JP2007178621A - Positive resist composition and pattern forming method using the positive resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition for use in the production process of a semiconductor, such as IC, in the production of a circuit substrate of liquid crystal, thermal head and the like or in other photofabrication processes and a pattern forming method, using the positive resist composition, which are a positive resist composition capable of satisfying both of improvement of exposure latitude (EL) and pattern collapse and scum-preventing properties on a high level and a pattern-forming method by using the positive resist composition. <P>SOLUTION: The positive resist composition comprises (A) a resin comprising at least two kinds of repeating units, having a cyano group, at least one of which is a repeating unit (A1) further having a lactone structure, and, having solubility in an alkali developer, increased by the action of an acid, and (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation. The pattern forming method using the positive resist composition is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  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 improvements have also been made on acid-decomposable resins that are main constituents of chemically amplified resist compositions. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2004-53822) discloses specific methacrylic repeating units. An acid-decomposable resin having is disclosed.

  However, it is further desired to improve the exposure latitude (EL), pattern collapse and scum prevention characteristics at a high level.

JP 2004-53822 A

  Accordingly, an object of the present invention is to provide an exposure latitude (EL) improvement, pattern collapse and scum prevention characteristics, a positive resist composition that enables high-dimensional alignment and a pattern forming method using the positive resist composition. It is to provide.

  The present invention is as follows.

一般式（Ａ１−２）中、
Ｒ_1A〜Ｒ_6Aは、各々独立に、水素原子又は置換基を表す。但し、Ｒ_1A〜Ｒ_6Aの内の少なくとも一つは、シアノ基又はシアノ基を有する置換基を表す。Ｒ_1A〜Ｒ_6Aの内の少なくとも２つは、互いに結合して環構造を形成してもよい。 (1) (A) a resin containing at least two types of repeating units having a cyano group, wherein at least one of the repeating units having a cyano group is a repeating unit (A1) further having a lactone structure, A resin whose solubility in an alkaline developer is increased by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
A positive resist composition comprising:
(2) The positive resist composition as described in (1) above, wherein the repeating unit (A1) is a repeating unit having a structure represented by the following general formula (A1-2).

In general formula (A1-2),
R _{1A to} R _6A each independently represents a hydrogen atom or a substituent. However, at least one of R _{1A to} R _6A represents a cyano group or a substituent having a cyano group. At least two of R _{1A to} R _6A may be bonded to each other to form a ring structure.

一般式（Ａ１−６）中、
Ｒ_18Aは、水素原子又は置換基を表す。
Ｌ₁は、ラクトン環の２位の炭素原子と、ラクトン環の酸素原子とを連結してラクトン環構造を形成する連結基を表す。
Ｒ_18A及びＬ₁は、互いに結合して環構造を形成してもよい。
（４） 上記（１）〜（３）のいずれかに記載のポジ型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。 (3) The positive resist composition as described in (1) above, wherein the repeating unit (A1) is a repeating unit having a structure represented by the following general formula (A1-6).

In general formula (A1-6),
R _18A represents a hydrogen atom or a substituent.
L ₁ represents a linking group that links the carbon atom at the 2-position of the lactone ring and the oxygen atom of the lactone ring to form a lactone ring structure.
R _18A and L ₁ may combine with each other to form a ring structure.
(4) A pattern forming method comprising a step of forming a resist film from the positive resist composition according to any one of (1) to (3), and exposing and developing the resist film.

  According to the present invention, there are provided a positive resist composition that enables high-order alignment with respect to improved exposure latitude (EL), pattern collapse, and scum prevention characteristics, and a pattern forming method using the positive resist composition. be able to.

The present invention will be described in detail below.
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).

[1] (A) a resin containing at least two types of repeating units having a cyano group, wherein at least one of the repeating units having a cyano group is a repeating unit (A1) further having a lactone structure, Resin whose solubility in an alkaline developer is increased by the action of an acid The positive resist composition of the present invention contains (A) at least two types of repeating units having a cyano group, and among the repeating units having the cyano group, Resin in which at least one kind is a repeating unit (A1) further having a lactone structure and has increased solubility in an alkali developer by the action of an acid (hereinafter referred to as “acid-decomposable resin (A)” or “resin” (A) ").

<Repeating unit (A1) having a cyano group and a lactone group>
Examples of the lactone structure in the repeating unit (A1) include a 4- to 15-membered ring lactone structure, and a 4- to 8-membered ring lactone is preferable from the viewpoint of polarity and stability. It is more preferably a 6-membered ring lactone, and particularly preferably a 5-membered ring lactone.

  Hereinafter, although the specific example of a lactone structure is shown, this invention is not limited to this.

1-4 are preferable and, as for the number of the cyano group which a repeating unit (A1) has, 1-2 are more preferable.
The cyano group is preferably directly connected to the lactone ring.

  As a suitable form of the repeating unit (A1), a repeating unit having a structure represented by the following general formula (A1-2) can be mentioned.

