxyimino) -phenylacetonitrile,? - (trifluoromethylsulfonyl (Ethylsulfonyloxyimino) -p-methoxyphenylacetonitrile,? - (propylsulfonyloxyimino) -p-methylphenyl acetonitrile,? - Sulfonyloxyimino) -p-bromophenylacetonitrile, and the like.

Specific examples of the oxime sulfonate-based acid generator include compounds represented by the following formulas.

[Chemical Formula 21]

Examples of preferred compounds among the compounds represented by the above formula (b-6) or (b-7) are shown below.

[Chemical Formula 22]

(23)

[0035] Specific examples of the bisalkyl or bisaryl sulfonyl diazomethanes among the diazomethane acid generators include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane and the like.

Examples of the poly (bis-sulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane (in the case of A = 3) having 1, (Phenylsulfonyldiazomethylsulfonyl) butane (in case of A = 4), 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane (in case of A = 6), 1,10- Bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane (when B = 2), 1,3-bis (phenylsulfonyldiazomethylsulfonyl) decane (when A = 10) (Cyclohexylsulfonyldiazomethylsulfonyl) propane (when B = 3), 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane (when B = 6), 1,10-bis (Cyclohexylsulfonyldiazomethylsulfonyl) decane (when B = 10), and the like.

&Lt; EMI ID =

As the component (B), these acid generators may be used singly or in combination of two or more.

The content of the component (B) in the resist composition of the present invention is 0.5 to 30 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the component (A). With the above range, the pattern formation is sufficiently performed. In addition, a homogeneous solution can be obtained and storage stability is improved, which is preferable.

&Lt; Component (C) >

(C) is a compound having radiation-absorbing ability. The component (C) has an ability to absorb in the wavelength band of the radiation used for exposure, and it is possible to reduce irregular reflection due to a change in the pattern dimension caused by the SW generated by the reflection from the substrate and a step on the surface of the substrate desirable.

Concretely, low molecular weight compounds such as dyes and high molecular weight compounds such as resins can be mentioned as compounds having an absorption capacity at, for example, 248 nm which is the wavelength of KrF excimer laser or 193 nm which is the wavelength of ArF excimer laser.

Specific examples of the component (C) include compounds represented by the following formula (1).

(25)

식 (1)

Equation (1)

[Wherein,

R ₁ and R ₂ are each independently a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a hydroxyl group, and one -CH ₂ - of the hydrocarbon groups or two or more non-adjacent -CH ₂ - _{O-, -S-, -NH-, -NR 3} -, -C (O) -, -OC (O) -, -OC (O) O-, -SO-, -SO 2 -, -CONH- , -CONR ₃ -, -OC (O) NH-, or -OC (O) NR ₃ -, wherein R ₃ is a hydrocarbon group of 1 to 10 carbon atoms.

n1, n2, m1 and m2 are each independently an integer of 0 to 5, and n1 + m1 and n2 + m2 do not both exceed 5.]

In the formula (1), the hydrocarbon group of R ₁ and R ₂ is a concept including an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group of R ₁ and R ₂ is a concept including a linear, branched or cyclic aliphatic hydrocarbon group and may be saturated or unsaturated, but more preferably saturated.

The linear hydrocarbon group is preferably a linear alkyl group and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- T-butyl, neopentyl and the like. The linear aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms.

As the branched aliphatic hydrocarbon group, a branched alkyl group is preferable, and specifically, -CH (CH ₃ ) CH ₃ , -C (CH ₃ ) ₂ CH ₃ , -CH (CH ₂ CH ₃ ) CH ₃ ; -CH (CH ₃ ) CH ₂ CH ₃ , and -CH ₂ CH (CH ₃ ) CH ₃ ; And an alkylbutyl group such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₃ and -CH ₂ CH (CH ₃ ) CH ₂ CH ₃ . The branched-chain aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group, but a monocyclic group is preferred. Examples of the monocyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic group include isobonyl, norbornyl, tricyclodecanyl, and the like. The cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 5 to 10 carbon atoms.

The aromatic hydrocarbon group of R ₁ and R ₂ is a concept including an aralkyl group and an alkylaryl group, and specifically includes a phenyl group, a phenylethyl group, a phenylpropyl group, a benzyl group and a naphthalene group.

When one -CH ₂ - of the hydrocarbon groups of R ₁ and R ₂ - or two or more non-adjacent -CH ₂ - are substituted, it is preferably replaced by -O-, -S- or -NH- , And among them, -O- is particularly preferable. Specific examples thereof include -OCH ₂ CH ₂ OH, -OCH ₂ CH ₂ CH ₂ OH, -OCH ₂ CH ₂ OCH ₂ CH ₂ OH and -CH ₂ OCH ₂ CH ₂ OH.

R ₁ and the hydrocarbon group of R _2, substituted or but may be unsubstituted by a hydroxy group, in particular if the m1 and m2 is 0, respectively, i.e., when the phenyl group does not have a hydroxyl group, with hydrogen, the hydroxyl group of R ₁ and R ₂ Is preferably substituted.

The hydrocarbon group of R ₁ and R ₂ may further have a substituent other than a hydroxyl group, and examples of the substituent include a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms.

R ₁ and R ₂ may be the same as or different from each other, but are preferably the same as each other.

In the formula (1), n1 and n2 each independently represent an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. n1 and n2 may be the same or different from each other and are preferably the same as each other.

When n1 and n2 are both an integer of 1 to 5, R ₁ and R ₂ may be the same as or different from each other, and are preferably the same as each other. Although the bonding position of R ₁ and R ₂ is not particularly limited, it is preferable that R ₁ and R ₂ are present at the p-position of the phenyl group, and the R ₁ and R ₂ are bonded at positions symmetrical in the component (C) desirable.

When n1 is 2 or 3, plural R _{1 s} may be the same as or different from each other, and when n2 is 2 or 3, plural R _{2 s} may be the same or different.

