JP4406591B2 - Resist composition and pattern forming method using the resist composition - Google Patents

Description

  The present invention relates to a resist composition whose properties change upon reaction with irradiation of actinic rays or radiation, and a pattern forming method using the resist composition. More specifically, semiconductor manufacturing processes such as IC, manufacturing of circuit boards such as liquid crystal and thermal head, other photofabrication processes, lithographic printing plates, resist compositions used in acid curable compositions, and the resist compositions The present invention relates to a pattern forming method using

  The chemically amplified resist composition generates an acid in the exposed area by irradiation with actinic rays or radiation such as far ultraviolet light, and a reaction solution using the acid as a catalyst to develop a developing solution for the irradiated and non-irradiated areas of the active light or radiation It is a pattern forming material that changes the solubility in the substrate and forms a pattern on the substrate.

  When a KrF excimer laser is used as an exposure light source, a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption mainly in the 248 nm region is used as a main component. A pattern is formed, which is a better system than the conventional naphthoquinone diazide / novolak resin system.

On the other hand, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group exhibits a large absorption in the 193 nm region. It wasn't.
For this reason, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed.

  Various compounds have also been found for acid generators that are main constituents of chemically amplified resist compositions. For example, compounds that generate fluorine-substituted alkanesulfonic acids upon irradiation with actinic rays or radiation (for example, patent documents) 1) and perfluoroalkanesulfonic acid sulfonium salts (for example, see Patent Document 2).

  However, there are still many insufficient points, and improvement in PEB temperature dependency and density dependency, sensitivity in EUV light exposure, and improvement in dissolution contrast are desired.

JP 2002-268224 A JP 2000-275845 A

  Accordingly, an object of the present invention is to provide a resist composition having improved PEB temperature dependency and density dependency, improved sensitivity and dissolution contrast in EUV light exposure, and a pattern forming method using the resist composition. There is to do.

  The above problems have been solved by a resist composition having the following constitution and a pattern forming method using the resist composition.

(1) (A) containing a compound that generates pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid upon irradiation with actinic rays or radiation, and (F) a basic compound represented by the following general formula (N). A resist composition.

In general formula (N), R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
Two or more of R ^{250 to} R ²⁵² may be bonded to form an alkylene group to form a ring. The alkylene group may have a hetero atom.

(2) (A) compounds of the component is at least selected from the sulfonium salt compound of pentafluorobenzene ethanesulfonic acid or perfluoro sulfonic acid or iodonium salt compound and an ester compound of pentafluorobenzene ethanesulfonic acid or perfluoro sulfonic acid The resist composition as described in (1), which is a kind of compound.

( 3 ) The resist composition as described in (1) or (2) , wherein the compound of component (F) is at least one compound selected from an aliphatic amine compound and an aniline compound.

(4) The resist composition according to any one of (1) to (3), wherein the compound of component (A) is a compound represented by the following general formula (A1).

In general formula (A1),
  R _201a , R _202a And R _203a Each independently represents an organic group. R _201a , R _202a as well as
R _203a Two of these may combine to form a ring structure.
  Xa ^- Is -SO of pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid _Three It represents a sulfonate anion from which a hydrogen atom of H has been removed.
  (5) In the general formula (A1), R _201a , R _202a And R _203a (2), wherein two of these are bonded to form an alkylene group.
(6) In the general formula (A1), R _201a , R _202a And R _203a At least one of these is an aryl group, The resist composition as described in (4) or (5) characterized by the above-mentioned.

( 7 ) The positive type as described in any one of (1) to ( 6 ) above, further comprising (B) a resin that decomposes by the action of an acid and increases the solubility in an alkaline developer. Resist composition.

( 8 ) The above (1), further comprising (D) a resin soluble in an alkali developer and (E) an acid crosslinking agent that crosslinks the resin soluble in the alkali developer by the action of an acid. ) To ( 6 ), the negative resist composition according to any one of the above.

( 9 ) The positive resist composition as described in ( 7 ) above, wherein the resin that decomposes by the action of an acid and has increased solubility in an alkaline developer has a hydroxystyrene structural unit.

一般式（ＡＩ）中、
Ｒb ₀ は、水素原子、ハロゲン原子、又は炭素数１〜４のアルキル基を表す。
Ａbは、単結合、アルキレン基、単環または多環の脂環炭化水素構造を有する２価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又はこれらを組み合わせた２価の基を表す。
Ｖは、下記一般式（ＬＣ１−１）〜（ＬＣ１−１６）のうちのいずれかで示される基を表す。

ここにおいて、Ｒｂ _２ は、置換基を表す。
ｎ _２ は、０〜４の整数を表す。ｎ _２ が、２以上の時、複数存在するＲｂ _２ は、同一でも異なっていてもよく、また、複数存在するＲｂ _２ 同士が結合して環を形成してもよい。
（１２） （１）〜（１１）のいずれかに記載のレジスト組成物により、レジスト膜を形成し、該レジスト膜を露光、現像する工程を含むことを特徴とするパターン形成方法。
（１３） （１）〜（１１）のいずれかに記載のレジスト組成物により、レジスト膜を形成し、該レジスト膜を液浸露光、現像する工程を含むことを特徴とするパターン形成方法。 ( 10 ) The resin according to ( 7 ), wherein the resin that decomposes by the action of an acid and has increased solubility in an alkali developer has a repeating unit having a monocyclic or polycyclic hydrocarbon structure. A positive resist composition.
(11) The positive electrode as described in (10) above, wherein the resin that is decomposed by the action of an acid and has increased solubility in an alkaline developer has a repeating unit represented by the following general formula (AI): Type resist composition.

In general formula (AI),
Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express.
V represents a group represented by any one of the following general formulas (LC1-1) to (LC1-16).

Here, Rb ₂ represents a substituent.
n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to form a ring.
(12) A pattern forming method comprising a step of forming a resist film from the resist composition according to any one of (1) to (11), and exposing and developing the resist film.
(13) A pattern forming method comprising a step of forming a resist film from the resist composition according to any one of (1) to (11), and subjecting the resist film to immersion exposure and development.

The preferred embodiments of the present invention will be further described below.
( 14 ) The above-mentioned ( 7 ) and (9) to (11), wherein the resin which is decomposed by the action of an acid and has increased solubility in an alkaline developer has a repeating unit having an alcoholic hydroxyl group . The positive resist composition according to any one of the above.

( 15 ) The positive unit as described in ( 14 ) above, wherein the repeating unit having an alcoholic hydroxyl group is a repeating unit having at least one selected from a monohydroxyadamantane structure, a dihydroxyadamantane structure or a trihydroxyadamantane structure. Type resist composition.

( 16 ) The above-mentioned (7), (9), (10), wherein the resin that is decomposed by the action of an acid and has increased solubility in an alkaline developer is a resin having a repeating unit having a lactone structure. ), (14) and (15) .

( 17 ) A resin that decomposes by the action of an acid and has increased solubility in an alkaline developer is a resin having a repeating unit of at least one methacrylate ester and a repeating unit of at least one acrylic ester. The positive resist composition as described in any one of (7), (9) to (11) and (14) to (16) above,

( 18 ) The positive type as described in ( 7 ) above, wherein the resin which decomposes by the action of an acid and has increased solubility in an alkaline developer has a fluorine atom in at least one of the main chain and the side chain. Resist composition.

( 19 ) The positive resist composition as described in ( 18 ) above, wherein the resin having a fluorine atom in at least one of the main chain or the side chain has a hexafluoro-2-propanol structure.

( 20 ) (C) The above (7), (9) to (11), comprising a dissolution inhibiting compound having a molecular weight of 3000 or less, which decomposes by the action of an acid and increases the solubility in an alkaline developer. ) And the positive resist composition according to any one of (14) to (19) .

( 21 ) Further described in any one of (7), (9) to (11) and (14) to (20) above, further comprising (G) fluorine and / or a silicon-based surfactant. A positive resist composition.

( 22 ) Repeating resin selected from 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate, which is decomposed by the action of an acid and has increased solubility in an alkaline developer Any one of the above (7), (20) and (21) , which has at least one type of unit, at least one type of repeating unit having a lactone structure, and at least one type of repeating unit having 1 to 3 hydroxyl groups The positive resist composition as described.

( 23 ) The resin (7), (9) to (11), wherein the resin that decomposes by the action of an acid and has increased solubility in an alkaline developer has a repeating unit having a carboxy group. The positive resist composition according to any one of 14) to (22) .

( 24 ) Repeating resin selected from 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate, wherein the resin decomposes by the action of an acid and increases the solubility in an alkaline developer. (7) having at least one unit and at least one repeating unit having a hydroxystyrene structure
), (20), (21) and the positive resist composition according to any one of (23) .

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resist composition with improved PEB temperature dependency and density dependency, improved sensitivity and dissolution contrast in EUV light exposure, and a pattern forming method using the resist composition. .