In general formula (A1-2),
R _{1A to} R _6A each independently represents a hydrogen atom or a substituent. However, at least one of R _{1A to} R _6A represents a cyano group or a substituent having a cyano group. At least two of R _{1A to} R _6A may be bonded to each other to form a ring structure.
The repeating unit having the structure represented by the general formula (A1-2) has the structure represented by the general formula (A1-2) at a position that can be a hydrogen atom in R _{1A to} R _6A (that is, R _1A to as at least one bond of the hydrogen atoms) included in the substituents represented by hydrogen atoms and R _1A to R _6A as R _6A, only to have any of the main chain and side chain of the repeating unit.

The substituents as R _{1A to} R _6A are not particularly limited. For example, in addition to a cyano group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido Groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, nitro groups and the like. The substituent may further have a substituent. R _1A and R _2A , R _3A and R _4A , and R _5A and R _6A , which are substituents on the same carbon atom, are all the same atoms (for example, carbon atom, oxygen atom, sulfur atom, nitrogen atom) A double bond represented by C = C, C = O, C = S, C = N bond or the like may be formed. Any two of R _{1A to} R _6A may be bonded to the same atom to form a three-membered ring structure or a bridged ring structure.
The substituent having a cyano group as R _{1A to} R _6A is not particularly limited, and examples thereof include those in which the above-described substituent is substituted with a cyano group. The number of carbon atoms is 12 except for the carbon atom of the cyano group. The following is preferable, and 6 or less is more preferable.
The cyano group is particularly preferably directly connected to the lactone ring.

  Another preferred form of the repeating unit (A1) includes a repeating unit having a structure represented by the following general formula (A1-3).

In general formula (A1-3),
R _{7A to} R _13A each independently represents a hydrogen atom or a substituent. At least two of R _{7A to} R _13A may be bonded to each other to form a ring structure.
X is, -O -, - S -, - N (R N) 2 - or - (CH _{2) n} - represents a. In the formula, R ^N represents a hydrogen atom or a substituent. n represents 1 or 2.
However, at least one of R _{7A to} R _13A and X represents a cyano group or a substituent having a cyano group.
In the repeating unit having the structure represented by the general formula (A1-3), the structure represented by the general formula (A1-3) can be substituted with a portion that can be a hydrogen atom in R _{7A to} R _13A and X (that is, R _{7A to} R _13A and a hydrogen atom in R _{7A to} R _13A , and a substituent as X) having at least one of them as a bond, in either the main chain or the side chain of the repeating unit Good.

  As a preferable form of the repeating unit (A1-2), a repeating unit having a structure represented by the following general formula (A1-4) can be given.

In general formula (A1-4),
R _14A and R _15A each independently represents a hydrogen atom or a substituent.
L ₂ represents a linking group forming a ring structure.
At least two of R _14A , R _15A and L ₂ may be bonded to each other to form a ring structure.
However, at least one of R _14A , R _15A and L ₂ represents a cyano group or a substituent having a cyano group.
The repeating unit having the structure represented by the general formula (A1-4) has the structure represented by the general formula (A1-4) as a portion that can be a hydrogen atom in R _{14A to} R _15A and L ₂ (that is, R _14A hydrogen atom as to R _15A and R _14A to R _15A, as at least one bond of the hydrogen atoms) included in the substituents represented by L _2, have any of the main chain and side chain of the repeating unit Just do it.

  Another preferred form of the repeating unit (A1-2) includes a repeating unit having a structure represented by the following general formula (A1-5).

In general formula (A1-5),
R _16A and R _17A each independently represents a hydrogen atom or a substituent.
L ₃ represents a linking group forming a ring structure.
At least two of R _16a , R _17A and L ₃ may be bonded to each other to form a ring structure.
However, at least one of R _16a , R _17A and L ₃ represents a cyano group or a substituent having a cyano group.
The repeating unit having the structure represented by the general formula (A1-5) has the structure represented by the general formula (A1-5) at a position that can be a hydrogen atom in R _{16A to} R _17A and L ₃ (that is, _A hydrogen atom as R _{16A to} R _17A and a hydrogen atom in a substituent as R _{16A to} R _17A and L ₃ ) as a bond, and has either a main chain or a side chain of the repeating unit. Just do it.

  Another preferred form of the repeating unit (A1) includes a repeating unit having a structure represented by the following general formula (A1-6).

In general formula (A1-6),
R _18A represents a hydrogen atom or a substituent.
L ₁ represents a linking group that links the carbon atom at the 2-position of the lactone ring and the oxygen atom of the lactone ring to form a lactone ring structure.
R _18A and L ₁ may combine with each other to form a ring structure.
The repeating unit having the structure represented by the general formula (A1-6) has the structure represented by the general formula (A1-6) as a portion that can be a hydrogen atom in R _18A and L ₁ (that is, as R _18A And at least one of the hydrogen atom in the substituent as R _18A and L ₁ ) as a bond, it may be in either the main chain or the side chain of the repeating unit.