In the formula (1), m1 and m2 are each independently an integer of 0 to 5, more preferably 0 or 1, and particularly preferably 1. m1 and m2 may be the same as or different from each other, and the sum of m1 and m2 is more preferably 0 to 2.

In the formula (1), the bonding position of each hydroxyl group bonded to the phenyl group is not particularly limited.

Specific examples of the component (C) are listed below.

(26)

As the component (C), one type may be used alone, or two or more types may be used in combination.

The content of the component (C) in the resist composition of the present invention is preferably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass, still more preferably 2 to 15 parts by mass, per 100 parts by mass of the component (A) Particularly preferably 2 to 10 parts by weight, and most preferably 2 to 8 parts by weight.

When the content of the component (C) is lower than the preferable lower limit value, it is possible to sufficiently reduce the irregular reflection due to the change in the pattern size caused by the reflection from the substrate and the step difference on the surface of the substrate. On the other hand, If it is not more than the upper limit, it is preferable because the resolution is excellent.

On the other hand, in the case of using the component (C) defined in the present invention, the absorption rate to the exposure light is high at a small addition amount as compared with the case of using a compound having an anthracene skeleton or a benzophenone skeleton, It is possible not only to effectively suppress the pattern dimension change but also to solve the toxicity problem.

&Lt; Component (D) >

The resist composition of the present invention is a resist composition wherein the component (A) contains the structural units (a1) and (a3), or the structural units (a4) and / or (a6) Etc.), a crosslinking agent may be contained as the component (D). The component (D) is not particularly limited and may be arbitrarily selected from among the crosslinking agents used so far in the resist composition.

Specifically, for example, a melamine crosslinking agent, a urea crosslinking agent and a glycoluril crosslinking agent can be mentioned.

Examples of the melamine crosslinking agent include a compound obtained by reacting melamine and formaldehyde to replace the hydrogen atom of the amino group with a hydroxymethyl group, a compound obtained by reacting melamine and formaldehyde with an alcohol to replace the hydrogen atom of the amino group with an alkoxymethyl group have. Specific examples thereof include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine. Of these, hexamethoxymethylmelamine is preferable.

The melamine-based crosslinking agent may be used singly or in combination of two or more.

Examples of the urea crosslinking agent include compounds obtained by reacting urea and formaldehyde to replace the hydrogen atom of the amino group with a hydroxymethyl group and compounds obtained by reacting urea and formaldehyde with an alcohol to replace the hydrogen atom of the amino group with an alkoxymethyl group have. Specific examples thereof include bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bishbutoxymethyl urea. Of these, bismethoxymethyl urea is preferable.

As the urea-based crosslinking agent, an alkylene urea-based crosslinking agent can also be preferably used.

As specific examples of the alkylene urea-based crosslinking agent, there may be mentioned a compound represented by the following formula (III).

(27)

Wherein R ^{1 '} and R ^2' are each independently a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, and R ^{3 '} and R ^4' each independently represent a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms , v is 0 or an integer of 1 to 2.]

The compound represented by the above formula (III) can be obtained by condensation reaction of an alkylene urea and formalin, and further reacting the product with an alcohol.

Specific examples of the alkylene urea-based crosslinking agent include, for example, mono and / or dihydroxymethylated urea, mono and / or dimethoxymethylated urea, mono and / or diethoxymethylated urea, mono and / Mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethylated propylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dihydroxymethylated propylene urea, Or dipropoxymethylated propylene urea, mono and / or dibutoxymethylated propylene urea, 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone, Dimethoxy-2-imidazolidinone, and the like.

The urea crosslinking agent may be used alone or in combination of two or more.

As the glycoluril-based crosslinking agent, a glycoluril derivative in which the N position is substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms may be mentioned. Such a glycoluril derivative can be obtained by condensation reaction of glycoluril and formalin, or by reacting the product with an alcohol.

Examples of the glycoluril-based crosslinking agent include mono, di- and / or tetrahydroxymethylated glycoluril mono, di- and / or tetramethoxymethylated glycoluril mono, di- and / or tetra Methoxymethylated glycoluril, mono, di-tri and / or tetra-propoxymethylated glycoluril, mono-, di- and / or tetrabutoxymethylated glycoluril.

As the glycoluril-based crosslinking agent, one type may be used alone, or two or more types may be used in combination.

The content of the component (D) in the resist composition of the present invention is preferably from 6 to 50 parts by mass, more preferably from 10 to 20 parts by mass, per 100 parts by mass of the component (A). When the content of the component (D) is at least the lower limit value, the crosslinking formation proceeds sufficiently, and a good resist pattern is obtained. On the other hand, if it is not more than the upper limit, the storage stability of the resist coating liquid is good, and deterioration of sensitivity over time is suppressed.

<Other optional components>

The resist composition of the present invention may further contain, as optional components, a nitrogen-containing organic compound (E) (hereinafter referred to as component (E)) in order to improve the resist pattern shape and storage stability over time have.

As the component (E) has already been proposed variously, it may be used arbitrarily from known ones, and an aliphatic amine, especially a secondary aliphatic amine or a tertiary aliphatic amine is preferable.

Examples of the aliphatic amine include an amine (alkylamine or alkyl alcohol amine) in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms. Specific examples thereof include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; Dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine and dicyclohexylamine; N-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-pentylamine, tri- trialkylamines such as n-nonylamine, tri-n-decenylamine and tri-n-dodecylamine; And alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine and tri-n-octanolamine. Among these, alkyl alcohol amine and trialkyl amine are preferable, and alkyl alcohol amine is most preferable. Of the alkyl alcohol amines, triethanolamine and triisopropanolamine are most preferred.

These may be used alone or in combination of two or more.

The component (E) is usually used in a range of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A).