Hereinafter, the present invention will be described in detail.
In addition, although this invention is invention concerning said (1)-(24), the other matter was also described for reference.
In addition, in the description of a group (atomic group) in this specification, the description which does not describe substituted and unsubstituted includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The positive resist composition of the present invention comprises a compound (A) that generates pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid upon irradiation with actinic rays or radiation, and a basic compound (F) represented by the general formula (N) And a resin (B) that decomposes by the action of an acid and increases the solubility in an alkali developer, and further decomposes by the action of an acid to increase the solubility in an alkali developer as necessary. A dissolution inhibiting compound (C) having a molecular weight of 3000 or less is contained.

The negative resist composition of the present invention comprises a compound that generates pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid upon irradiation with actinic rays or radiation, a basic compound (F) represented by the general formula (N), an alkali A resin (D) soluble in the developer and an acid crosslinking agent (E) that crosslinks with the resin soluble in the alkali developer by the action of an acid are contained.

[1] (A) Compound upon irradiation with actinic rays or radiation to generate a pentafluorobenzenesulfonic ethanesulfonic acid or perfluoro sulfonic acid resist composition of the present invention, pentafluorobenzene ethanesulfonic acid or par upon irradiation with actinic rays or radiation Other compounds that contain fluoropropanesulfonic acid (also referred to as “compound (A)”) but generate an acid upon irradiation with actinic rays or radiation are also described for reference.

  Examples of the fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms include 1,1,2,3,3,3-hexafluoropropanesulfonic acid, 1,1,1,3,3,3-hexafluoro- Examples include 2-propanesulfonic acid, 2,2,2-trifluoroethanesulfonic acid, perfluoroethanesulfonic acid, perfluoro-n-propanesulfonic acid, and perfluoroisopropanesulfonic acid. More preferred are sulfonic acids in which the α-position of the sulfonic acid is substituted with a fluorine atom, and more preferred are perfluoroethanesulfonic acid, perfluoro-n-propanesulfonic acid, and perfluoroisopropanesulfonic acid. Particularly preferred is perfluoro-n-propanesulfonic acid.

  Examples of the compound that generates a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms by irradiation with actinic rays or radiation include a fluorine-substituted sulfonium salt compound or iodonium salt compound of an alkanesulfonic acid having 2 or 3 carbon atoms, and A fluorine-substituted ester compound of alkanesulfonic acid having 2 or 3 carbon atoms is preferable, and a compound represented by any one of the following general formulas (A1) to (A5) is more preferable.

The compound represented by the general formula (A1) or (A2) is a compound in which Xa- is an anion of a C2 or C3 alkanesulfonic acid substituted with fluorine, and represented by the general formulas (A3) to (A5) The compound represented is a compound in which X _1a is fluorine-substituted, and the hydrogen atom of —SO ₃ H of an alkanesulfonic acid having 2 or 3 carbon atoms is removed and bonded as a monovalent group.

In the general formula (A1), R _201a , R _202a and R _203a each independently represents an organic group.
Xa ⁻ represents a sulfonate anion from which a hydrogen atom of —SO ₃ H of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms is removed.

The carbon number of the organic group as _R201a , _R202a and _R203a is generally 1-30, preferably 1-20.
Two of R _{201a to} R _203a may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group.
Examples of the group formed by combining two _{members out} of R _{201a to} R _203a include an alkylene group (eg, butylene group, pentylene group).
Specific examples of the organic group as R _201a , R _202a and R _203a include corresponding groups in the compounds (A1a), (A1b) and (A1c) described later.

In addition, the compound which has two or more structures represented by general formula (A1) may be sufficient. For example, the general formula at least one of R _201a to R _203a of a compound represented by (A1) is at least one bond with structure of R _201a to R _203a of another compound represented by formula (A1) It may be a compound.
More preferred components (A1) include compounds (A1a), (A1b), and (A1c) described below.

Compound (A1a) is at least one is an aryl group R _201a to R _203a in formula (A1), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R _{201a to} R _203a may be an aryl group, or a part of R _{201a to} R _203a may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, and compounds in which the alkyl group in these compounds is a cycloalkyl group.
Examples of the aryl group of the arylsulfonium compound include an aryl group composed of a hydrocarbon and a heteroaryl group containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom. The aryl group composed of hydrocarbon is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, and a thiophene group, and an indole group is preferable. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R _{201a to} R _203a may have include a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group Examples thereof include a group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) can be further mentioned as a substituent.

Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, particularly preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201a to} R _203a or may be substituted with all three. Moreover, about an aryl group, an alkyl group (for example, C1-C15) can be mentioned as a substituent further. The substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (A1b) will be described.
The compound (A1b) is a compound in the case where R _{201a to} R _203a in the general formula (A1) each independently represents an organic group not containing an aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R _201a to R _203a generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201a to} R _203a are each independently preferably an alkyl group (particularly an alkoxycarbonylmethyl group as a substituted alkyl group), a cycloalkyl group, a linear, branched or cyclic group which may have a double bond in the chain. It is an oxoalkyl group, an allyl group or a vinyl group, more preferably a linear, branched or cyclic 2-oxoalkyl group, and most preferably a linear or branched 2-oxoalkyl group.
The alkyl group as R _{201a to} R _203a may be linear or branched, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group, pentyl group).
The cycloalkyl group as R _201a to R _203a may preferably be mentioned a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).

2-oxoalkyl group as R _201a to R _203a may be linear, branched, or cyclic, may have a double bond. Preferable examples include a group having> C═O at the 2-position of the alkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as the substituted alkyl group for R _{201a to} R _203a is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group). Can do.
Each group as R _201a to R _203a is a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, may be substituted by nitro group.

  The compound (A1c) is a compound represented by the following general formula (A1c), and is a compound having an arylacylsulfonium salt structure.

In general formula (A1c):
_R213 represents an aryl group, which may have a substituent, and is preferably a phenyl group or a naphthyl group. Examples of the substituent which may be possessed by the aryl group R _213, e.g., an alkyl group, an alkoxy group, an acyl group, a nitro group, a hydroxyl group, an alkoxycarbonyl group and a carboxy group.
R ₂₁₄ and R ₂₁₅ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Y ₂₀₁ and Y ₂₀₂ each independently represents an alkyl group, a cycloalkyl group, an aryl group or a vinyl group.
Xa ⁻ represents a sulfonate anion from which a hydrogen atom of —SO ₃ H of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms is removed.

R ₂₁₃ and R ₂₁₄ may be bonded to form a ring structure, R ₂₁₄ and R ₂₁₅ may be bonded to form a ring structure, and Y ₂₀₁ and Y ₂₀₂ are bonded to each other. To form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond. A group formed by combining R ₂₁₃ and R ₂₁₄ , a group formed by combining R ₂₁₄ and R _215, and a group formed by combining Y ₂₀₁ and Y ₂₀₂ , respectively, are a butylene group. And a pentylene group.

The alkyl group as R ₂₁₄ and R ₂₁₅ is a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group). Is preferred.
The cycloalkyl group as R ₂₁₄ and R ₂₁₅ is preferably a cycloalkyl group having 3 to 20 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclohexyl group).

The alkyl group as Y ₂₀₁ and Y ₂₀₂ may have a substituent, may have an oxo group in the alkylene chain, and is a linear or branched alkyl group having 1 to 20 carbon atoms (for example, (Methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group) are preferred.
Examples of the alkyl group having a substituent include an alkoxycarbonylalkyl group and a carboxyalkyl group, and examples of the alkyl group having an oxo group include a 2-oxoalkyl group.

Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group.
The alkoxycarbonyl group in the alkoxycarbonylalkyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.

The cycloalkyl group as Y ₂₀₁ and Y ₂₀₂ is preferably a cycloalkyl group having 3 to 20 carbon atoms (for example, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group), and has a substituent similarly to the above alkyl group. The alkylene chain may have an oxo group.

The aryl group as Y ₂₀₁ and Y ₂₀₂ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

Each group as R ₂₁₄ , R ₂₁₅ , Y ₂₀₁ and Y ₂₀₂ may have a substituent, and examples of the substituent include an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, carbon (Chemical formula 1-15), an alkoxycarbonyl group (C2-C20), a carboxyl group, a halogen atom, a hydroxyl group, a phenylthio group, etc. can be mentioned. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) can be further mentioned as a substituent.

Y ₂₀₁ and Y ₂₀₂ are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably an alkyl group or cycloalkyl group having 4 to 16, and more preferably 4 to 12.
In addition, at least one of R ₂₁₄ or ₂₁₅ is preferably an alkyl group or a cycloalkyl group, and more preferably both R ₂₁₄ and R ₂₁₅ are an alkyl group or a cycloalkyl group.

In general formula (A2),
_R204a and _R205a each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Xa ⁻ represents a sulfonate anion from which a hydrogen atom of —SO ₃ H of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms is removed.
The aryl group for R _204a and R _205a is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
As the alkyl group and cycloalkyl group as _R204a and _R205a , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), Examples thereof include a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

In general formula (A3),
A represents an alkylene group, an alkenylene group or an arylene group.
X _1a represents a monovalent group formed by removing a —SO ₃ H hydrogen atom of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms.

