JP6145303B2 - Resist composition and method for producing resist pattern - Google Patents

Description

  The present invention relates to a resist composition, a method for producing a resist pattern using the resist composition, and the like.

Patent Document 1 describes a resist composition comprising a resin composed of a structural unit represented by the formula (u-A) and a structural unit represented by the formula (u-C), and triphenylsulfonium triflate. ing.
Further, it is known that when a resist pattern is formed from a resist composition by photolithography, a positive resist pattern is obtained when developed with an alkaline developer, and a negative resist pattern is obtained when developed with an organic solvent ( Non-patent document 1).

JP 2000-122294 A

Monthly display '11 June issue issued by Techno Times p. 31

  A resist pattern formed by a conventional resist composition may not always satisfy the pattern collapse resistance (PCM).

The present invention includes the following inventions.
[1] A resist composition comprising a resin comprising a structural unit represented by formula (I) and a structural unit having an acid labile group, an acid generator, and a compound represented by formula (II).
[In the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —O—, ^* —A ² —CO—O—, ^* —A ² —CO—O—A ³ —CO—O—, or ^* —A ² —O—CO. -A ³ represents a -O-.
* Represents a bond with -O-.
A ² and A ³ each independently represents an alkanediyl group having 1 to 6 carbon atoms. ]
[In the formula (II),
Ring W ¹ represents a saturated heterocyclic ring having 2 to 36 carbon atoms.
R ³ represents a hydrocarbon group having 1 to 30 carbon atoms, and one or more —CH ₂ — contained in the hydrocarbon group is replaced with —O— or —CO—. ]
[2] The resist composition according to [1], wherein the compound represented by the formula (II) is a compound represented by the formula (II-1).
[In the formula (II-1),
Ring W ¹ represents the same meaning as described above.
A ²⁰ represents a divalent hydrocarbon group having 1 to 29 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—. ]
[3] The resist composition according to [1] or [2], further containing a solvent.
[4] (1) A step of applying the resist composition according to any one of [1] to [3] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) A method for producing a resist pattern, comprising a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

  An object of the present invention is to provide a resist composition capable of producing a resist pattern having excellent pattern collapse resistance (PCM).

The term "(meth) acrylic monomer" as used herein means at least one monomer having a structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " . Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

<Resist composition>
The resist composition of the present invention comprises:
A resin comprising a structural unit represented by formula (I) and a structural unit having an acid labile group (hereinafter sometimes referred to as “resin (A)”),
An acid generator (hereinafter sometimes referred to as “acid generator (B)”), and
A compound represented by the formula (II) (hereinafter sometimes referred to as “compound (II)”) is contained.
It is preferable that the resist composition of the present invention further contains a solvent (E).
The resist composition of the present invention may further contain a basic compound (C).

<Resin (A)>
The resin (A) has a structural unit represented by the formula (I) and a structural unit having an acid labile group, and may further have a structural unit having no acid labile group. .
In the present specification, the “acid labile group” is a group having a leaving group and forming a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group by contact with an acid. Means.

<Structural unit represented by formula (I)>
The resin (A) has a structural unit represented by the formula (I) (hereinafter sometimes referred to as “structural unit (I)”).
[In the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —O—, ^* —A ² —CO—O—, ^* —A ² —CO—O—A ³ —CO—O—, or ^* —A ² —O—CO. -A ³ represents a -O-.
* Represents a bond with -O-.
A ² and A ³ each independently represents an alkanediyl group having 1 to 6 carbon atoms. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. , Preferably it is a C1-C4 alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom of R ¹ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro group. Examples include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group of A ² and A ³ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group and hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples include 4-diyl group and 2-methylbutane-1,4-diyl group.
A ¹ is preferably a single bond or ^* —A ² —CO—O—, more preferably a single bond, —CH ₂ —CO—O— or —C ₂ H ₄ —CO—O—. .

Specific examples of the structural unit (I) are shown below.

Regarding the structural units represented by formula (aa-1) to formula (aa-6), structural units in which the methyl group corresponding to R ¹ is replaced with a hydrogen atom are also exemplified as specific examples of structural unit (I). Can do.