The resist composition of the present invention may further contain, as optional additional components, an organic peroxide (hereinafter referred to as &quot; organic peroxide &quot;) for the purpose of preventing deterioration of sensitivity due to the blending of the component (E) (Hereinafter referred to as a component (F)) of a carboxylic acid, a carboxylic acid, a carboxylic acid or a phosphoric acid or a phosphoric acid or a derivative thereof (F). The component (E) and the component (F) may be used in combination, or any one of them may be used.

As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are preferable.

Examples of the phosphoric acid or its derivative include phosphoric acid or a derivative thereof such as phosphoric acid or ester thereof such as phosphoric acid, di-n-butyl ester phosphate or diphenyl phosphate, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid-di- , Phosphonic acids and their esters such as phenylphosphonic acid, phosphonic acid diphenyl ester and phosphonic acid dibenzyl ester, phosphinic acids such as phosphinic acid and phenylphosphinic acid, and derivatives thereof such as esters thereof, among which Particularly preferred is phosphonic acid.

The component (F) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of the component (A).

The resist composition of the present invention can be produced by dissolving a material in an organic solvent.

The organic solvent may be any one which can dissolve each component to be used and can form a homogeneous solution, and any one or two or more kinds of solvents conventionally known as solvents for chemically amplified resists can be suitably selected and used .

Lactones such as? -Butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; Monomethyl ether, monopropyl ether, monopropyl ether, monoethyl ether of monoacetate, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate Polyhydric alcohols such as butyl ether or monophenyl ether and derivatives thereof; Cyclic ethers such as dioxane; And esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate.

These organic solvents may be used alone or in combination of two or more.

Further, a mixed solvent obtained by mixing propylene glycol monomethyl ether acetate (PGMEA) and a polar solvent is preferable. The compounding ratio (mass ratio) may be suitably determined in consideration of the compatibility of the PGMEA and polar solvent, and is preferably within the range of 1: 9 to 9: 1, more preferably 2: 8 to 8: 2 desirable.

More specifically, in the case of mixing EL as a polar solvent, it is preferable that the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. When propylene glycol monomethyl ether (PGME) is blended as a polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.

As the organic solvent, a mixed solvent of γ-butyrolactone and at least one selected from PGMEA and EL is also preferable. In this case, as the mixing ratio, the mass ratio of the former to the latter is preferably 70:30 to 95: 5.

The amount of the organic solvent to be used is not particularly limited, but may be appropriately determined depending on the thickness of the coating film, such as a concentration that can be applied to a substrate. In general, the concentration of the solid content of the resist composition is preferably 2 to 20 mass%, more preferably 5 to 15 mass% %. &Lt; / RTI &gt;

The resist composition of the present invention can further contain miscible additives such as an additional resin for improving the performance of a resist film, a surfactant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, Antistatic agents and the like can be properly added and contained.

As described above, the resist composition of the present invention forms a resist pattern sufficiently suppressed in pattern size change by SW in a thin film having a thickness that can be used for a thin film implantation process, particularly a thin film of 500 nm or less The resist composition of the present invention is preferable for a thin film implantation process. Further, the resist composition of the present invention is excellent in sensitivity and resolution. Since the resist pattern used in the implantation process is used as a mask for implanting impurity ions, it is possible to form a fine pattern with good reproducibility as well as a small change in the pattern dimension due to the SW, The resist composition of the present invention is preferable for an implantation process.

In addition, the resist composition of the present invention can solve the toxicity problem that occurs when a compound having an anthracene skeleton or a benzophenone skeleton is used as the component (C).

In manufacturing an integrated circuit device having a three-dimensional structure, incident light and diffuse reflection from the substrate during exposure from the stepped substrate can be sufficiently reduced, and defective shape (SW) of the resist pattern can be suppressed.

< Resist  Pattern formation>

In the present invention, the resist pattern can be formed by forming a resist film on the support using the above-mentioned resist composition, exposing the resist film, and developing the resist film to form a resist pattern.

The resist pattern forming method of the present invention can be carried out, for example, as follows.

First, the resist composition of the present invention is coated on a substrate such as a silicon wafer with a spinner or the like and then baked (post-apply baking (PAB)) at a temperature of 80 to 150 DEG C for 40 to 120 seconds Is performed for 60 to 90 seconds to form a resist film. Subsequently, the resist film is selectively exposed through a desired mask pattern using an exposure apparatus, and then subjected to a heat treatment (post exposure bake (PEB)) at a temperature of 80 to 150 DEG C for 40 to 120 seconds , Preferably 60 to 90 seconds.

Next, the resist film is developed.

The developing process is carried out using a developing solution (organic developing solution) containing an alkaline developing solution in the case of the alkali developing process and an organic solvent in the case of the solvent developing process.

After the developing treatment, rinsing treatment is preferably carried out. In the case of the alkaline development process, rinsing is preferably performed using purified water, and in the case of the solvent development process, a rinsing solution containing an organic solvent is preferably used.

In the case of the solvent developing process, a treatment for removing the developing solution or the rinsing liquid adhering to the pattern by the supercritical fluid may be performed after the developing treatment or the rinsing treatment.

After the development treatment or the rinsing treatment, drying is performed. In some cases, a baking process (post-baking) may be performed after the above development process. In this manner, a resist pattern can be obtained.

The processes up to this point can be carried out by a known technique. The operating conditions and the like are preferably set appropriately according to the composition and properties of the resist composition to be used.

Examples of the alkali developing solution used in the developing treatment in the alkali development process include an aqueous solution of 0.1 to 10 mass% tetramethylammonium hydroxide (TMAH).

The organic solvent contained in the organic developing solution used in the developing treatment in the solvent developing process may be any solvent that can dissolve the component (A) (component (A) before exposure) and may be appropriately selected from known organic solvents. Specifically, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent or an ether solvent and a hydrocarbon solvent may be used.