In general formula (A4),
R _208a represents an alkyl group, a cycloalkyl group, or an aryl group.
R _209a represents an alkyl group, a cycloalkyl group, a cyano group, or an alkoxycarbonyl group, preferably a halogen-substituted alkyl group, a cycloalkyl group, or a cyano group.
The alkyl group and cycloalkyl group as R _209a may be an oxoalkyl group or oxocycloalkyl group having an oxo group in the alkylene chain.
X _1a represents a monovalent group formed by removing a —SO ₃ H hydrogen atom of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms.

In general formula (A5),
R _210a and R _211a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyano group, a nitro group or an alkoxycarbonyl group, preferably a halogen-substituted alkyl group or a cycloalkyl group, a nitro group or a cyano group. is there.
R _212a represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group.
X _1a represents a monovalent group formed by removing a —SO ₃ H hydrogen atom of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms.

  Each group in the above general formulas (A3) to (A5) may have a substituent. Examples of the substituent include an aryl group (for example, 6 to 15 carbon atoms) and an alkoxy group (for example, 1 carbon atom). -15), halogen atoms, hydroxyl groups, phenylthio groups and the like. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) can be further mentioned as a substituent.

  Preferably, it is a compound represented by general formula (A1), More preferably, it is a compound represented by general formula (A1a)-(A1c).

  Specific examples of the preferred compound (A) are given below.

  The content of the compound (A) in the resist composition (solid content) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and 1 to 7% by mass. Even more preferably.

(Combination acid generator)
In the present invention, in addition to the compound (A), a compound (acid generator) that generates an acid upon irradiation with actinic rays or radiation may be used in combination.

The addition amount of other acid generators that can be used in combination is usually 100/0 to 20/80, preferably 100/0 to 40/60, and more preferably in molar ratio (compound (A) / other acid generators). Is 100/0 to 50/50.
Examples of such an acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or an actinic ray or radiation used for a microresist. A known compound that generates an acid by irradiation and a mixture thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62-153853, The compounds described in JP-A 63-146029 can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation that may be used in combination, compounds represented by the following general formula (ZI), (ZII), or (ZIII) can be exemplified.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ⁴⁻ , PF ⁶⁻ , SbF ^{6− and the} like. An organic anion having a carbon atom is preferable.

  Preferable organic anions include organic anions represented by the following general formula.

In the above organic anion,
Rc ₁ represents an organic group.
Examples of the organic group for Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, an aryl group, or a plurality thereof, which may be substituted, is a single bond, —O—, —CO ₂ —. , —S—, —SO ₃ —, —SO ₂ N (Rd ₁ ) — and the like.
Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group.
Preferred examples of the organic group for Rc ₃ , Rc ₄ , and Rc ₅ include the same organic groups as those for Rb ₁ , and most preferably a perfluoroalkyl group having 1 to 4 carbon atoms.
Rc ₃ and Rc ₄ may combine to form a ring. Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred.
The organic group of Rc ₁ and Rc _{3 to} Rc ₅ is most preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
It is also possible to form the two members ring structure of the R ₂₀₁ to R _203, an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, most preferably They are a C1-C4 alkyl group and a C1-C4 alkoxy group. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, a linear, branched, cyclic 2-oxoalkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2 -An oxoalkyl group, an alkoxycarbonylmethyl group, and most preferably a linear, branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, e.g., methyl group, ethyl group, propyl Group, butyl group, pentyl group and the like. The alkyl group is particularly preferably an alkoxycarbonylmethyl group.
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cycloalkyl group having 3 to 10 carbon atoms, e.g., cyclopentyl, cyclohexyl group and a norbornyl group.
The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear, branched or cyclic, and is preferably a group having> C═O at the 2-position of the above alkyl group or cycloalkyl group Can be mentioned.
The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), an alkoxycarbonyl group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an allyl group, or a vinyl group.
Any two or more of R _{1c to} R _5c , R _6c and R _7c , and Rx and Ry may be bonded to each other to form a ring structure, which is an oxygen atom, sulfur atom, ester A bond or an amide bond may be included. Any two or more of R _1c to R _5c, as the group R _6c and R _7c, and the Rx and Ry are formed in combination, there can be mentioned a butylene group and a pentylene group.
Z _c ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of X ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be linear or branched, for example, a linear and branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group.
Preferred examples of the cycloalkyl group as R _{1c to} R _7c include a cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopentyl group and a cyclohexyl group.
The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).
Preferably, any one of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _1c to R _5c is 2 ~ 15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl groups and cycloalkyl groups as R _{1c to} R _7c . The alkyl group as R _x and R _y is particularly preferably an alkoxycarbonylmethyl group.
Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _5c .
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _{1c to} R _5c .

R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

Formula (ZII), (ZIII) in, R ₂₀₄ to R ₂₀₇ each independently organic optionally substituted aryl group, an alkyl group or a substituted group which may have a substituent Represents an optionally substituted cycloalkyl group.
The aryl group of R ₂₀₄ to R _207, a phenyl group, a naphthyl group, more preferably a phenyl group.
The alkyl group as R ₂₀₄ to R ₂₀₇ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, e.g., methyl group, ethyl group, propyl Group, butyl group, pentyl group and the like.
The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably a cycloalkyl group having 3 to 10 carbon atoms, e.g., cyclopentyl, cyclohexyl group and a norbornyl group.
The R ₂₀₄ to R ₂₀₇ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.
X ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of X ^{− in} formula (I).

  Examples of the compound capable of decomposing upon irradiation with actinic rays or radiation that may be used in combination include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI), Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.
R ₂₀₆ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.
R ₂₀₇ and R ₂₀₈ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a cyano group.
A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group.

  Of the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by general formulas (ZI) to (ZIII) are more preferable.

  Among the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, examples of particularly preferable compounds are listed below.

[2] (B) Resin that decomposes by the action of an acid and increases the solubility in an alkaline developer (hereinafter also referred to as “component (B)”)
Resins that are decomposed by the acid used in the positive resist composition of the present invention and have increased solubility in an alkaline developer are acid in the main chain or side chain of the resin, or both the main chain and side chain. It is a resin having a group capable of decomposing (hereinafter also referred to as “acid-decomposable group”). Among these, a resin having a group capable of decomposing with an acid in the side chain is more preferable.

A group preferable as a group that can be decomposed by an acid is a group in which a hydrogen atom of a —COOH group or —OH group is substituted with a group capable of leaving with an acid.
In the present invention, the acid-decomposable group is preferably an acetal group or a tertiary ester group.

  The base resin in the case where these acid-decomposable groups are bonded as side chains is an alkali-soluble resin having —OH or —COOH groups in the side chains. For example, the alkali-soluble resin mentioned later can be mentioned.

  The alkali dissolution rate of these alkali-soluble resins is preferably 170 A / second or more as measured with 0.261 N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 A / second or more (A is angstrom).

  From this point of view, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene). Hydroxystyrene structural units such as a part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogenated novolak resin, etc. An alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

  Preferred examples of the repeating unit having an acid-decomposable group in the present invention include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, (meth) acrylic acid tertiary alkyl ester, and the like. Alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate are more preferred.

  Component (B) used in the present invention is decomposed with an acid into an alkali-soluble resin, as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259 and the like. It is possible to obtain an alkali-soluble resin monomer having a group capable of being decomposed or reacting with an acid-decomposable group by copolymerization with various monomers.

When the positive resist composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light (EUV, etc.) having a wavelength of 50 nm or less, the resin of component (B) contains hydroxystyrene repeating units. It is preferable to have. More preferably, hydroxystyrene / hydroxystyrene copolymer protected with an acid-decomposable group and hydroxystyrene / (meth) acrylic acid tertiary alkyl ester are preferred.
Specific examples of the component (B) used in the present invention are shown below, but the present invention is not limited thereto.

  In the above specific example, tBu represents a t-butyl group.

  The content of the group that can be decomposed by an acid is determined by the number of groups (B) that can be decomposed by an acid in the resin and the number of alkali-soluble groups that are not protected by a group capable of leaving by an acid (S). B + S). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  When irradiating the positive resist composition of the present invention with ArF excimer laser light, the resin of component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure, and is decomposed by the action of an acid. A resin that increases the solubility in an alkali developer is preferred.

As a resin that has a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposes by the action of an acid, and increases its solubility in an alkaline developer (hereinafter also referred to as “alicyclic hydrocarbon-based acid-decomposable resin”) , At least selected from the group consisting of repeating units having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pV) and repeating units represented by the following general formula (II-AB) A resin having one kind is preferred.

In general formulas (pI) to (pV),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (II-AB),
R ₁₁ ′ and R ₁₂ ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

  The general formula (II-AB) is more preferably the following general formula (II-AB1) or general formula (II-AB2).