The structural unit (I) is derived from a compound represented by the formula (I ′) (hereinafter sometimes referred to as “compound (I ′)”).
[In formula (I ′), R ¹ and A ¹ represent the same meaning as described above. ]

The compound represented by the formula (I′-1), wherein A ¹ in the compound (I ′) is * —CH ₂ —CO—O— (* represents a bond to —CO—O—), The compound represented by formula (I′-1-a) can be obtained by reacting the compound represented by formula (I′-1-b) in a solvent. Here, methylene chloride, tetrahydrofuran, acetonitrile, and the like are preferably used as the solvent.
[Wherein R ¹ represents the same meaning as described above. ]

The compound represented by the formula (I′-1-a) is obtained by reacting the compound represented by the formula (I′-1-c) with the compound represented by the formula (I′-1-d). Can be obtained. This reaction is preferably carried out in the presence of a solvent such as methylene chloride, tetrahydrofuran and acetonitrile.
[Wherein R ¹ represents the same meaning as described above. ]
In this reaction, a condensation catalyst such as dicyclohexylcarbodiimide may be used.

Examples of the compound represented by the formula (I′-1-c) include the following compounds.
If a compound having A ¹ and R ¹ corresponding to the target compound (I ′) is used as the compound represented by the formula (I′-1-c), the target compound (I ′) can be obtained. . The compounds represented by formula (I′-1-c) and formula (I′-1-d) are easily available from the market.

Examples of compound (I ′) include the following.

In the compound (I ′) represented by each of the formulas (aa′-1) to (aa′-6), the structural unit in which the methyl group corresponding to R ¹ is replaced by a hydrogen atom is also represented by the compound (I ′). Specific examples can be given.

  The content of the structural unit (I) is preferably from 1 to 80 mol%, more preferably from 2 to 75 mol%, still more preferably from 3 to 70 mol%, based on all structural units of the resin (A). It is particularly preferably 5 to 65 mol%.

<Structural unit having acid labile group>
A structural unit having an acid labile group (hereinafter sometimes referred to as “acid labile structural unit”) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “acid labile monomer (a1)”). .
Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2).

[In the formula (1), R ^a1 , R ^a2 and R ^a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof. R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]
[In Formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent hydrocarbon group. May be replaced by -O- or -S-. ]

^Examples of the alkyl group represented by R ^a1 , R ^a2 and R ^a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group represented by R ^a1 , R ^a2 and R ^a3 may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group is an alkyl group. May be substituted. In this case, the carbon number of the alicyclic hydrocarbon group is 20 or less including the carbon number of the alkyl group.
Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond).
Examples of the alicyclic hydrocarbon group substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
In the formula (1), the alicyclic hydrocarbon group represented by R ^a1 , R ^a2 and R ^a3 preferably has 3 to 16 carbon atoms.

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group include the following groups. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms. In each formula, R ^a3 has the same meaning as described above, and * represents a bond to —O—.

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are alkyl groups, preferably a tert-butoxycarbonyl group), 2-alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 , R ^a2 and a carbon atom form an adamantyl group, and R ^a3 is an alkyl group) and 1- (adamantane-1- Yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

Examples of the hydrocarbon group represented by R ^{a1 ′} , R ^{a2 ′} and R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenylyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the divalent hydrocarbon group formed by combining R ^{a2 ′} and R ^{a3 ′} include groups in which one hydrogen atom has been removed from the hydrocarbon groups of R ^{a1 ′ to} R ^{a3 ′} .

In Formula (2), it is preferable that at least one of R ^{a1 ′} and R ^{a2 ′} is a hydrogen atom.
Specific examples of the group represented by the formula (2) include the following groups. * Represents a bond.

  The acid labile monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond, more preferably a (meth) acrylic monomer having an acid labile group.

  The (meth) acrylic monomer having an acid labile group is preferably one having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. When the resist composition of the present invention uses a resin having a structural unit derived from an acid labile monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group, the resolution of the resist pattern is improved. be able to.

  As a structural unit derived from a (meth) acrylic monomer having an acid labile group represented by the formula (1), preferably a structural unit represented by the formula (a1-1) or a formula (a1-2) Structural units. These may be used alone or in combination of two or more. In this specification, the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) are represented by the structural unit (a1-1) and the structural unit (a1-2), respectively. The monomer that derives the structural unit (a1-1) and the monomer that derives the structural unit (a1-2) may be referred to as a monomer (a1-1) and a monomer (a1-2), respectively.