If necessary, known additives may be added to the organic developer. Examples of the additive include a surfactant. The surfactant is not particularly limited and, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.

When a surfactant is blended, the blending amount thereof is usually 0.001 to 5 mass%, preferably 0.005 to 2 mass%, and more preferably 0.01 to 0.5 mass%, based on the total amount of the organic developer.

The developing process can be carried out by a known developing method. For example, a method of dipping the support in a developer for a predetermined time (dip method), a method of mounting the developer on the surface of the support by surface tension, A method of spraying a developing solution onto the surface of a support (spraying method), a method of continuously discharging a developing solution while scanning a developer discharging nozzle at a constant speed on a support rotating at a constant speed (dynamic dispensing method), and the like .

The rinsing treatment (rinsing treatment) using the rinsing liquid can be carried out by a known rinsing method. Examples of the method include a method (spin coating method) in which the rinsing liquid is continuously ejected onto a support rotating at a constant speed, a method (dip method) in which the support is immersed in the rinsing liquid for a certain period of time, And spraying method (spraying method).

When the thickness of the resist film is 500 nm or less, it can be preferably used for a thin film implantation process, preferably 100 to 450 nm, and more preferably 200 to 400 nm.

The radiation used for exposure is not particularly limited and may be carried out using an ArF excimer laser, KrF excimer laser, F ₂ laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), electron beam, X-ray, . The resist composition of the present invention is preferably used for a KrF excimer laser, an ArF excimer laser, an electron beam or an EUV (extreme ultraviolet), and is particularly preferable for a KrF excimer laser.

Further, an organic or inorganic anti-reflection film may be formed between the substrate and the resist film or on the resist film.

The resist pattern obtained in this manner is preferable for a thin film implantation process because it has a small dimensional change even if it is a thin film of 500 nm or less. It is also preferable that the resist pattern is formed on the stepped substrate because the dimensional change is small.

[ Example ]

Hereinafter, the embodiments of the present invention will be described, but the scope of the present invention is not limited to these embodiments.

< Resist  Preparation of composition &gt;

Example  1 to 3 and Comparative Example  One

The components shown in Table 1 were mixed and dissolved to prepare negative resist compositions of Examples 1 to 3 and Comparative Example 1.

(A) Component Component (B) (C) Component (D) Component (E) Component (F) Component (S) component Example 1 (A) -1
[100] (B) -1
[2.5] (C) -1
[2.4] (D) -1
[10] (E) -1
[0.38] (F) -1
[0.23] (S) -1
[900] Example 2 (A) -1
[100] (B) -1
[2.5] (C) -1
[4] (D) -1
[10] (E) -1
[0.38] (F) -1
[0.23] (S) -1
[900] Example 3 (A) -1
[100] (B) -1
[2.5] (C) -1
[6] (D) -1
[10] (E) -1
[0.38] (F) -1
[0.23] (S) -1
[900] Comparative Example 1 (A) -1
[100] (B) -1
[2.5] - (D) -1
[10] (E) -1
[0.38] (F) -1
[0.23] (S) -1
[900]

In Table 1, the respective abbreviations each indicate the following, and the numerical value in [] is the compounding amount (parts by mass).

(HS / ST = 80/20 (molar ratio), Mw = 8,000)) (A) -1: hydroxystyrene (HS) / styrene

(B) -1: Triphenylsulfonium camphorsulfonate (TPS-Cs)

(C) -1: A compound represented by the following formula (2)

(28)

(2)

(2)

(D) -1: A cross-linking agent (trade name: NIKARAK MX-270, manufactured by Sanwa Chemical Co., Ltd.) represented by the following formula (3)

[Chemical Formula 29]

(3)

(3)

(E) -1: Triethylamine

(F) -1: Salicylic acid

(S) -1: a mixed solvent of PGMEA and PGME (PGMEA: PGME = 60: 40 (mass ratio))

Example  4 to 6 and Comparative Example  2

The components shown in Table 2 were mixed and dissolved to prepare positive resist compositions of Examples 4 to 6 and Comparative Example 2.

(A) Component Component (B) (C) Component (E) Component (F) Component (S) component Example 4 (A) -2
[100] (B) -2
[6.0] (B ') - 2 [3.0] (C) -1
[4.5] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700] Example 5 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] (C) -1
[6.0] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700] Comparative Example 6 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] (C) -1
[7.5] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700] Comparative Example 2 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] - (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700]

In Table 2, the respective abbreviations each indicate the following, and the numerical value in [] is the compounding amount (parts by mass).

(A / B = 65/35 (mass ratio)) of the copolymer (resin A) represented by the following formula (4) and the copolymer (resin B)

(30)

(4)

(4)

[Wherein, m ¹ : n ¹ = 61: 39 (molar ratio), mass average molecular weight = 8,000]

(31)

(5)

(5)

[In the formula, m ² : n ² = 61: 39 (molar ratio), mass average molecular weight = 8,000]

(B) -2: bis (cyclohexylsulfonyl) diazomethane represented by the following formula (6)

(32)

(6)

(6)

(B ') - 2: bis (1,1-dimethylethylsulfonyl) diazomethane represented by the following formula (7)

(33)

(7)

(7)

(C) -1: The compound represented by the formula (2) used in the above Examples 1 to 3

(E) -2: Triethanolamine

(F) -2: Maleic acid

(S) -2: mixed solvent of PGMEA and EL (PGMEA: EL = 80: 20 (mass ratio))

Example  7-11 and Comparative Example  3 to 6

The components shown in Table 3 were mixed and dissolved to prepare positive resist compositions of Examples 7 to 11 and Comparative Examples 3 to 6