In general formulas (II-AB1) and (II-AB2),
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —XA ′. -R ₁₇ ', an alkyl group or a cycloalkyl group.
Wherein, R ₅ represents an alkyl group, a cycloalkyl group or a group having a lactone structure.
X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.
A ′ represents a single bond or a divalent linking group.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or a group having a lactone structure.
R ₆ represents an alkyl group or a cycloalkyl group.
Further, at least two of R ₁₃ ′ to R ₁₆ ′ may be bonded to form a ring.
n represents 0 or 1.

In the general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. , N-butyl group, sec-butyl group, t-butyl group and the like.

The cycloalkyl group represented by R _{12 to} R ₂₅ or the cycloalkyl group formed by Z and the carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These cycloalkyl groups may have a substituent.

  Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group, and a tricyclodecanyl group.

These alkyl groups and cycloalkyl groups may further have a substituent. As further substituents for alkyl groups and cycloalkyl groups, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (2 to 2 carbon atoms). 6). The above alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have a substituent. Examples of the substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

  The structures represented by the general formulas (pI) to (pV) in the resin can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

  Specific examples include a structure in which a hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, or a thiol group is substituted with a structure represented by the general formulas (pI) to (PV), preferably a carboxylic acid Group, the hydrogen atom of a sulfonic acid group is the structure substituted by the structure represented by general formula (pI)-(PV).

  As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (pI) to (pV), a repeating unit represented by the following general formula (pA) is preferable.

In the general formula (pA), R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, or a combination of two or more groups. Represents. A single bond is preferable.
Rp1 represents any one of the general formulas (pI) to (pV).

  The repeating unit represented by the general formula (pA) is most preferably a repeating unit of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  Specific examples of the repeating unit represented by the general formula (pA) are shown below.

In the above structural formulas, Rx represents H, CH ₃ , CF ₃ or CH ₂ OH, and Rxa and Rxb each independently represents an alkyl group having 1 to 4 carbon atoms.

In the general formula (II-AB), examples of the halogen atom represented by R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

As the alkyl group for R ₁₁ ′ and R ₁₂ ′, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, linear group Or a branched butyl group, pentyl group, hexyl group, heptyl group, etc. are mentioned.

  The atomic group for forming the alicyclic structure of Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in a resin, and among them, a bridged type alicyclic group. An atomic group for forming a bridged alicyclic structure forming a cyclic hydrocarbon repeating unit is preferred.

As the skeleton of alicyclic hydrocarbon formed are the same as those of the cycloalkyl group in R ₁₂ to R ₂₅ in formulas (pI) ~ (pVI).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2).

  In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the group decomposed by the action of an acid has a partial structure containing the alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pV). It can be contained in at least one kind of repeating unit among the repeating unit having, the repeating unit represented by formula (II-AB), and the repeating unit of the copolymerization component described later.

Various substituents of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or the general formula (II-AB2) are atomic groups for forming an alicyclic structure in the general formula (II-AB). It can also be a substituent of the atomic group Z for forming a bridged alicyclic structure.

  Specific examples of the repeating unit represented by the general formula (II-AB1) or (II-AB2) include the following specific examples, but the present invention is not limited to these specific examples.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having a lactone group. As the lactone group, any group having a lactone structure can be used, but a group having a 5- to 7-membered ring lactone structure is preferred, and a bicyclo structure or spiro is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed to form a structure are preferred. The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). . Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and a specific lactone structure is used. This improves line edge roughness and development defects.

  The lactone structure moiety may or may not have a substituent (Rb2). As preferred substituents (Rb2), an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, Examples thereof include a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb2s may be the same or different, and a plurality of Rb2s may be bonded to form a ring.

As the repeating unit having a group having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-16), R _{13 in the} general formula (II-AB1) or (II-AB2) is used. A group having a group represented by general formula (LC1-1) to (LC1-16) in at least one of 'to R ₁₆ ' (for example, R _{5 of} -COOR ₅ is represented by formulas (LC1-1) to ( And a repeating unit represented by the following general formula (AI).

In general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group for Rb ₀ include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. The alkyl group for Rb ₀ may have a substituent. Preferable substituents that the alkyl group of Rb ₀ may have include, for example, a hydroxyl group and a halogen atom.

Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.

Ab is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express. Preferably, it is a linking group represented by a single bond or -Ab ₁ -CO _2- .
Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexyl residue, an adamantyl residue, or a norbornyl residue.

  V represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).

The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
Specific examples of the repeating unit having a group having a lactone structure are given below, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. This improves the substrate adhesion and developer compatibility. The polar group is preferably a hydroxyl group or a cyano group.
Examples of the alicyclic hydrocarbon structure substituted with a polar group include structures represented by the following general formula (VIIa) or (VIIb).

In the general formula _{(VIIa), R 2 c~R 4} c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom, more preferably _two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. It is.

  The group represented by the general formula (VIIa) is preferably a dihydroxy body or a monohydroxy body, and more preferably a dihydroxy body.

The repeating unit having a group represented by the general formula (VIIa) or (VIIb) includes at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2). Having the group represented by the above general formula (VIIa) or (VIIb) (for example, R _{5 in} —COOR ₅ represents a group represented by the general formula (VIIa) or (VIIb)), or the following general group Mention may be made of the repeating units of the formula (AIIa) or (AIIb).

In the general formulas (AIIa) and (AIIb), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c have the same meanings as in R ₂ c to R ₄ c in formula (VIIa).

  Specific examples of the repeating unit having an alicyclic hydrocarbon structure substituted with a polar group represented by the general formula (AIIa) or (AIIb) will be given below, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may have a repeating unit represented by the following general formula (VIII).

In General Formula (VIII), Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having an alkali-soluble group, and more preferably has a repeating unit having a carboxyl group. By having this, the resolution in contact hole applications increases. The repeating unit having a carboxyl group includes a repeating unit in which a carboxyl group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a carboxyl group in the main chain of the resin through a linking group. Any of the bonded repeating units is preferable, and the linking group may have a monocyclic or polycyclic hydrocarbon structure. Most preferred are acrylic acid and methacrylic acid.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may have a repeating unit having 1 to 3 groups represented by the following general formula (F1). This improves line edge roughness performance.

In general formula (F1), R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group, or an alkoxycarbonyl group).

The alkyl group of R _{50 to} R ₅₅ may be substituted with a halogen atom such as a fluorine atom, a cyano group, etc., preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group or a trifluoromethyl group. be able to.
R _{50 to} R ₅₅ are preferably all fluorine atoms.

  Examples of the organic group represented by Rx include an acid-decomposable protective group and an optionally substituted alkyl group, cycloalkyl group, acyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylmethyl group, alkoxymethyl group. , 1-alkoxyethyl group is preferable.

  Preferred examples of the repeating unit having a group represented by the general formula (F1) include a repeating unit represented by the following general formula (F2).

In General Formula (F2), Rx represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rx may have include a hydroxyl group and a halogen atom.
Fa represents a single bond or a linear or branched alkylene group, preferably a single bond.
Fb represents a monocyclic or polycyclic hydrocarbon group.
Fc represents a single bond or a linear or branched alkylene group, preferably a single bond or a methylene group.
F1 is a group represented by the general formula (F1).
P1 represents 1-3.

  The cyclic hydrocarbon group in Fb is preferably a cyclopentyl group, a cyclohexyl group, or a norbornyl group.

  Specific examples of the repeating unit having the structure of the general formula (F1) are shown below.

  In addition to the above repeating structural units, the alicyclic hydrocarbon-based acid-decomposable resin of the present invention has a dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power that is a general necessary characteristic of a resist. It can have various repeating structural units for the purpose of adjusting heat resistance, sensitivity and the like.

  Examples of such a repeating structural unit include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the alicyclic hydrocarbon-based acid-decomposable resin, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In alicyclic hydrocarbon-based acid-decomposable resins, the molar ratio of each repeating structural unit is the resist's dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution that is a general required performance of resists. In order to adjust heat resistance, sensitivity, etc., it is set appropriately.

Preferred embodiments of the alicyclic hydrocarbon-based acid-decomposable resin of the present invention include the following.
(1) What contains the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by the said general formula (pI)-(pV) (side chain type). Those having a repeating unit of (meth) acrylate preferably having a structure of (pI) to (pV).
(2) One having a repeating unit represented by the general formula (II-AB) (main chain type).
However, in (2), for example, the following can be further mentioned.
(3) Those having a repeating unit represented by the general formula (II-AB), a maleic anhydride derivative structure and a (meth) acrylate structure (hybrid type).

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having an acid-decomposable group is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, still more preferably 25 in all repeating structural units. -40 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 25 to 70 in all the repeating structural units. The mol% is preferable, more preferably 35 to 65 mol%, and still more preferably 40 to 60 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit represented by the general formula (II-AB) is preferably 10 to 60 mol%, more preferably 15 to 55 mol% in all repeating structural units. More preferably, it is 20-50 mol%.

  In addition, the content of the repeating structural unit based on the monomer of the further copolymer component in the resin can also be appropriately set according to the performance of the desired resist. ) To 99 p% with respect to the total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by (pV) and the repeating unit represented by the general formula (II-AB). The following is preferable, More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.