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]

L ^a1 and L ^a2 are preferably —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, more preferably —O—. k1 is preferably an integer of 1 to 4, more preferably 1.
R ^a4 and R ^a5 are preferably methyl groups.
The alkyl group for R ^a6 and R ^a7 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alkyl group. In this case, the carbon number of the alicyclic hydrocarbon group is 18 or less including the carbon number of the alkyl group. The alicyclic hydrocarbon group preferably has 8 or less carbon atoms, more preferably 6 or less.
Examples of the alkyl group and the alicyclic hydrocarbon group represented by R ^a6 and R ^a7 include the same groups as those represented by R ^a1 , R ^a2 and R ^a3 in the formula (1).
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

As a monomer (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned. Among these, a monomer represented by any one of formula (a1-1-1) to formula (a1-1-8) is preferable, and any one of formula (a1-1-1) to formula (a1-1-4) is preferable. The monomer represented by is more preferable.

Examples of the monomer (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, and 1-ethylcycloheptan-1-yl (meth). Examples include acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, and 1-isopropylcyclopentan-1-yl (meth) acrylate. Monomers represented by the formula (a1-2-1) to the formula (a1-2-12) are preferred, and the formula (a1-2-3) to the formula (a1-2-4) or the formula (a1-2-9) The monomer represented by formula (a1-2-10) is more preferable, and the monomer represented by formula (a1-2-3) or formula (a1-2-9) is more preferable.

  When the resin (A) includes a structural unit represented by the formula (a1-1) and / or a structural unit represented by the formula (a1-2), the total content thereof is the total structure of the resin (A). It is 10-95 mol% normally with respect to a unit, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

As another acid labile monomer (a1), for example, a monomer represented by formula (a1-5) which is a (meth) acrylic monomer having an acid labile group represented by formula (2) (hereinafter “ Monomer (a1-5) ”may be used.
In formula (a1-5),
R ³¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ¹ represents a single bond or a * — [CH ₂ ] _k4 —CO—L ⁴ — group. Here, k4 represents an integer of 1 to 4. * Represents a bond with L ¹ .
L ¹ , L ² , L ³ and L ⁴ each independently represent —O— or —S—.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3.

In formula (a1-5), R ³¹ is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.
L ¹ is preferably an oxygen atom.
One of L ² and L ³ is preferably an oxygen atom and the other is a sulfur atom.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ¹ is preferably a single bond or * —CH ₂ —CO—O—.

Examples of the monomer (a1-5) include the following monomers.

  When the resin (A) has a structural unit derived from the monomer (a1-5), the content is preferably from 1 to 50 mol%, preferably from 3 to 45 mol, based on all structural units of the resin (A). % Is more preferable, and 5 to 40 mol% is more preferable.

<Structural unit without acid labile group>
The structural unit having no acid labile group (hereinafter sometimes referred to as “acid stable structural unit”) is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “acid stable monomer”).
As an acid stable monomer, Preferably, the monomer which has a hydroxyl group or a lactone ring is mentioned. Acid-stable monomer having a hydroxy group (hereinafter sometimes referred to as “acid-stable monomer having a hydroxy group (a2)”) or acid-stable monomer having a lactone ring (hereinafter referred to as “acid-stable monomer having a lactone ring (a3)”) And a resin having a structural unit derived from (sometimes). When the resin has a structural unit derived from such an acid stable monomer, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Acid-stable monomer having a hydroxy group (a2)>
When the resist composition is used for high energy beam exposure such as KrF excimer laser exposure (248 nm), electron beam or EUV (ultra-ultraviolet light), the acid-stable monomer (a2) having a hydroxy group is preferably a hydroxystyrene. An acid stable monomer having a certain phenolic hydroxy group is used. When using short-wavelength ArF excimer laser exposure (193 nm) or the like, the acid-stable monomer (a2) having a hydroxy group is preferably an acid-stable monomer having a hydroxyadamantyl group represented by the formula (a2-1). use. The acid-stable monomer (a2) having a hydroxy group may be used alone or in combination of two or more.

Examples of the acid stable monomer having a hydroxyadamantyl group include a monomer represented by the formula (a2-1).
In formula (a2-1),
L ^a3 represents —O— or ^* —O— (CH ₂ ) _k2 —CO—O—,
k2 represents an integer of 1 to 7. * Represents a bond with -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10.