(A)
ingredient (B)
ingredient (C)
ingredient (E)
ingredient (F)
ingredient (F ')
ingredient (S)
ingredient Example 7 (A) -3
[100] (B) -4
[1.6] (B) -5
[1.41] (B) -6
[0.1] (C) -1
[10] - (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 8 (A) -3
[100] (B) -4
[1.6] (B) -5
[1.41] (B) -6
[0.5] (C) -1
[10] - (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 9 (A) -3
[100] (B) -4
[1.6] (B) -5
[1.41] (B) -6
[0.5] (C) -1
[15] - (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 10 (A) -3
[100] (B) -4
[3.2] - (B) -6
[0.5] (C) -1
[10] - (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 11 (A) -3
[100] (B) -4
[2.5] - (B) -6
[0.5] (C) -1
[10] - (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Comparative Example 3 (A) -3
[100] (B) -4
[1.6] (B) -5
[1.41] (B) -6
[0.1] - - (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Comparative Example 4 (A) -3
[100] (B) -4
[3.2] - (B) -6
[0.5] - - (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 12 (A) -3
[100] (B) -4
[1.6] (B) -5
[1.41] - (C) -1
[10] (E) -3
[0.28] (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 13 (A) -3
[100] (B) -4
[1.6] (B) -5
[1.41] - (C) -1
[10] (E) -3
[0.56] (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 14 (A) -4
[100] (B) -4
[1.6] (B) -5
[1.41] - (C) -1
[10] (E) -3
[0.56] (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 15 (A) -5
[100] (B) -4
[1.6] (B) -5
[1.41] - (C) -1
[10] (E) -3
[0.56] (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 16 (A) -6
[100] (B) -4
[1.6] (B) -5
[1.41] - (C) -1
[10] (E) -3
[0.56] (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Comparative Example 5 (A) -3
[100] (B) -4
[1.6] (B) -5
[1.41] - - (E) -3
[0.28] (F) -1
[0.5] - (S) -3
[3,200] (S) -4
[30] Example 17 (A) -3
[100] (B) -3
[3.04] - (B) -6
[0.1] (C) -1
[2.0] - (F) -1
[0.5] (F ') - 1
[2.0] (S) -3
[3,200] (S) -4
[30] Example 18 (A) -3
[100] (B) -3
[3.04] - (B) -6
[0.1] (C) -1
[5.0] - (F) -1
[0.5] (F ') - 1
[2.0] (S) -3
[3,200] (S) -4
[30] Example 19 (A) -3
[100] (B) -3
[3.04] - (B) -6
[0.1] (C) -1
[10] - (F) -1
[0.5] (F ') - 1
[2.0] (S) -3
[3,200] (S) -4
[30] Comparative Example 6 (A) -3
[100] (B) -3
[3.04] - (B) -6
[0.1] - - (F) -1
[0.5] (F ') - 1
[2.0] (S) -3
[3,200] (S) -4
[30]

(A) -3 to (A) -6: See Table 4 below:

Suzy Monomer Composition ratio (molar ratio) Mw Mw / Mn (A) -3 1/2/3/4/8 25/30/20/15/10 9,000 1.75 (A) -4 1/5 50/50 9,000 1.68 (A) -5 1/6/8 45/45/10 7,000 1.59 (A) -6 1/6/7/8 45/40/5/10 7,000 1.65

(34)

(B) -3 to (B) -6:

(35)

(C) -1: The compound represented by the formula (2) used in the above Examples 1 to 3

(E) -3: Tripentylamine

(F) -1: Salicylic acid

(F ') - 1: fluorine-containing polymer compound represented by the following formula (7)

(36)

(7)

(7)

[The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 17,100 and the molecular weight dispersion degree (Mw / Mn) was 1.71. ^The copolymer composition ratio (ratio (molar ratio) of each constitutional unit in the structural formula) obtained by ¹³ C-NMR is l / m = 52/48]

(S) -3: mixed solvent of PGMEA and PGME (PGMEA: PGME = 70: 30 (mass ratio))

(S) -4: gamma -butyrolactone

Example  20 ~ 27

The components shown in Table 5 were mixed and dissolved to prepare negative resist compositions of Examples 20 to 27.

(A) Component Component (B) (C) Component (D) Component (E) Component (F) Component (S) component Example 20 (A) -1
[100] (B) -1
[2.5] (C) -2
[8.26] (D) -1
[10] (E) -3
[0.38] (F) -1
[0.23] (S) -1
[900] Example 21 (A) -1
[100] (B) -1
[2.5] (C) -2
[2.4] (D) -1
[10] (E) -3
[0.38] (F) -1
[0.23] (S) -1
[900] Example 22 (A) -1
[100] (B) -1
[2.5] (C) -2
[4.0] (D) -1
[10] (E) -3
[0.38] (F) -1
[0.23] (S) -1
[900] Example 23 (A) -1
[100] (B) -1
[2.5] (C) -2
[6.25] (D) -1
[10] (E) -3
[0.38] (F) -1
[0.23] (S) -1
[900] Example 24 (A) -1
[100] (B) -1
[2.5] (C) -3
[2.4] (D) -1
[10] (E) -3
[0.38] (F) -1
[0.23] (S) -1
[900] Example 25 (A) -1
[100] (B) -1
[2.5] (C) -3
[4.0] (D) -1
[10] (E) -3
[0.38] (F) -1
[0.23] (S) -1
[900] Example 26 (A) -1
[100] (B) -1
[2.5] (C) -3
[6.25] (D) -1
[10] (E) -3
[0.38] (F) -1
[0.23] (S) -1
[900] Example 27 (A) -1
[100] (B) -1
[2.5] (C) -3
[10.24] (D) -1
[10] (E) -3
[0.38] (F) -1
[0.23] (S) -1
[900]

In Table 5, the respective abbreviations each indicate the following, and the numerical value in [] is the compounding amount (parts by mass).

(A) -1, (B) -1, (D) -1, (F) -1 and (S) -1 are as defined below in Table 1.