When the composition of the present invention is for ArF exposure, the resin preferably has no aromatic group from the viewpoint of transparency to ArF light.
The alicyclic hydrocarbon-based acid-decomposable resin used in the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units may be methacrylate, all of the repeating units may be acrylate, or a mixture of methacrylate / acrylate, but the acrylate repeating unit is preferably 50 mol% or less of the entire repeating unit.

  More preferably, the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 25 to 50%, the repeating unit having the lactone structure is 25 to 50%, and the polarity is A ternary copolymer having 5 to 30% of repeating units having an alicyclic hydrocarbon structure substituted with a group, or a repeating unit having a structure represented by a carboxyl group or general formula (F1) It is a quaternary copolymer having 20%.

The alicyclic hydrocarbon-based acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as that used in the resist composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50 to 100 ° C.

  When the composition of the present invention is used for the upper resist of the multilayer resist, the resin as the component (B) preferably has a silicon atom.

As the resin having a silicon atom and decomposing by the action of an acid to increase the solubility in an alkaline developer, a resin having a silicon atom in at least one of a main chain and a side chain can be used. Examples of the resin having a siloxane structure in the side chain of the resin include, for example, an olefin monomer having a silicon atom in the side chain, maleic anhydride and a (meth) acrylic acid monomer having an acid-decomposable group in the side chain. Mention may be made of copolymers.
As the resin having a silicon atom, a resin having a trialkylsilyl structure or a monocyclic or polycyclic siloxane structure is preferable, and a resin having a structure represented by the following general formulas (SS-1) to (SS-4) is used. The resin which has the structure represented by general formula (SS-1)-(SS-4) is more preferable, and the resin which has a (meth) acrylate type repeating unit which has a structure represented by general formula (SS-1)-(SS-4), or an allyl type repeating unit is more. preferable.

  In general formulas (SS-1) to (SS-4), Rs represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group.

The resin having a silicon atom preferably has a repeating unit having two or more different types of silicon atoms, more preferably (Sa) a repeating unit having 1 to 4 silicon atoms and (Sb) 5 to 10 silicon atoms. A resin having both of the repeating units, and more preferably, at least one repeating unit having a structure represented by formulas (SS-1) to (SS-3) and formula (SS-4). It is resin which has a repeating unit which has the structure represented by these.

When the positive resist composition of the present invention is irradiated with F ₂ excimer laser light, the resin of component (B) has a structure in which fluorine atoms are substituted on the main chain and / or side chain of the polymer skeleton, and A resin that decomposes by the action of an acid and increases the solubility in an alkaline developer (hereinafter also referred to as a fluorine group-containing resin) is preferred, and more preferably, a hydroxyl group substituted with a fluorine atom or a fluoroalkyl group at the 1-position or the 1-position A resin containing a group in which a hydroxyl group substituted with a fluorine atom or a fluoroalkyl group is protected with an acid-decomposable group, and most preferably a hexafluoro-2-propanol structure or a hydroxyl group of hexafluoro-2-propanol is protected with an acid-decomposable group It is a resin containing a structure. By introducing fluorine atoms, it is possible to improve transparency to far ultraviolet light, particularly F ₂ (157 nm) light.

  (B) Preferred examples of the fluorine group-containing resin in the acid-decomposable resin include resins having at least one repeating unit represented by the following general formulas (FA) to (FG).

In the general formula,
R _{100 to} R ₁₀₃ each represent a hydrogen atom, a fluorine atom, an alkyl group or an aryl group.
R ₁₀₄ and R ₁₀₆ are each a hydrogen atom, a fluorine atom or an alkyl group, and at least one of R ₁₀₄ and R ₁₀₆ is a fluorine atom or a fluoroalkyl group. R ₁₀₄ and R ₁₀₆ are preferably both trifluoromethyl groups.
R ₁₀₅ is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or a group that decomposes under the action of an acid.
A ₁ is a single bond, a divalent linking group, for example, a linear, branched, cyclic alkylene group, alkenylene group, arylene group, —OCO—, —COO—, or —CON (R ₂₄ ) —, and of these It is a linking group containing a plurality. R ₂₄ is a hydrogen atom or an alkyl group.
R ₁₀₇ and R ₁₀₈ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or a group that decomposes under the action of an acid.
R ₁₀₉ is a hydrogen atom, an alkyl group, a cycloalkyl group, or a group that decomposes under the action of an acid.
a is 0 or 1.
b is 0, 1 or 2;
R ₁₀₀ and R ₁₀₁ in the general formulas (FA) and (FC) may form a ring via an alkylene group (having 1 to 5 carbon atoms) which may be substituted with fluorine.

  The repeating units represented by the general formulas (FA) to (FG) contain at least one, preferably three or more fluorine atoms per one repeating unit.

  The weight average molecular weight of the resin of component (B) is preferably 2,000 to 200,000 as a polystyrene conversion value by GPC method. By making the weight average molecular weight 2,000 or more, heat resistance and dry etching resistance can be improved, and by making the weight average molecular weight 200,000 or less, developability can be improved. And since a viscosity becomes low, film forming property can be improved. The molecular weight is more preferably 5,000 to 50,000, and still more preferably 7,000 to 30,000. By adjusting the molecular weight, it is possible to achieve both heat resistance, resolution, development defects, and the like of the composition. The dispersity (Mw / Mn) of the component (B) resin is preferably 1.0 to 3.0, more preferably 1.2 to 2.5, and even more preferably 1.2 to 1.6. It is. The line edge roughness performance can be improved by adjusting the degree of dispersion to an appropriate range.

  In the positive resist composition of the present invention, the blending amount of the resin of the component (B) according to the present invention in the entire composition is preferably 40 to 99.99 mass%, more preferably 50 to 99 in the total solid content. It is 80 mass%, More preferably, it is 80-96 mass%.

[3] (C) Dissolution-inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “(C) component” or “dissolution-inhibiting compound”) that is decomposed by the action of an acid to increase the solubility in an alkaline developer.
(C) As a dissolution-inhibiting compound having a molecular weight of 3000 or less that decomposes by the action of an acid and increases its solubility in an alkaline developer, the transmittance of 220 nm or less is not lowered, so Proceeding of SPIE, 2724,355 (1996) An alicyclic or aliphatic compound containing an acid-decomposable group is preferred, such as a cholic acid derivative containing an acid-decomposable group described in 1). Examples of the acid-decomposable group and alicyclic structure are the same as those described above for the alicyclic hydrocarbon-based acid-decomposable resin.

  When the resist composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.

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

  The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the solid content of the resist composition.

  Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

[4] (D) Resin soluble in alkali developer (hereinafter also referred to as “component (D)” or “alkali-soluble resin”)
The alkali dissolution rate of the alkali-soluble resin is preferably 20 kg / sec or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 200 Å / second or more (Å is angstrom).

  Examples of the alkali-soluble resin used in the present invention include novolak resin, hydrogenated novolak resin, acetone-pyrogalol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, and halogen. Alternatively, alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, partially O-alkylated product of hydroxyl group of polyhydroxystyrene (for example, 5- 30 mol% O-methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-butoxycarbonyl) methylated product, etc.) Or O-acylated product (for example, 5 to 30 mol) O-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic acid Examples thereof include, but are not limited to, resins and derivatives thereof, and polyvinyl alcohol derivatives.

  Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrenes, partially O-alkylated polyhydroxystyrenes, Alternatively, O-acylated product, styrene-hydroxystyrene copolymer, and α-methylstyrene-hydroxystyrene copolymer.

  The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

  Moreover, the weight average molecular weight of alkali-soluble resin is 2000 or more, Preferably it is 5000-200000, More preferably, it is 5000-100000.

  Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

  These (D) alkali-soluble resins in the present invention may be used in combination of two or more.

  The usage-amount of alkali-soluble resin is 40-97 mass% with respect to solid content of the whole composition of a resist composition, Preferably it is 60-90 mass%.

[5] (E) Acid crosslinking agent that crosslinks with the alkali-soluble resin by the action of acid (hereinafter also referred to as “(E) component” or “crosslinking agent”)
A crosslinking agent is used in the negative resist composition of the present invention.

Any crosslinking agent can be used as long as it is a compound that crosslinks a resin soluble in an alkaline developer by the action of an acid, but the following (1) to (3) are preferred.
(1) Hydroxymethyl, alkoxymethyl, and acyloxymethyl forms of phenol derivatives.
(2) A compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group.
(3) A compound having an epoxy group.

  The alkoxymethyl group preferably has 6 or less carbon atoms, and the acyloxymethyl group preferably has 6 or less carbon atoms.

  Of these crosslinking agents, particularly preferred are listed below.

In the formula, L ^{1 to} L ⁸ may be the same or different and each represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.
The crosslinking agent is generally used in an amount of 3 to 70% by mass, preferably 5 to 50% by mass, in the solid content of the resist composition.

[6] (F) Basic compound The resist composition of the present invention contains a basic compound represented by the following general formula (N).