  As a preferable form of the repeating unit (A1-6), a repeating unit having a structure represented by the following general formula (A1-7) can be given.

In general formula (A1-7),
R _{19A to} R _23A each independently represents a hydrogen atom or a substituent. At least two of R _{19A to} R _23A may be bonded to each other to form a ring structure.
The repeating unit having the structure represented by the general formula (A1-7) has the structure represented by the general formula (A1-7) at a position that can be a hydrogen atom in R _{19A to} R _23A (that is, R _19A to as at least one bond of the hydrogen atoms) included in the substituents represented by hydrogen atoms and R _19A to R _23A as R _23A, only to have any of the main chain and side chain of the repeating unit.

  Examples of the repeating unit having a structure represented by the general formulas (A1-2) to (A1-7) include, for example, the general formulas (A1-2) to (A1-7) at any position in the skeleton of the following repeating unit. ) Can be mentioned. That is, it is obtained by substituting an arbitrary hydrogen atom in the following repeating unit with at least one of the hydrogen atom in the structure represented by the general formulas (A1-2) to (A1-7) as a bond. .

  The repeating unit (A1) is preferably a repeating unit derived from an ethylenic double bond, and more preferably a repeating unit derived from a (meth) acrylic acid derivative.

  As more preferred embodiments of the repeating units represented by the general formulas (A1-2) to (A1-7), there can be mentioned the repeating units represented by the following general formula (A1-8).

In general formula (A1-8),
R ^a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
Lac represents a structure represented by any one of the general formulas (A1-2) to (A1-7).

The substituents in formulas (A1-3) to (A1-7) are the same as those in formula (A1-2).
The substituent having a cyano group in formulas (A1-3) to (A1-7) is the same as that in formula (A1-2).
In the general formulas (A1-2) to (A1-7), examples of the ring structure formed by combining at least two substituents with each other include a 5- to 6-membered ring. The ring structure may have a substituent such as a cyano group.
In the general formulas (A1-4) to (A1-5), examples of the ring structure formed by L ₂ and L ₃ include a norbornane structure. The ring structure may have a substituent such as a cyano group.

  Hereinafter, although the specific example of a repeating unit (A1) is given, this invention is not limited to this. The methyl group present at the α-position in the methacrylate of the specific example may be a hydrogen atom.

<Repeating unit having a cyano group (A2)>
Resin (A) of this invention contains the repeating unit (A2) which has a cyano group different from a repeating unit (A1) with the repeating unit (A1) which has the said cyano group and lactone group.
The repeating unit (A2) having a cyano group may contain a lactone structure as long as it is different from the repeating unit (A1).

  1-4 are preferable and, as for the number of the cyano groups which the repeating unit (A2) which has a cyano group has, 1-2 pieces are more preferable.

  Examples of the repeating unit (A2) having a cyano group include those in which a substituent having a cyano group is bonded to an arbitrary position in the skeleton of the following repeating unit.

  Hereinafter, preferred specific examples of the repeating unit (A2) having a cyano group are shown. In addition, examples in which the methyl group existing at the α-position in the methacrylate of the specific example is substituted with a hydrogen atom, a hydroxymethyl group, a trifluoromethyl group, and a lower alkyl group having 2 to 4 carbon atoms may be mentioned as preferable examples. I can do it.

The method for synthesizing the monomer corresponding to the repeating unit (A1) is not particularly limited, but the monomer is synthesized via the alkenyl carboxylic acid (intermediate I) or its ester (intermediate II) shown in Scheme 1 and Scheme 2 below. Is preferred. Epoxidation in Scheme 1 may use a general method using mCPBA or dimethyldioxirane. When starting from Intermediate II, the same epoxycarboxylic acid can be obtained by hydrolyzing the ester moiety after epoxidation. The resulting epoxide is treated under acidic conditions to lead to hydroxylactone, and a monomer can be efficiently obtained by attaching a polymerizable group to the resulting hydroxyl group. Monomerization may use any esterification reaction.
For the lactonization in Scheme 2, a general lactonization reaction may be used. For example, a halolactonization reaction can be exemplified, and an iodolactonization reaction can be preferably exemplified. By substituting the iodine atom of the obtained iodolactone with a substituent containing a polymerizable group, it can be led to a monomer.
The monomer corresponding to the repeating unit (A2) can be synthesized by a known method.

The acid-decomposable resin (A) is a resin whose solubility in an alkaline developer increases by the action of an acid, and decomposes into the main chain or side chain of the resin or both the main chain and side chain by the action of an acid. And a group that generates an alkali-soluble group (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 capable of decomposing with an acid is a group in which a hydrogen atom of an alkali-soluble group such as a —COOH group or —OH group is substituted with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ , R ₃₆ and R ₃₉ may be bonded to each other to form a ring.
R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
In the present invention, the acid-decomposable group is preferably an acetal group or a tertiary ester group.