(C) -2: a compound represented by the following formula (8)

(37)

(8)

(8)

(C) -3: a compound represented by the following formula (9)

(38)

(9)

(9)

(E) -3: Tripentylamine

Example  28 to 33

The components shown in Table 6 were mixed and dissolved to prepare positive resist compositions of Examples 28 to 33.

(A) Component Component (B) (C) Component (E) Component (F) Component (S) component Example 28 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] (C) -2
[4.5] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700] Example 29 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] (C) -2
[6.0] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700] Example 30 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] (C) -2
[7.5] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700] Example 31 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] (C) -3
[4.5] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700] Example 32 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] (C) -3
[6.0] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700] Example 33 (A) -2
[100] (B) -2
[6.0] (B ') - 2
[3.0] (C) -3
[7.5] (E) -2
[0.29] (F) -2
[0.09] (S) -2
[700]

In Table 6, the respective abbreviations each indicate the following, and the numerical value in [] is the compounding amount (parts by mass).

(A) -2, (B) -2, (B ') - 2, (E) -2, (F) -2 and (S) -2 are as defined below in Table 2.

(C) -2 and (C) -3 are as defined below in Table 5.

< Resist  Evaluation of composition &gt;

Using the resist composition solutions obtained in Examples 1 to 33 and Comparative Examples 1 to 6, the following evaluations were carried out.

Example  1 to 3 and Comparative Example 1 of  evaluation

[Measurement of B-A value]

As the negative resist compositions of Examples 1 to 3 and Comparative Example 1, a TEOS (Tetra ethyl orthosilicate) substrate having a step difference as described above was used, and SW was a B-A Respectively.

[Evaluation of Resolution]

The negative resist composition solutions obtained in Examples 1 to 3 and Comparative Example 1 were uniformly coated on a TEOS substrate having 8-inch steps by using a spinner and subjected to PAB treatment at 100 DEG C for 60 seconds on a hot plate Thereby forming a resist film having a thickness of 370 nm.

Subsequently, a KrF exposure apparatus (wavelength: 248 nm) NSR-S210 (manufactured by Nikon, NA (numerical aperture) = 0.8, sigma = 0.6) was selectively exposed through a binary mask.

Then, PEB treatment was performed at 110 DEG C for 60 seconds, paddle development was performed at 23 DEG C with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then water rinsed with pure water for 30 seconds, Lt; / RTI &gt; A resist pattern (hereinafter referred to as an L / S pattern) of 200 nm line and space (1: 1) was formed by heating at 100 캜 for 60 seconds and drying, and a scanning electron microscope , CD4000) to obtain an exposure amount Exp (sensitivity) (unit: mJ / cm 2) capable of forming an L / S pattern of 200 nm.

The results of the resolution evaluation were evaluated as &quot; Good &quot; 200 nm L / S, equal or finer patterns were formed, and the results are shown in Table 7.

[SW evaluation]

Using the resist composition solutions obtained in Examples 1 to 3 and Comparative Example 1, the presence or absence of suppression of the pattern dimension change by SW at the Exp was observed by a scanning electron microscope.

In the SW evaluation, the cross-sectional shape was observed by a cross-sectional SEM, the side was raised almost vertically, the SW was suppressed, the X side was pattern side, the SW was not suppressed, The results are shown in Table 7.

(C) Amount added Resolution SW suppression effect B-A (nm) Example 1 Negative type 2.4 ○ ○ 16 Example 2 Negative type 4 ○ ○ 10 Example 3 Negative type 6 ○ ○ 8 Comparative Example 1 Negative type 0 ○ × 65

As is clear from the results shown in Table 7, the resist composition of the present invention has an excellent effect on the suppression of the dimensional change due to resolution and SW.

From the above results, it can be seen that the use of the composition of the present invention enables formation of a fine pattern in which SW is suppressed even in the case of forming a pattern without using an antireflection film (BARC) and in the case of forming a pattern on a stepped substrate I can confirm that I can do it.

Example  4 to 6 and Comparative Example 2 of  evaluation

[Evaluation of Resolution]

The positive resist composition solutions obtained in Examples 4 to 6 and Comparative Example 2 were uniformly coated on a bare silicon wafer of 12 inches using a spinner and treated by PAB treatment at 110 캜 on a hot plate to obtain a film thickness A resist film of 280 nm was formed.

Subsequently, a KrF exposure apparatus (wavelength: 248 nm) NSR-S210 (manufactured by Nikon, NA (numerical aperture) = 0.8, sigma = 0.6) was selectively exposed through a binary mask.

Then, PEB treatment was performed at 110 DEG C for 60 seconds, paddle development was performed at 23 DEG C with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then water rinsed with pure water for 30 seconds, Lt; / RTI &gt; A resist pattern (hereinafter referred to as an L / S pattern) of 200 nm line and space (1: 1) was formed by heating at 100 캜 for 60 seconds and drying, and a scanning electron microscope , CD4000) to obtain an exposure amount Exp (sensitivity) (unit: mJ / cm 2) capable of forming an L / S pattern of 200 nm.

The resolution criteria are the same as those applied in Table 7, and the results are shown in Table 8.

[SW evaluation]

Using the resist composition solutions obtained in Examples 4 to 6 and Comparative Example 2, the presence or absence of suppression of the pattern dimension change by SW at the Exp was observed by a scanning electron microscope.

The SW evaluation criteria are the same as those applied in Table 7, and the results are shown in Table 8.

(C) Amount added Resolution SW suppression effect B-A (nm) Example 4 Positive type 4.5 ○ ○ - Example 5 Positive type 6 ○ ○ - Example 6 Positive type 7.5 ○ ○ - Comparative Example 2 Positive type 0 ○ × -

As is apparent from the results shown in Table 8, the resist composition of the present invention has an excellent effect on the suppression of the dimensional changes due to resolution and SW.