In general formula (N), R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
Two or more of R ^{250 to} R ²⁵² may be bonded to form an alkylene group to form a ring. The alkylene group may have a hetero atom. In addition, as a hetero atom which the alkylene group may have, an oxygen atom, a sulfur atom, and a nitrogen atom can be mentioned.

In the compound represented by the general formula (N), one of R ^{250 to} R ²⁵² is bonded to another compound via a linking group, and has two or more structures represented by the general formula (N). May be.

In general formula (N), the alkyl group as R ²⁵⁰ , R ²⁵¹ and R ²⁵² is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, specifically a methyl group or an ethyl group. Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, octyl group, dodecyl group, hexadecyl group and the like. As R ²⁵⁰ , R ²⁵¹ and R ²⁵² , the alkyl group may have a substituent and may have a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain.
The cycloalkyl group as R ²⁵⁰ , R ²⁵¹ and R ²⁵² is preferably a cycloalkyl group having 3 to 20 carbon atoms, and specific examples include a cyclopentyl group and a cyclohexyl group. The alkyl group as R ²⁵⁰ , R ²⁵¹ and R ²⁵² may have a substituent, and may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom in the cycloalkyl chain. .
The aryl group as R ²⁵⁰ , R ²⁵¹ and R ²⁵² is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. The aryl group as R ²⁵⁰ , R ²⁵¹ and R ²⁵² may have a substituent.
The heteroaryl group as R ²⁵⁰ , R ²⁵¹ and R ²⁵² is preferably a heteroaryl group having 5 to 20 carbon atoms, and examples thereof include a pyridyl group. The heteroaryl group as R ²⁵⁰ , R ²⁵¹ and R ²⁵² may have a substituent.
Examples of the substituent which the alkyl group in R ²⁵⁰ , R ²⁵¹ and R ²⁵² may have include a hydroxyl group, a nitro group, a cyano group, an alkoxycarbonyl group, an alkoxy group and a carboxyl group.
Examples of the substituent that the cycloalkyl group, aryl group, and heteroaryl group in R ²⁵⁰ , R ²⁵¹ , and R ²⁵² may have include an alkyl group, a hydroxyl group, a nitro group, a cyano group, an alkoxycarbonyl group, and an alkoxy group. And carboxyl group.

  Preferred examples of the basic compound represented by the general formula (N) include aliphatic amine compounds, aniline compounds, and aminopyridine compounds.

Examples of the aliphatic amine compound include primary, secondary and tertiary aliphatic amine compounds, and preferably a tertiary aliphatic amine in which all of R ²⁵⁰ , R ²⁵¹ and R ²⁵² are alkyl groups or cycloalkyl groups. A compound. When R ²⁵⁰ , R ²⁵¹ and R ²⁵² are a hydrogen atom or an alkyl or cycloalkyl group having no substituent, the sum of the carbon numbers of R ²⁵⁰ , R ²⁵¹ and R ²⁵² is preferably 6 or more. More preferably, it is 10 or more, More preferably, it is 12 or more. A good profile can be obtained by adjusting the carbon number.
The aliphatic amine compound may have a substituent. Preferred examples of the substituent that the aliphatic amine compound may have include a hydroxyl group, a cyano group, and an alkoxycarbonyl group.
Preferred specific examples of the aliphatic amine compound are shown below.
Hexylamine, octylamine, dodecylamine, cyclohexylamine, primary aliphatic amines such as adamantylamine, hydroxyl-substituted primary amines such as ethanolamine, diisopropylamine, dibutylamine, dihexylamine, dicyclohexylamine, dioctylamine, didodecylamine Secondary aliphatic amines such as, cyclic amines such as piperidine, pyrrolidine, morpholine, hydroxyl-substituted secondary amines such as diethanolamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, trioctylamine, tridodecyl Tertiary aliphatic amines such as amine, dicyclohexylmethylamine, dicyclohexylethylamine, diisopropylethylamine, dioctylmethylamine, N- Cyclic tertiary amines such as tilpiperidine, N-butylpiperidine, N-methylmorpholine, hydroxyl-substituted tertiary amines such as triethanolamine, N-methyldiethanolamine, N-octyldiethanolamine, tris (methoxyethyl) amine, tris (methoxy) Such as amines containing an ether bond in the chain such as ethoxyethyl) amine, amines having a bicyclo structure such as diazabicyclo [2.2.2] octane, N, N, N ′, N′-tetramethylethylenediamine, etc. Examples include amines having a plurality of structures of the general formula (N).

Preferred specific examples of the aniline compound are shown below.
N, N-dialkylanilines (for example, N, N-dimethylaniline, N, N-diethylaniline, N, N-dipropylaniline, N, N-dibutylaniline, N-butyl-N-methylaniline, N, N -Dioctylaniline, N-phenylpiperidine and the like), N, N-dihydroxyalkylanilines (for example, N-phenyldiethanolamine, N- (4-methylphenyl) diethanolamine, N-phenyldipropanolamine, N- (4 -Methylphenyl) dipropanolamine), cyanoalkylanilines (for example, N-cyanoethylaniline, N, N-biscyanoethylaniline, N-methyl-N-cyanoethylaniline, etc.), alkoxyalkylanilines Class (for example, N, N-bi (Methoxyethylaniline), N, N-bis (ethoxyethyl) aniline, N-phenylmorpholine, etc.), anilines having a substituent on the aromatic ring (for example, 2,6-dimethylaniline, 2,6 -Diisopropylaniline, 2,4,6-tri-t-butylaniline, 2,6-dinitroaniline, N, N-diethylphenylenediamine, 2-aminobiphenyl, pentafluoroaniline, 4,4'methylenebis (2,6- Diisopropylaniline) and the like.
Preferred are aniline compounds substituted at the 2,6-position, N, N-dialkylaniline, and N, N-bis (hydroxyalkyl) aniline.

  The amount of the basic compound used is generally 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the resist composition as a total amount, and further the total weight of the acid generator. The content is 5 to 50% by weight, preferably 7 to 20% by weight. By adjusting the addition amount of the basic compound, the effect of addition of the above components can be obtained, and the tendency of the sensitivity to decrease and the developability of the non-exposed area to deteriorate can be prevented.

[7] (G) Fluorine and / or silicon-based surfactant The resist composition of the present invention further comprises a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant, fluorine atom Or a surfactant containing both silicon atoms), or preferably two or more.

  When the resist composition of the present invention contains fluorine and / or a silicon-based surfactant, when using an exposure light source of 250 nm or less, particularly 220 nm or less, good sensitivity and resolution, and less adhesion and development defects. A resist pattern can be provided.

  Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.

  Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. It may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

  The amount of fluorine and / or silicon surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the resist composition (excluding the solvent). .

[8] (H) Organic solvent The resist composition of the present invention is used by dissolving each component in a predetermined organic solvent.

Examples of the organic solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl. Ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc.

  In the present invention, the organic solvent may be used alone or in combination, but it is preferable to use a mixed solvent containing two or more solvents having different functional groups. As the mixed solvent having different functional groups, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group are mixed, or a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed. Is preferably used. Thereby, the generation of particles during storage of the resist solution can be reduced.

  Examples of the solvent having a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Propylene glycol monomethyl ether and ethyl lactate are more preferable.

  Examples of the solvent having no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide. Of these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxypropio Nate, 2-heptanone and cyclohexanone are particularly preferred.

  The mixing ratio (mass) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is usually 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. is there. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.

In a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed, examples of the solvent having a ketone structure include cyclohexanone and 2-heptanone, and cyclohexanone is preferable. Examples of the solvent having an ester structure include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, γ-butyrolactone, and butyl acetate, with propylene glycol monomethyl ether acetate being preferred.
The mixing ratio (mass) of the solvent having an ester structure and the solvent having a ketone structure is usually 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. is there. A mixed solvent containing 50% by mass or more of a solvent having an ester structure is particularly preferable from the viewpoint of coating uniformity.

<Other additives>
If necessary, the resist composition of the present invention further contains a dye, a plasticizer, a surfactant other than the component (G), a photosensitizer, a compound that promotes solubility in a developer, and the like. Can do.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable.

  A preferable addition amount of these dissolution promoting compounds is 2 to 50% by mass, and more preferably 5 to 30% by mass with respect to the resin of the component (B) or the resin of the component (D). 50 mass% or less is preferable at the point of development residue suppression and the pattern deformation prevention at the time of image development.

  Such phenol compounds having a molecular weight of 1000 or less can be obtained by referring to methods described in, for example, JP-A-4-1222938, JP-A-2-28531, U.S. Pat. No. 4,916,210 and European Patent 219294. Can be easily synthesized.

  Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

  In the present invention, a surfactant other than the above (G) fluorine-based and / or silicon-based surfactant may be added. Specifically, nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan aliphatic esters, polyoxyethylene sorbitan aliphatic esters, etc. Mention may be made of activators.

  These surfactants may be added alone or in some combination.