  When the positive resist composition of the present invention is irradiated with ArF excimer laser light, the acid-decomposable resin (A) 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 preferable.

  Examples of the resin having a monocyclic or polycyclic alicyclic hydrocarbon structure that decomposes by the action of an acid and increases the solubility in an alkali developer include the following general formulas (pI) to (pV) A resin having a repeating unit having a partial structure containing a cyclic hydrocarbon and at least one repeating unit selected from the group of repeating units represented by the following general formula (II-AB) is preferable.

In general formulas (pI) to (pV),
R ₁₁ represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and Z represents an atomic group necessary for forming a cycloalkyl group together with the carbon atom.
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.

  Among (pI) to (pV), the following structures can be given as particularly preferred forms.

In the general formula (pI ′),
R ₁₁ ′ represents an alkyl group having 1 to 8 carbon atoms.
X _p1 represents an oxygen atom or a methylene group which may have a substituent.
R _{p1 to} R _p4 may be the same as or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R _{p1 to} R _p4 may be bonded to each other to form a ring structure.
In the general formula (pI '')
R ₁₁ ″ represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, preferably a cycloalkyl group having 3 to 8 carbon atoms.
Z _p1 represents a single bond or —C (R _p7 ) ═C (R _p8 ) —.
R _{p5 to} R _p8 may be the same or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and may be bonded to each other to form a ring structure.
n represents an integer of 2 to 8.

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 ′ represents an alkyl group or a cycloalkyl group.
Here, 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 in R _{11 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, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and 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 structure represented by the general formulas (pI) to (pV) in the resin can form an acid-decomposable group by using it for protecting an alkali-soluble group. 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, a hydrogen atom of a sulfonic acid group is substituted with a structure represented by general formulas (pI) to (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 general formula (II-AB),
Examples of the halogen atom for 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.

Examples of the skeleton of the alicyclic hydrocarbon formed include those similar to the cycloalkyl groups of R _{12 to} R _{25 in} the general formulas (pI) to (pV).

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 acid-decomposable resin (A) according to the present invention, the group capable of decomposing by the action of an acid is a repeating group having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pI) to general formula (pV). It can be contained in at least one repeating unit among the units, the repeating unit represented by the general 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 acid-decomposable resin (A) of the present invention does not have a cyano group and may have 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 acid-decomposable resin (A) of the present invention more 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 (Rb ₂ ). Preferred substituents (Rb ₂ ) include 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, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. n2 represents an integer of 0 to 4. When n2 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.

As the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-16), R _{13 in the} above general formula (II-AB1) or (II-AB2) may be used. A group having a group represented by general formula (LC1-1) to (LC1-16) at least one of 'to R ₁₆ ' (for example, R _{5 of} -COOR ₅ is represented by formula (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 acid-decomposable resin (A) 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 general formula (VIIa),
R ₂ c to 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). A group having the group represented by the above general formula (VIIa) or (VIIb) (for example, R _{5 of} —COOR ₅ represents a group represented by the general formula (VIIa) or (VIIb)), and the following general group The repeating unit etc. which are represented by a formula (AIIa) or (AIIb) can be mentioned.

In 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 acid-decomposable resin (A) 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 acid-decomposable resin (A) 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, and 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 acid-decomposable resin (A) 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.
R _f1 represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group or an optionally substituted alkyl group, cycloalkyl group, acyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylmethyl group. , Alkoxymethyl group, 1-alkoxyethyl 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.

  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), R _f2 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group represented by R _f2 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 represents 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 acid-decomposable resin (A) of the present invention has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution and heat resistance, which are general necessary characteristics of resist. Various repeating structural units can be included for the purpose of adjusting properties, sensitivity and the like.

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

  As a result, the performance required for the acid-decomposable resin (A), in particular, (1) solubility in coating solvents, (2) film-formability (glass transition point), (3) alkali developability, (4) film Fine adjustments such as slippage (hydrophobic and hydrophobic group selection), (5) adhesion of unexposed portions to the substrate, and (6) dry etching resistance are possible.

  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 the acid-decomposable resin (A), the molar ratio of each repeating structural unit is the resist dry etching resistance, the standard developer suitability, the substrate adhesion, the resist profile, and the general required performance of the resist, resolving power and heat resistance. It is appropriately set to adjust the property, sensitivity, etc.

Preferred embodiments of the acid-decomposable resin (A) of the present invention include the following.
(1) What contains the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by 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) Those having a repeating unit represented by 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 acid-decomposable resin (A), 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 to 40 in all repeating structural units. Mol%.

  In the acid-decomposable resin (A), the content of the repeating unit (A1) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol% in all repeating units. .

  In the acid-decomposable resin (A), the content of the repeating unit having a cyano group (the total amount of (A1) and (A2)) is preferably from 5 to 100 mol%, more preferably from 10 to 90% in all repeating units. It is mol%, More preferably, it is 20-80 mol%.