From the above results, it can be seen that the use of the composition of the present invention enables formation of a fine pattern in which SW is suppressed even in the case of forming a pattern without using an antireflection film (BARC) and in the case of forming a pattern on a stepped substrate I can confirm that I can do it.

Example  7-11 and Comparative Example  3 ~ 4 of  evaluation

[Evaluation of Resolution]

The positive resist composition solutions obtained in Examples 7 to 11 and Comparative Examples 3 and 4 were uniformly coated on a bare silicon wafer of 12 inches using a spinner and heated on a hot plate at a temperature of 110 캜 for 60 seconds for PAB And dried to form a resist film having a film thickness of 200 nm.

Subsequently, a KrF exposure apparatus (wavelength: 248 nm) NSR-S210 (Nikon Corporation, NA (numerical aperture) = 0.82, sigma = 0.83) was selectively exposed through a binary mask.

In the case of Examples 7 and 8 and Comparative Example 3, PEB treatment was performed at a temperature of 90 캜 for 60 seconds. In the case of Examples 9 to 11 and Comparative Example 4, PEB treatment was performed at a temperature of 100 캜 for 60 seconds , Followed by puddle development with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 30 seconds, followed by water rinsing with pure water for 30 seconds, and drying while being shaved. Further, the substrate was heated at 100 占 폚 for 60 seconds and dried to form a L / S pattern of 200 nm and observed with a scanning electron microscope (measurement SEM, CD4000) manufactured by Hitachi, Ltd. to form an L / S pattern of 200 nm (Unit: mJ / cm &lt; 2 &gt;). The resolution criterion is the same as the criterion applied in Table 7, and the results are shown in Table 9.

[SW evaluation]

The resist composition solutions obtained in Examples 7 to 11 and Comparative Examples 3 and 4 were used and the presence or absence of suppression of pattern dimension change by SW at the Exp was observed by a scanning electron microscope. The SW evaluation criteria are the same as those applied in Table 7, and the results are shown in Table 9. [

(C) Amount added Resolution SW suppression effect Example 7 Positive type 10 ○ ○ Example 8 Positive type 10 ○ ○ Example 9 Positive type 15 ○ ○ Example 10 Positive type 10 ○ ○ Example 11 Positive type 10 ○ ○ Comparative Example 3 Positive type 0 ○ × Comparative Example 4 Positive type 0 ○ ×

As is clear from the results shown in Table 9, the resist composition of the present invention has an excellent effect on the suppression of the dimensional change due to resolution and SW.

Example  12-16 and Comparative Example 5 of  evaluation

[Evaluation of Resolution]

On the 12-inch bare silicon wafer, the positive resist composition solutions obtained in Examples 12 to 16 and Comparative Example 5 were uniformly applied using a spinner and subjected to PAB treatment on a hot plate at a temperature of 90 캜 for 60 seconds And dried to form a resist film having a film thickness of 200 nm.

Subsequently, a KrF exposure apparatus (wavelength: 248 nm) NSR-S210 (Nikon Corporation, NA (numerical aperture) = 0.82, sigma = 0.83) was selectively exposed through a binary mask.

In the case of Examples 12 and 13 and Comparative Example 5, PEB treatment was carried out at a temperature of 95 캜 for 60 seconds. In the case of Examples 14 to 16, PEB treatment was carried out at a temperature of 100 캜 for 60 seconds, ° C in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 30 seconds, rinsed with pure water for 30 seconds, and dried while being shaved. Further, a resist pattern of 200 nm line and space (1: 1) was formed (300 nm pitch / 130 nm line, mask size of 130 nm) by heating at 100 캜 for 60 seconds and drying, and a scanning electron microscope SEM, CD4000) to obtain an exposure amount Exp (sensitivity) (unit: mJ / cm 2) capable of forming an L / S pattern of 200 nm. The resolution criteria are the same as those applied in Table 7, and the results are shown in Table 10.

[SW evaluation]

Using the resist composition solutions obtained in Examples 12 to 16 and Comparative Example 5, the presence or absence of suppression of pattern dimension change by SW at the Exp was observed by a scanning electron microscope. The SW evaluation criteria are the same as those applied in Table 7, and the results are shown in Table 10.

(C) Amount added Resolution SW suppression effect Example 12 Positive type 10 ○ ○ Example 13 Positive type 10 ○ ○ Example 14 Positive type 10 ○ ○ Example 15 Positive type 10 ○ ○ Example 16 Positive type 10 ○ ○ Comparative Example 5 Positive type 0 ○ ×

As is clear from the results shown in Table 10, the resist composition of the present invention has an excellent effect on the suppression of the dimensional change due to resolution and SW.

Example  17 to 19 and Comparative Example 6 of  evaluation

[Evaluation of Resolution]

On the 12-inch bare silicon wafer, the positive resist composition solutions obtained in Examples 17 to 19 and Comparative Example 6 were uniformly coated using a spinner and subjected to PAB treatment at a temperature of 110 DEG C for 60 seconds on a hot plate And dried to form a resist film having a film thickness of 200 nm.

Subsequently, a KrF exposure apparatus (wavelength: 248 nm) NSR-S210 (Nikon Corporation, NA (numerical aperture) = 0.82, sigma = 0.83) was selectively exposed through a binary mask.

PEB treatment was performed at a temperature of 90 캜 for 60 seconds and then puddle development with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23 캜 for 30 seconds, followed by rinsing with pure water for 30 seconds, And dried. Further, a resist pattern of 200 nm line and space (1: 1) was formed (300 nm pitch / 130 nm line, mask size of 130 nm) by heating at 100 캜 for 60 seconds and drying, and a scanning electron microscope SEM, CD4000) to obtain an exposure amount Exp (sensitivity) (unit: mJ / cm 2) capable of forming an L / S pattern of 200 nm. The resolution criteria are the same as those applied in Table 7, and the results are shown in Table 11.