(Pattern formation method)
The resist composition of the present invention is used by dissolving each component in a predetermined organic solvent, preferably the mixed solvent, and applying the solution onto a predetermined support as follows.

For example, a resist composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater, and dried to form a resist film. .
The resist film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
Exposure (immersion exposure) may be performed by filling a liquid having a higher refractive index than air between the resist film and the lens during irradiation with actinic rays or radiation. Thereby, resolution can be improved.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, etc., but preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc. ArF excimer laser, F ₂ excimer laser, EUV (13 nm) An electron beam is preferred.

In the development step, an alkaline developer is used as follows. As an alkaline developer of the resist composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

Synthesis Example 1 (Synthesis of Compound (A1-1))
7.8 g of triphenylsulfonium iodide was dissolved in 100 ml of acetonitrile / 50 ml of water, and 3.5 g of silver acetate was added thereto. The mixture was stirred at room temperature for 30 minutes, and the precipitated silver iodide was removed by filtration. To the filtrate, 5.0 g of potassium pentafluoroethanesulfonate was dissolved in water and added. This was extracted with chloroform, and the organic layer was washed successively with water, an aqueous ammonium chloride solution, and water. The organic layer was filtered through a 0.1 micron tetrafluoroethylene filter and concentrated to obtain 8.6 g of Compound (A1-1).

Synthesis Example 2 (Synthesis of Compound (A2-1))
3.8 g of triphenylsulfonium iodide was dissolved in 100 ml of acetonitrile / 50 ml of water, and 1.8 g of silver acetate was added thereto. The mixture was stirred at room temperature for 30 minutes, and the precipitated silver iodide was removed by filtration. To the filtrate, 3.0 g of potassium perfluoropropanesulfonate was dissolved in water / acetonitrile and added. The reaction solution was concentrated, and ethyl acetate was added thereto. This was washed sequentially with water, an aqueous ammonium chloride solution and water, and the organic layer was filtered and concentrated with a 0.1 micron tetrafluoroethylene filter to obtain 3.5 g of compound (A2-1).

  Other acid generators were synthesized in the same manner.

<Resin (B)>
The structure, molecular weight, and dispersity of the resin (B) used in the examples are shown.

Examples 1-20 and Comparative Examples 1-3
<Resist preparation>
The components shown in Table 1 below were dissolved in a solvent to prepare a solution having a solid concentration of 10% by mass, and this was filtered through a 0.1 μm polytetrafluoroethylene filter or a polyethylene filter to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method, and the results are also shown in Table 1.

Hereinafter, abbreviations in the table are shown.
[Acid generator]
TPSB: Triphenylsulfonium nonafluorobutane sulfonate TPST: Triphenylsulfonium trifluoromethanesulfonate

[Basic compounds]
DBA: N, N-dibutylaniline DIA: 2,6-diisopropylaniline
PEA: N-phenyldiethanolamine CEA: N-cyanoethylaniline TBA: tributylamine TOA: trioctylamine TEA: triethanolamine TMEA: tris (methoxyethoxy) amine DCMA: dicyclohexylmethylamine TPA: tripentylamine HEP: N-hydroxyethyl Piperidine HAP: Hydroxyantipyrine TPSA: Triphenylsulfonium acetate N1: 2,4,5-triphenylimidazole N2: 1,5-diazabicyclo [4.3.0] -5-nonene

[Surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.)
(Fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Silicon)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

〔solvent〕
S1: Propylene glycol methyl ether acetate S2: 2-heptanone S3: Cyclohexanone S4: γ-Butyrolactone S5: Propylene glycol methyl ether S6: Ethyl lactate

[Dissolution inhibitor compound]
LCB: lithocholic acid-t-butyl

<Resist evaluation>
An antireflection film DUV-42 manufactured by Brewer Science Co., Ltd. was uniformly applied to 600 Å on a silicon substrate subjected to hexamethyldisilazane treatment with a spin coater, dried on a hot plate at 100 ° C. for 90 seconds, and then at 190 ° C. Heat drying was performed for 240 seconds. Thereafter, each positive resist solution was applied by a spin coater and dried at 120 ° C. for 90 seconds to form a 0.20 μm resist film.
The resist film was exposed with an ArF excimer laser stepper (NA = 0.75 manufactured by ASML) through a mask, and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. Further, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a line pattern.

Density dependency:
Evaluated by the line width of an isolated pattern (line / space = 1/10) at an exposure dose that reproduces a mask pattern of a dense pattern (line / space = 1/1) of 0.10 μm, and the difference from 0.10 μm (nm) ).
The smaller the value, the smaller the performance difference between the dense pattern and the isolated pattern, and the better the density dependency.

PEB temperature dependence:
The exposure amount that reproduces the line and space 1/1 with a mask size of 100 nm when post-heated at 120 ° C. for 90 seconds is the optimum exposure amount, and after performing exposure at the optimum exposure amount, Post-heating was performed at two temperatures of + 2 ° C. and −2 ° C. (122 ° C., 118 ° C.), and the obtained line and space were measured to determine their line widths L ₁ and L ₂ . The PEB temperature dependency was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ℃) = | L 1 -L 2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.

  From Table 1, it is clear that the resist composition of the present invention has good density dependency and PEB temperature dependency.

[Immersion exposure evaluation]
<Resist preparation>
The components of Examples 1 to 20 shown in Table 1 were dissolved in a solvent to prepare a solution having a solid content concentration of 8% by mass, and this was filtered through a 0.1 μm polyethylene filter to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method.
<Resolution evaluation>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The prepared resist composition was applied thereon and baked at 120 ° C. for 60 seconds to form a 150 nm resist film. The wafer thus obtained was subjected to two-beam interference exposure (wet exposure) using pure water as the immersion liquid. In the two-beam interference exposure (wet), as shown in FIG. 1, a laser 1, an aperture 2, a shutter 3, three reflecting mirrors 4, 5, 6 and a condenser lens 7 are used, and a prism 8, liquid The wafer 10 having an antireflection film and a resist film was exposed through an immersion liquid (pure water) 9. The wavelength of the laser 1 is 193 nm, and a prism that forms a 65 nm line and space pattern 8 is used. Immediately after the exposure, the resist pattern obtained by heating at 120 ° C. for 60 seconds, developing with an aqueous tetramethylammonium hydroxide solution (2.38%) for 60 seconds, rinsing with pure water, and spin drying is applied to the scanning pattern. When observed using a microscope (S-9260, manufactured by Hitachi), a 65 nm line and space pattern was resolved.
The compositions of Examples 1 to 20 had good image forming ability even in the exposure method through the immersion liquid.

Examples 21-25 and Comparative Examples 4-6
(1) Formation of lower resist layer FHi-028DD resist (resist for i-line manufactured by Fuji Film Orin) was applied to a 6-inch silicon wafer using a spin coater Mark8 manufactured by Tokyo Electron, and baked at 90 ° C. for 90 seconds to form a film. A uniform film having a thickness of 0.55 μm was obtained.
This was further heated at 200 ° C. for 3 minutes to form a lower resist layer having a thickness of 0.40 μm.

(2) Formation of the upper resist layer The components shown in Table 2 below are dissolved in a solvent to prepare a solution having a solid content of 11% by mass, and the solution is precisely filtered through a membrane filter having a diameter of 0.1 μm to prepare an upper resist composition. did.
An upper resist composition was applied on the lower resist layer in the same manner as the lower layer, and heated at 130 ° C. for 90 seconds to form an upper resist layer having a thickness of 0.20 μm.

  Resins (SI-1) to (SI-5) in Table 2 are as follows.

(3) Resist evaluation The wafer thus obtained was exposed with an ArF excimer laser stepper (NAML = 0.75 manufactured by ASML) through a mask, and immediately after exposure, heated on a hot plate at 120 ° C. for 90 seconds. Further, the film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to form a line pattern. The PEB temperature dependency was evaluated.
The evaluation results are shown in Table 2.

  From the results in Table 2, it can be seen that the resist composition of the present invention has good density dependency and PEB temperature dependency even when used as a two-layer resist.

Examples 26-30 and Comparative Examples 7-9
<Resist preparation>
The components shown in Table 3 below were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 14% by mass, and evaluated as follows. .

  The weight average molecular weights and dispersities of the resins (R-1) to (R-5) used in Table 3 are shown in Table 4 below.

<Resist evaluation>
The prepared positive resist solution is uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 90 seconds to obtain a 0.4 μm resist. A film was formed.
The resist film was subjected to pattern exposure using a line and space mask using a KrF excimer laser stepper (NA = 0.63), and heated on a hot plate at 110 ° C. for 90 seconds immediately after the exposure. Further, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to form a line pattern.

Density dependency:
Evaluation was performed by the line width of an isolated pattern (line / space = 1/10) at an exposure amount for reproducing a mask pattern of a dense pattern (line / space = 1/1) of 130 nm, and displayed as a difference (nm) from 130 nm. .
The smaller the value, the smaller the performance difference between the dense pattern and the isolated pattern, and the better the density dependency.