  In the acid-decomposable resin (A), 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 mol% in all repeating structural units. Is more preferable, more preferably 35 to 65 mol%, still more preferably 40 to 60 mol%.

  In the acid-decomposable resin (A), the content of the repeating unit represented by the general formula (II-AB) is preferably from 10 to 60 mol%, more preferably from 15 to 55 mol%, more preferably from all repeating structural units. 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. 99 mol% 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 above 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 acid-decomposable resin (A) 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.

The acid-decomposable resin (A) 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, the generation of particles during storage 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 acid-decomposable resin (A) 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 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 acid-decomposable resin (A) has a structure in which fluorine atoms are substituted on the main chain and / or side chain of the polymer skeleton, In addition, a resin that decomposes by the action of an acid and increases the solubility in an alkali developer is preferable, and more preferably, a hydroxyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group or a 1-position substituted with a fluorine atom or a fluoroalkyl group A resin containing a group in which the hydroxyl group is protected with an acid-decomposable group, and particularly preferably a resin containing a hexafluoro-2-propanol structure or a structure in which the hydroxyl group of hexafluoro-2-propanol is protected with an acid-decomposable group. By introducing fluorine atoms, it is possible to improve transparency to far ultraviolet light, particularly F ₂ (157 nm) light.

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

In general formulas (FA) to (FG),
R ₁₀₀ to R ₁₀₃ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an aryl group.
R ₁₀₄ and R ₁₀₆ each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and at least one of R ₁₀₄ and R ₁₀₆ represents a fluorine atom or a fluoroalkyl group. R ₁₀₄ and R ₁₀₆ are preferably both a trifluoromethyl group.
R ₁₀₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or a group capable of decomposing by 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 Represents a linking group in which a plurality of the groups are bonded. R ₂₄ represents a hydrogen atom or an alkyl group.
R ₁₀₇ and R ₁₀₈ each independently represent 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 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a group capable of decomposing by 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 acid-decomposable resin (A) is preferably 2,000 to 200,000 as a polystyrene conversion value by the GPC method. By setting the weight average molecular weight to 2,000 or more, heat resistance, dry etching resistance, and exposure latitude can be improved, and by setting the weight average molecular weight to 200,000 or less, development defects due to improved developability. The improvement effect is obtained, and the film forming property can be improved because the viscosity is lowered. The molecular weight is more preferably 5,000 to 50,000, still more preferably 7,000 to 30,000, and most preferably 8000 to 16000.
The dispersity (Mw / Mn) of the acid-decomposable resin (A) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1.0 to 2. 0. 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 acid-decomposable resin (A) according to the present invention in the whole composition is preferably 40 to 99.99% by mass in the total solid content, more preferably 50 to 50%. It is 99 mass%, More preferably, it is 80-96 mass%.

[3] (B) Compound that generates acid upon irradiation with actinic ray or radiation Compound that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generator”) used in the positive resist composition of the present invention. Will be described below.
The acid generator used in the present invention can be selected from compounds generally used as an acid generator.
In other words, photoinitiators for photocationic polymerization, photoinitiators for radical photopolymerization, photodecolorants for dyes, photochromic agents, or active rays or radiations such as far ultraviolet rays and X-rays used in micro resists, etc. 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.

  Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ 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.

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, aryldicycloalkylsulfonium compounds, and the like.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like. 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 (e.g., having from 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, a phenylthio group, or the like, 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 alkoxy groups having 1 to 12 carbon atoms, most preferably alkyl having 1 to 4 carbon atoms. Group, an alkoxy group having 1 to 4 carbon atoms. 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.

Examples of the non-nucleophilic anion as X ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

  Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  Examples of the aliphatic group in the aliphatic sulfonate anion include, for example, an alkyl group having 1 to 30 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- Butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl And an eicosyl group and a cycloalkyl group having 3 to 30 carbon atoms, specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, and the like.

  The aromatic group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.

  Examples of such substituents include nitro groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), carboxyl groups, hydroxyl groups, amino groups, cyano groups, and alkoxy groups (preferably having 1 to 5 carbon atoms). ), A cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms). ), An alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  Examples of the aliphatic group in the aliphatic carboxylate anion include those similar to the aliphatic group in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aromatic groups as in the aromatic sulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylmethyl group.

  The aliphatic group, aromatic group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent include aliphatic sulfonic acid The same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like as in the anion can be exemplified.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. These alkyl groups may have a substituent, and examples of the substituent include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, and the like, which are substituted with a fluorine atom. Alkyl groups are preferred.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the non-nucleophilic anion of X ⁻ include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is particularly preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, an aromatic sulfonic acid anion having a fluorine atom, most preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

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 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 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, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, or an alkoxycarbonylmethyl group, most preferably Is a linear, branched 2-oxoalkyl group.