[SW evaluation]

Using the resist composition solutions obtained in Examples 17 to 19 and Comparative Example 6, the suppression of the pattern dimension change by SW at the Exp was observed by a scanning electron microscope. The SW evaluation criteria are the same as those applied in Table 7, and the results are shown in Table 11.

(C) Amount added Resolution SW suppression effect Example 17 Positive type 2 ○ ○ Example 18 Positive type 5 ○ ○ Example 19 Positive type 10 ○ ○ Comparative Example 6 Positive type 0 ○ ×

As is apparent from the results shown in Table 11, the resist composition of the present invention has an excellent effect in terms of the resolution and the suppression of pattern dimensional changes due to SW.

Example  20 ~ 33 of  evaluation

[Evaluation of Resolution]

The resist composition solutions obtained in Examples 20 to 33 were applied uniformly on a 12-inch silicon wafer treated with HMDS (hexamethyldisiloxane) using a spinner and pre-baked on a hot plate at 90 DEG C for 60 seconds And dried to form a resist film having a film thickness of 240 nm.

Subsequently, a KrF exposure apparatus (wavelength: 248 nm) NSR-S210 (Nikon Corporation, NA (numerical aperture) = 0.82, sigma = 0.83) was selectively exposed through a binary mask.

Then, PEB treatment was performed at 110 占 폚 for 60 seconds, puddle development was performed at 23 占 폚 in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then water rinsing was performed using pure water for 30 seconds, Lt; / RTI &gt; Further, post-baking and drying at 110 占 폚 for 60 seconds to form an L / S pattern (target CD: 140 nm line / 425 nm pitch) was observed with a scanning electron microscope (measurement SEM, CD4000) An exposure amount Exp (sensitivity) (unit: mJ / cm 2) capable of forming an L / S pattern of nm was obtained. The resolution criteria are the same as those applied in Table 7, and the results are shown in Table 12.

[SW evaluation]

Using the resist composition solution obtained in the above Examples 20 to 33, the presence or absence of suppression of the pattern dimension change by SW at the Exp was observed by a scanning electron microscope. The SW evaluation criteria are the same as those applied in Table 7, and the results are shown in Table 12.

(C) Amount added Resolution SW suppression effect Example 20 Negative 8.26 ○ ○ Example 21 Negative 2.4 ○ ○ Example 22 Negative 4 ○ ○ Example 23 Negative 6.25 ○ ○ Example 24 Negative 2.4 ○ ○ Example 25 Negative 4 ○ ○ Example 26 Negative 6.25 ○ ○ Example 27 Negative 10.24 ○ ○ Example 28 Positive type 4.5 ○ ○ Example 29 Positive type 6 ○ ○ Example 30 Positive type 7.5 ○ ○ Example 31 Positive type 4.5 ○ ○ Example 32 Positive type 6 ○ ○ Example 33 Positive type 7.5 ○ ○

As is apparent from the results shown in Table 12, the resist composition of the present invention has an excellent effect in terms of suppressing the change of the pattern dimension due to the resolution and SW.

Claims (11)

(C) represented by the following formula (1): (A) a resin component (A) in which the solubility in a developer is changed by the action of an acid, an acid generator component .

Equation (1)
[Wherein,
R ₁ and R ₂ are each independently a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a hydroxyl group, and one -CH ₂ - of the hydrocarbon groups or two or more non-adjacent -CH ₂ - _{O-, -S-, -NH-, -NR 3} -, -C (O) -, -OC (O) -, -OC (O) O-, -SO-, -SO 2 -, -CONH- , -CONR ₃ -, -OC (O) NH- or -OC (O) NR ₃ -, wherein R ₃ is a hydrocarbon group of 1 to 10 carbon atoms.
n1, n2, m1 and m2 are each independently an integer of 0 to 5, and n1 + m1 and n2 + m2 do not both exceed 5.] The method according to claim 1,
M1 = m2 = 1 in the compound (C) having radiation absorbing ability represented by the formula (1). The method according to claim 1,
In the compound (C) having radiation-absorbing ability represented by the formula (1), R ₁ and R ₂ are each independently a hydrocarbon group of 1 to 5 carbon atoms substituted with a hydroxyl group, and one of -CH ₂ - And at least _two -CH ₂ - not adjacent to each other are replaced with -O-, -S-, or -NH-. The method according to claim 1,
Wherein the resin component (A) contains a structural unit (a1) derived from hydroxystyrene represented by the following formula (a1-1).

[Wherein,
R is a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen atom.
R ⁶ is a hydrocarbon group of 1 to 10 carbon atoms.
p is an integer of 1 to 3;
q is an integer of 0 to 2.] The method according to claim 1,
Wherein the resin component (A) contains a polymer compound (A-2) having a structural unit (a4) derived from an acrylate ester represented by the following formula (a4-1) or (a4-2).

[Wherein,
R is a hydrocarbon group of 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen atom.
Va ¹ is a divalent hydrocarbon group of 1 to 30 carbon atoms which may have an ether bond, a urethane bond or an amide bond.
n _a1 is an integer of 0 to 2;
Ra ¹ is an acid dissociable group.
n _a2 is an integer of 1 to 3;
Wa ¹ is an n _a2 +1 -valent hydrocarbon group having 1 to 30 carbon atoms.] The method according to claim 1,
Wherein the resin component (A) is a resin whose alkaline solubility is increased by the action of an acid. The method according to claim 1,
Wherein the resin component (A) is an alkali-soluble resin and further comprises a crosslinking component (D). The method according to claim 1,
And further contains a nitrogen-containing organic compound (E). The method according to claim 1,
A resist composition for a thin film implantation process. The method according to claim 1,
A resist composition used for forming a resist pattern on a stepped substrate. A resist film is formed on a substrate by using the resist composition as described in any one of claims 1 to 10. The resist film is subjected to selective exposure treatment and then subjected to development treatment to form a resist pattern Wherein the resist pattern is a resist pattern.