In the formula (a2-1), L ^a3 is preferably, -O -, - O- (CH 2) f1 -CO-O- and is (wherein f1 is an integer from 1 to 4), more preferably Is —O—.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

As an acid stable monomer (a2-1) which has a hydroxyadamantyl group, the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A monomer represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferable, and represented by any one of formula (a2-1-1) to formula (a2-1-4). The monomer represented by Formula (a2-1-1) or Formula (a2-1-3) is more preferable.

  When the resin (A) includes a structural unit derived from the monomer represented by the formula (a2-1), the content is usually 1 to 45 mol% with respect to all the structural units of the resin (A). , Preferably it is 1-40 mol%, More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

<Acid-stable monomer having a lactone ring (a3)>
The lactone ring possessed by the acid stable monomer (a3) may be, for example, a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, and a monocyclic lactone ring and other rings The condensed ring may be used. Among these lactone rings, a γ-butyrolactone ring or a condensed ring of γ-butyrolactone ring and another ring is preferable. Compound (I ′) is not included in the acid stable monomer (a3).

  The acid-stable monomer (a3) having a lactone ring is preferably represented by the formula (a3-1), the formula (a3-2) or the formula (a3-3). These 1 type may be used independently and may use 2 or more types together.

In formula (a3-1), formula (a3-2) and formula (a3-3),
L ^a4 , L ^a5 and L ^a6 each independently represent —O— or ^* —O— (CH ₂ ) _k3 —CO—O—.
k3 represents an integer of 1 to 7. * Represents a bond with -CO-.
R ^a18 , R ^a19 and R ^a20 each independently represents a hydrogen atom or a methyl group.
R ^a21 represents an alkyl group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5.
R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group, or an alkyl group having 1 to 4 carbon atoms.
q1 and r1 each independently represents an integer of 0 to 3. When p1 is 2 or more, a plurality of R ^a21 are the same or different, when q1 is 2 or more, a plurality of R ^a22 are the same or different, and when r1 is 2 or more, a plurality of R ^a23 are the same or different Different.

^Examples of the alkyl group for R ^a21 , R ^a22 and R ^a23 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and a sec-butyl group.

In formula (a3-1), formula (a3-2) and formula (a3-3), L ^a4 , L ^a5 and L ^a6 are each independently —O— or ^* —O— (CH ₂ ) _k3 —. CO-O- is preferable, and -O- is more preferable. k3 is preferably an integer of 1 to 4, more preferably 1.
R ^a18 , R ^a19 , R ^a20 and R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably 0 to 2, more preferably 0 or 1.

  Examples of the acid-stable monomer (a3) having a lactone ring include monomers described in JP 2010-204646 A. In the following formulas (a3-1-1) to (a3-1-4), (a3-2-1) to (a3-2-4), (a3-3-1) to (a3-3-4) Monomers represented by the following formulas (a3-1-1) to (a3-1-2) and (a3-2-3) to (a3-2-4) are more preferred, A monomer represented by formula (a3-1-1) or (a3-2-3) is more preferable.

  When the resin (A) includes a structural unit derived from the acid-stable monomer (a3) having a lactone ring, the content is usually 5 to 70 mol% with respect to all the structural units of the resin (A), Preferably it is 10-65 mol%, More preferably, it is 10-60 mol%.

When the resin (A) is a resin composed only of the structural unit (I) and the acid labile structural unit, these contents are respectively relative to the total structural unit of the resin (A),
Structural unit (I); 1 to 80 mol%
Acid-labile structural unit; 20-99 mol%
Is preferred,
Structural unit (I); 5-65 mol%
Acid labile structural unit; 35-95 mol%
Is more preferable.

When the resin (A) is a resin composed of the structural unit (I), the acid labile structural unit, and the acid stable structural unit, these content rates are respectively based on the total structural units of the resin (A),
Structural unit (I); 1 to 80 mol%
Acid-labile structural unit; 17-96 mol%
Acid stable structural unit; 3-82 mol%
Is preferred,
Structural unit (I); 2-75 mol%
Acid-labile structural unit; 20 to 93 mol%
Acid stable structural unit; 5-78 mol%
Is more preferred,
Structural unit (I); 5-65 mol%
Acid-labile structural unit; 30 to 90 mol%
Acid stable structural unit; 5 to 65 mol%
Is more preferable.