The alkyl group as R _{201 to} R ₂₀₃ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. Butyl group, pentyl group and the like. More preferable examples of the alkyl group include a 2-linear or branched oxoalkyl group and 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. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

  The 2-oxoalkyl group may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group or cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, 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), 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, an allyl group or a vinyl group.

Any two or more of R _1c to R _7c, and R _x and R _y may be bonded to each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond May be included. Examples of the group formed by combining any two or more of R _{1c to} R _7c and R _x and R _y are a butylene group and a pentylene group.

Zc ⁻ 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 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, A linear or branched pentyl group can be exemplified.

The cycloalkyl group as R _{1c to} R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include 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, such} as a 2-oxoalkyl group and a 2-oxocycloalkyl group. An alkoxycarbonylmethyl group is more preferable.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

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.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like.

The alkyl group as R ₂₀₄ to R ₂₀₇ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group.

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 non-nucleophilic anion as X ^{− in} formula (ZI).

  Preferred examples of the acid generator include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formula (ZIV), two Ar ₃ each independently represents an aryl group.
R ₂₀₈ in the general formulas (ZV) and (ZVI) each independently represents an alkyl group, a cycloalkyl group or an aryl group, and the alkyl groups as R _{204 to} R ₂₀₇ in the general formulas (ZI) to (ZIII) , Cycloalkyl group or aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

  Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

  As the acid generator in the present invention, particularly preferably, an anion structure containing an alkyl group having 4 or less carbon atoms substituted with a fluorine atom, a cycloalkyl group substituted with a fluorine atom, or an aromatic group substituted with a fluorine atom; An acid generator having a triarylsulfonium cation structure. Such acid generators are preferably those represented by the following general formulas (B1) to (B3).

In general formulas (B1) to (B3),
R ₁ represents an alkyl group, an alicyclic hydrocarbon group, a hydroxyl group, a carboxyl group, an alkoxy group or a halogen atom.
y represents 0 or an integer of 1 to 5 independently of each other. When y is an integer of 2 or more, two or more R _{1 s} may be the same or different.
Q _{1 to} Q ₄ are each independently an alkyl group having 1 to 8 carbon atoms substituted with a fluorine atom, a cycloalkyl group substituted with a fluorine atom, an aryl group substituted with a fluorine atom, or a fluorinated alkyl group. Represents a substituted aryl group.
In particular, in the general formula (B2), Q ₂ and Q _{3 which} are bonded to form a ring structure are preferable from the viewpoint of improving exposure latitude.

As the alkyl group for R ₁ , a linear or branched alkyl group having 1 to 15 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Can be mentioned.
The alicyclic hydrocarbon group for R ₁ is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The alkyl group substituted with a fluorine atom Q ₁ to Q _4, for _{example, -CF 3, -C 2 F 5} , -n-C 3 F 7, -n-C 4 F 9, -n-C 8 _{F 17, -CF (CF 3)} 2, -CH (CF 3) 2, - (CF 2) 2 OCF 2 CF 3, - (CF 2) 2 O (CH 2) 3 CH 3, - (CF 2) _{2 O (CH 2) 13 CH} 3, - (CF 2) 2 O (CF 2) 2 (CH 2) 3 CH 3 and the like. The alkyl group having 4 or less carbon atoms substituted with a fluorine atom of Q _{1 to} Q ₄ may further have a substituent such as an alkoxy group or a fluoroalkoxy group.
Examples of the aryl group substituted with a fluorine atom of Q _{1 to} Q ₄ include 2,3,4,5,6-pentafluorophenyl group, 2,3,4-trifluorophenyl group, and 2,4-difluoro. A phenyl group, 4-fluorophenyl group, 4-undecanyloxy-2,3,5,6-tetrafluorophenyl group and the like can be mentioned.
Examples of the aryl group substituted with a fluorinated alkyl group of Q _{1 to} Q ₄ include a 3-trifluoromethylphenyl group, a 3,5-bis (trifluoromethyl) phenyl group, a 4-trifluoromethylphenyl group, And 4-n-nonafluorobutylphenyl group.

  Examples of particularly preferable acid generators are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the positive resist composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, still more preferably, based on the total solid content of the positive resist composition. Is 1-7 mass%.

[4] Solvent The positive resist composition of the present invention is used by dissolving each component in a predetermined solvent.
Solvents that can be used include, for example, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol, propylene glycol, 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, ethyl ethoxypropionate, toluene, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, pyruvin Acid methyl, ethyl pyruvate, propyl pyruvate, N, N-dimethylacetamide, N, - dimethylformamide, dimethyl sulfoxide, N- methylpyrrolidone, and tetrahydrofuran.

  In the present invention, the solvent may be used alone or mixed, but it is preferable to use a mixed solvent containing two or more kinds of 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.

[5] Basic Compound The positive resist composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.

  Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl having 1 to 20 carbons, a cycloalkyl group having 3 to 20 carbons or an aryl group having 6 to 20 carbons, R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a C 3-20 hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.

  Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and may have a substituent. More preferable compounds include compounds having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, a hydroxyl group and / or Or the aniline derivative which has an ether bond etc. can be mentioned.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undec-7-ene. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of aniline compounds include 2,6-diisopropylaniline and N, N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  In the positive resist composition of the present invention, the basic compound is used alone or in combination of two or more. 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 positive resist composition. In order to obtain a sufficient addition effect, 0.001% by mass or more is preferable, and 10% by mass or less is preferable in terms of sensitivity and developability of the non-exposed area.

[6] Dissolution-inhibiting compound The positive resist composition of the present invention decomposes by the action of an acid to increase the solubility in an alkaline developer, and has a molecular weight of 3000 or less (hereinafter referred to as “component (E)”). (Also referred to as “dissolution inhibitor compound”).
As a dissolution inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkaline developer, it does not decrease the permeability of 220 nm or less. An alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group is preferred. 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 positive 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 positive resist composition.

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

[7] Surfactant The positive resist composition of the present invention preferably contains a surfactant, and is a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant, fluorine It is more preferable to contain either one or two or more surfactants containing both atoms and silicon atoms.

  When the positive resist composition of the present invention contains fluorine and / or a silicon-based surfactant, adhesion and development defects are obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It is possible to provide a resist pattern with less.

  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, 4430 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189 , F113, F110, F177, F120, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (Manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M , EF135M, EF351, 352, EF801, EF802, EF 01 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218, 222D (manufactured by Neos) 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.

  Surfactants may be used alone or in several combinations.

  The amount of the 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 positive resist composition (excluding the solvent).

<Other additives>
In the positive resist composition of the present invention, if necessary, a dye, a light absorber, a plasticizer, a surfactant other than the component (F), a photosensitizer, and a compound that promotes solubility in a developer. Etc. can be contained.

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

  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 resin as the component (A). The amount is preferably 50% by mass or less from the viewpoint of suppressing development residue and preventing pattern deformation during development.

  Such phenolic 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, European Patent 219294, and the like. 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.

  As the plasticizer, in addition to a commercially available plasticizer, any compound having a molecular weight of 1000 or less that is compatible with the polymer to be used and has an effect of lowering the softening point of the film may be used without particular limitation. From the viewpoint of compatibility, a molecular weight of 750 or less is preferable, and a molecular weight of 500 or less is more preferable. A compound having a normal pressure boiling point of 300 ° C. or higher and a melting point of 20 ° C. or lower is preferable. Specific examples include diisobutyl phthalate, tricresyl phosphate, triethylene glycol diphenyl ether, diethylene glycol dibenzoate, and triethylene glycol diacetate.

  As the light absorber, any compound that has absorption at the exposure wavelength and does not generate an acid upon exposure can be used without particular limitation. When the light source wavelength is 193 nm, a compound containing an aromatic ring is preferred. Specific examples include benzene derivatives, naphthalene derivatives, anthracene derivatives, furan derivatives, thiophene derivatives, indole derivatives, and the like.

  In the present invention, a surfactant other than the (F) 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 positive resist composition of the present invention is used by dissolving the above components in a predetermined solvent, preferably the mixed solvent, and applying the solution on a predetermined support as follows.

For example, a positive resist composition is coated on a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate coating method such as a spinner or a coater, and dried to form a resist film. Form.
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 (monomer synthesis)
Compound A described in Monatsh.Chem. 1997 (128), 509-528 was reacted in acetone solvent under the conditions of 1.5 equivalents of methacrylic acid chloride, 2 equivalents of triethylamine, ice-cooled, reaction time of 1 hour, and column chromatography. By purifying with (hexane: ethyl acetate = 10: 1), oily monomer-1 was obtained in a yield of 72%.

Synthesis Example 1 (Synthesis of Resin (A-1))
Monomer-1, monomer-2, and monomer-3 represented by the following structural formula were charged at a ratio (molar ratio) of 30/30/40, and PGMEA (propylene glycol monomethyl ether acetate) / PGME (propylene glycol monomethyl ether) = It melt | dissolved in 7/3 (mass ratio), and 450 g of solutions with a solid content concentration of 15 mass% were prepared. 1 mol% of Wako Pure Chemical Co., Ltd. polymerization initiator V-601 was added to this solution, and PGMEA (propylene glycol monomethyl ether acetate) / PGME (propylene glycol monomethyl ether) heated to 100 ° C. for 6 hours under a nitrogen atmosphere. = 7/3 (mass ratio) was added dropwise to 50 g of the mixed solution. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of a mixed solvent of hexane / ethyl acetate = 9/1, and the precipitated white powder was collected by filtration to recover the target resin (A-1). did.
The polymer composition ratio determined from NMR was 30/30/40. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7700, and dispersion degree 1.71.