PEB temperature dependence:
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 130 nm when post-heated at 120 ° C. for 90 seconds is the optimal exposure amount, and after performing exposure at the optimal exposure amount, Post-heating was performed at two temperatures of + 2 ° C. and −2 ° C. (122 ° C., 118 ° C.), and the obtained line and space were measured to determine their line widths L ₁ and L ₂ . The PEB temperature dependency was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ℃) = | L 1 -L 2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
The evaluation results are shown in Table 3.

  From the results in Table 3, it can be seen that the resist composition of the present invention has good density dependency and PEB temperature dependency as a positive resist composition in KrF excimer laser exposure.

Examples 31-35 and Comparative Examples 10-12
<Resist preparation>
The components shown in Table 3 above were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 11% by mass, and evaluated as follows. .

<Resist evaluation>
The prepared positive resist solution is uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 60 seconds to obtain a 0.25 μm resist. A film was formed.
This resist film was irradiated with a pattern with an electron beam direct drawing device (acceleration voltage 50 keV), and immediately after irradiation, heated on a hot plate at 110 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern.

Density dependency:
Evaluated by the line width of an isolated space pattern (line / space = 10/1) at a dose that reproduces a dense pattern (line / space = 1/1) of 0.10 μm, and the difference (nm) from 0.10 μm displayed.
The smaller the value, the smaller the performance difference between the dense pattern and the isolated pattern, and the better the density dependency.

PEB temperature dependence:
The irradiation dose that reproduces 100 nm line-and-space 1/1 when post-heated at 120 ° C. for 90 seconds is the optimum irradiation dose, and after irradiation at the optimum irradiation dose, + 2 ° C. with respect to the post-heating temperature And after-heating was performed at two temperatures of −2 ° C. (122 ° C., 118 ° C.), the obtained line and space were measured, and their line widths L ₁ and L ₂ were obtained. The PEB temperature dependency was defined as the fluctuation of the line width per PEB temperature change of 1 ° C., and was calculated by the following formula.
PEB temperature dependency (nm / ℃) = | L 1 -L 2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
The evaluation results are shown in Table 5 below.

  From Table 5, it can be seen that the resist composition of the present invention has good density dependency and PEB temperature dependency even as a positive resist composition in electron beam exposure.

Examples 36-40 and Comparative Examples 13-15
The components shown in Table 3 were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 8% by mass, and evaluated as follows. .

<Resist evaluation>
The prepared positive resist solution is uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 60 seconds to obtain a 0.15 μm resist. A film was formed. The obtained resist film was subjected to surface exposure using EUV light (wavelength 13 nm) while changing the exposure amount by 0.5 mJ in the range of 0 to 10.0 mJ, and further baked at 110 ° C. for 90 seconds. Then, using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to obtain a sensitivity curve. In this sensitivity curve, the exposure amount when the dissolution rate of the resist is saturated was taken as sensitivity, and the dissolution contrast (γ value) was calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the better the dissolution contrast.
The evaluation results are shown in Table 6 below.

  From the results in Table 6, it can be seen that the resist composition of the present invention is superior in sensitivity and high contrast as compared with the composition of the comparative example in the property evaluation by irradiation with EUV light.

Examples 41-45 and Comparative Examples 16-18
The components shown in Table 7 below were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a negative resist solution with a solid content concentration of 11% by mass, and evaluated as follows. .

  The structure, molecular weight, molecular weight distribution, and crosslinking agent of the alkali-soluble resin in Table 7 are shown below.

<Resist evaluation>
The prepared negative resist solution is uniformly coated on a silicon substrate that has been subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 60 seconds to obtain a 0.25 μm resist. A film was formed.
This resist film was irradiated with a pattern with an electron beam direct drawing device (acceleration voltage 50 keV), and immediately after irradiation, heated on a hot plate at 110 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern.

Density dependency:
Evaluated by the line width of an isolated line pattern (line / space = 10/1) at a dose that reproduces a dense pattern (line / space = 1/1) of 0.10 μm, and the difference (nm) from 0.10 μm displayed.
The smaller the value, the smaller the performance difference between the dense pattern and the isolated pattern, and the better the density dependency.

PEB temperature dependence:
When post-heating at 120 ° C. for 90 seconds, the irradiation dose that reproduces 100 nm line and space 1/1 is set as the optimal irradiation dose, and then after irradiation at the optimal irradiation dose,
Post-heating was performed at two temperatures of + 2 ° C. and −2 ° C. (122 ° C., 118 ° C.), and the obtained line and space were measured to determine their line widths L ₁ and L ₂ . The PEB temperature dependency was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ℃) = | L 1 -L 2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.
The evaluation results are shown in Table 7.

  From Table 7, it can be seen that the resist composition of the present invention has good density dependency and PEB temperature dependency as a negative resist composition in electron beam exposure.

Examples 46-50 and Comparative Examples 19-21
<Resist preparation>
The components shown in Table 7 were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a negative resist solution having a solid content concentration of 8% by mass, and evaluated as follows. .

<Resist evaluation>
The prepared positive resist solution is uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 60 seconds to obtain a 0.15 μm resist. A film was formed. The obtained resist film was subjected to surface exposure using EUV light (wavelength 13 nm) while changing the exposure amount in steps of 0.5 mJ within a range of 0 to 10.0 mJ, and further baked at 110 ° C. for 90 seconds. Then, using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to obtain a sensitivity curve. In this sensitivity curve, the exposure amount when the residual film ratio at a development time of 60 seconds was 98% or more was taken as sensitivity, and the dissolution contrast (γ value) was calculated from the slope of the linear portion of the sensitivity curve. The larger the γ value, the better the dissolution contrast.
The evaluation results are shown in Table 8 below.

  From the results shown in Table 8, it can be seen that the resist composition of the present invention is superior in sensitivity and high contrast as compared with the composition of the comparative example in the property evaluation by irradiation with EUV light.

It is the schematic of a two-beam interference exposure experiment apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laser 2 Aperture 3 Shutter 4, 5, 6 Reflection mirror 7 Condensing lens 8 Prism 9 Immersion liquid 10 Wafer having antireflection film and resist film 11 Wafer stage

Claims (13)

(A) It contains a compound that generates pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid upon irradiation with actinic rays or radiation, and (F) a basic compound represented by the following general formula (N). Resist composition.

In general formula (N), R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
Two or more of R ^{250 to} R ²⁵² may be bonded to form an alkylene group to form a ring. The alkylene group may have a hetero atom. The compound (A) is at least one compound selected from pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid sulfonium salt compound or iodonium salt compound and pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid ester compound. The resist composition according to claim 1, wherein: The resist composition according to claim 1, wherein the compound of component (F) is at least one compound selected from an aliphatic amine compound and an aniline compound . The compound of (A) component is a compound represented by the following general formula (A1), The resist composition in any one of Claims 1-3 characterized by the above-mentioned.

In general formula (A1),
  R _201a , R _202a And R _203a Each independently represents an organic group. R _201a , R _202a And R _203a Two of these may combine to form a ring structure.
  Xa ^- Is -SO of pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid _Three It represents a sulfonate anion from which a hydrogen atom of H has been removed. In the general formula (A1), R _201a , R _202a And R _203a 5. The resist composition according to claim 4, wherein two of these are bonded to form an alkylene group. In the general formula (A1), R _201a , R _202a And R _203a 6. The resist composition according to claim 4, wherein at least one of the groups is an aryl group. The positive resist composition according to claim 1, further comprising (B) a resin that decomposes by the action of an acid and increases the solubility in an alkaline developer. Furthermore, (D) the resin soluble in an alkali developing solution and (E) the acid crosslinking agent which bridge | crosslinks with the resin soluble in an alkali developing solution by the effect | action of an acid are contained. The negative resist composition as described in any one of the above. The positive resist composition according to claim 7, wherein the resin that decomposes by the action of an acid and has increased solubility in an alkaline developer has a hydroxystyrene structural unit. 8. The positive resist according to claim 7, wherein the resin that is decomposed by the action of an acid and has increased solubility in an alkaline developer has a repeating unit having a monocyclic or polycyclic hydrocarbon structure. Composition. 11. The positive resist composition according to claim 10, wherein the resin that is decomposed by the action of an acid and has increased solubility in an alkaline developer has a repeating unit represented by the following general formula (AI): .

  In general formula (AI),
  Rb ₀ Represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
  Ab is a divalent chain having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure.
It represents a linking group, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these.
  V represents a group represented by any one of the following general formulas (LC1-1) to (LC1-16).

  Where Rb ₂ Represents a substituent.
  n ₂ Represents an integer of 0 to 4. n ₂ When R is 2 or more, there are multiple Rb ₂ May be the same or different, and a plurality of Rb ₂ They may combine to form a ring. A pattern forming method comprising: forming a resist film from the resist composition according to claim 1; and exposing and developing the resist film. A pattern forming method comprising: forming a resist film from the resist composition according to claim 1, and subjecting the resist film to immersion exposure and development.

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