Synthesis Example 3 (Synthesis of Resin (A-2))
Monomer-4, monomer-5, and monomer-6 represented by the following structural formula were charged at a ratio (molar ratio) of 40/30/30 and dissolved in cyclohexanone to prepare 450 g of a solution having a solid content concentration of 15% by mass. . To this solution, 1 mol% of a polymerization initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise to 50 g of cyclohexanone heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of methanol, and the precipitated white powder was collected by filtration to recover the target resin (A-2).
The polymer composition ratio determined from NMR was 40/30/30. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 9200, and dispersion degree 1.89.

Resin (A-3)-(A-22) and resin (P-1) and (P-2) were synthesize | combined like the synthesis examples 2-3.
Table 1 below shows the structures, composition ratios, weight average molecular weights, and dispersities of the resins (A-1) to (A-22) and the resins (P-1) and (P-2).

Examples 1-24 and Comparative Examples 1-2
<Resist preparation>
A solution shown in Table 2 below was prepared, 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 shown in Table 2.

<Resist 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. A positive resist solution prepared thereon was applied and baked at 115 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (PAS5500 / 1100, NA0.75, σo / σi = 0.85 / 0.55 manufactured by ASML). Thereafter, heating was performed at 110 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

Exposure latitude (EL):
The amount of exposure that allows post-heating immediately after exposure to reproduce the mask pattern of line and space with a line width of 80 nm is the optimum amount of exposure, and the pattern size allows 80 nm ± 10% when the amount of exposure is changed The exposure latitude was expressed as a percentage by dividing this value by the optimum exposure amount.

Pattern collapse:
An exposure amount that reproduces a 110 nm line and space 1: 1 mask pattern is an optimum exposure amount, and a dense pattern of line and space 1: 1 does not collapse at a finer mask size when exposed at the optimum exposure amount. The line width to be resolved was defined as the limit pattern collapse line width. A smaller value indicates that a finer pattern is resolved without falling, and that pattern falling is less likely to occur.

Scum:
Development residue (scum) at a line width of 80 nm was observed with a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.). The case where no scum was observed was marked with ○, the case where slight scum was observed was marked with Δ (not applicable), and the case where scum was markedly observed was marked with ×.

  Hereinafter, abbreviations in the table are shown.

  [Acid generator]

[Basic compounds]
N-1: N, N-dibutylaniline
N-2: 2-phenylbenzimidazole N-3: N, N-dihydroxyethylaniline
N-4: 2,4,5-triphenylimidazole
N-5: 2,6-diisopropylaniline
N-6: Hydroxyantipyrine
N-7: Trismethoxymethoxyethylamine
N-8: Triethanolamine

  〔Additive〕

[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-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: KH-20 (Asahi Kasei Corporation)
W-6: PF6320 (made by OMNOVA)

〔solvent〕
a-gun SL-1: Propylene glycol monomethyl ether acetate SL-2: Propylene glycol monomethyl ether propionate SL-3: 2-heptanone
b-gun SL-4: Ethyl lactate
SL-5: Propylene glycol monomethyl ether SL-6: Cyclohexanone
c-gun SL-7: γ-butyrolactone
SL-8: Propylene carbonate

  From Table 3, it is clear that the positive resist composition of the present invention has good characteristics of exposure latitude (EL), pattern collapse, and scum.

[Immersion exposure evaluation]
<Resist preparation>
The components of Examples 1 to 22 shown in Table 3 were dissolved in a solvent to prepare a solution, which 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. A positive resist solution prepared thereon was applied 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 22 had good image forming ability even in the exposure method through the immersion liquid.
Further, 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. A positive resist solution prepared thereon was applied and baked at 120 ° C. for 90 seconds to form a 250 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser immersion scanner (NA 0.85). As the immersion liquid, ultrapure water having impurities of 5 ppb or less was used. Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.
The positive resist composition of the present invention was able to obtain good results in immersion exposure as well as in normal exposure.

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 (4)

(A) A resin containing at least two types of repeating units having a cyano group, wherein at least one of the repeating units having a cyano group is a repeating unit (A1) further having a lactone structure, A resin whose solubility in an alkaline developer is increased by
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
A positive resist composition comprising: The positive resist composition according to claim 1, wherein the repeating unit (A1) is a repeating unit having a structure represented by the following general formula (A1-2).

In general formula (A1-2),
R _{1A to} R _6A each independently represents a hydrogen atom or a substituent. However, at least one of R _{1A to} R _6A represents a cyano group or a substituent having a cyano group. At least two of R _{1A to} R _6A may be bonded to each other to form a ring structure. The positive resist composition according to claim 1, wherein the repeating unit (A1) is a repeating unit having a structure represented by the following general formula (A1-6).

In general formula (A1-6),
R _18A represents a hydrogen atom or a substituent.
L ₁ represents a linking group that links the carbon atom at the 2-position of the lactone ring and the oxygen atom of the lactone ring to form a lactone ring structure.
R _18A and L ₁ may combine with each other to form a ring structure.   A pattern forming method comprising: forming a resist film from the positive resist composition according to claim 1; and exposing and developing the resist film.

Images