The resin (A) is preferably a resin comprising a structural unit (I), an acid labile structural unit, and an acid stable structural unit, that is, a compound (I ′), an acid labile monomer (a1), and an acid stable monomer. It is a copolymer.
The acid labile structural unit is preferably at least one of the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), more preferably the structural unit (a1- 1).
The acid stable structural unit is preferably at least one of a structural unit derived from the acid stable monomer (a2) and a structural unit derived from the acid stable monomer (a3). The acid stable monomer (a2) is preferably a monomer represented by the formula (a2-1). The acid stable monomer (a3) is preferably at least one of an acid stable monomer represented by the formula (a3-1) and an acid stable monomer represented by the formula (a3-2).

  The resin (A) may contain a structural unit derived from a monomer having an adamantyl group (particularly the structural unit (a1-1)) in an amount of 15 mol% or more based on the content of the acid labile structural unit. preferable. When the content of the structural unit having an adamantyl group is increased, the dry etching resistance of the resist pattern is improved.

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. can do.
The weight average molecular weight of the resin (A) is preferably 2,500 or more (more preferably 3,000 or more, more preferably 4,000 or more), 50,000 or less (more preferably 30,000 or less, and further preferably 15,000 or less).

  The content of the resin (A) is preferably 80% by mass or more and 99% by mass or less in the solid content of the resist composition. In the present specification, the “solid content in the composition” means the total amount of components excluding the solvent (E) from the total amount of the resist composition. The solid content in the composition and the content of the resin (A) relative thereto can be measured, for example, by a known analysis means such as liquid chromatography or gas chromatography.

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A).
The resin other than the resin (A) is not particularly limited as long as it does not contain the structural unit (I). For example, the structural unit derived from the acid labile monomer (a1) or the structural unit derived from the acid stable monomer In addition, resins composed of structural units derived from known monomers used in this field can be mentioned.
When the resist composition of this invention contains resin other than resin (A), these content rates are 0.1-50 mass% normally with respect to the total amount of resin, Preferably 0.5-30 It is mass%, More preferably, it is 1-20 mass%.

<Acid generator (B)>
The acid generator (B) is classified into a nonionic type and an ionic type, and any of them may be used in the resist composition of the present invention. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonates), sulfones (e.g. disulfone, ketosulfone, sulfonyldiazomethane) and the like. The ionic acid generator is typically an onium salt containing an onium cation (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712 The compound which generate | occur | produces an acid by the radiation as described in etc. can be used. Moreover, you may use the compound manufactured by the well-known method.

  The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a sulfonate represented by the formula (B1).

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group, and methylene constituting the saturated hydrocarbon group The group may be replaced by an oxygen atom or a carbonyl group.
Y represents a hydrogen atom, a fluorine atom, or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the methylene group constituting the alicyclic hydrocarbon group is an oxygen atom, A sulfonyl group or a carbonyl group may be substituted.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group of Q ¹ and Q ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. And perfluorohexyl group.
In formula (B1), Q ¹ and Q ² are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group for L ^b1 include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and these A combination of two or more of the groups may be used.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1, Linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group;
An alkyl group (particularly an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group); For example, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl A branched alkanediyl group such as a 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

Examples of the saturated hydrocarbon group represented by L ^{b1 in} which the methylene group is replaced with an oxygen atom or a carbonyl group include the same as those in formulas (b1-1) to (b1-7). In addition, Formula (b1-1)-Formula (b1-7) have described the right and left according to Formula (B1), and among two bonds represented by *, C (Q ¹ ) Combined with (Q ² )-and combined with -Y on the right side. The same applies to specific examples of the following formulas (b1-1) to (b1-7).

In formula (b1-1) to formula (b1-7),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b4 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. However, the total carbon number upper limit of L ^b3 and L ^b4 is 20.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms.
L ^b6 represents a divalent saturated hydrocarbon group having 1 to 22 carbon atoms. However, the total carbon number upper limit of L ^b5 and L ^b6 is 22.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms.
L ^b8 represents a divalent saturated hydrocarbon group having 1 to 22 carbon atoms. However, the total carbon number upper limit of L ^b7 and L ^b8 is 23.
L ^b9 and L ^b10 each independently represent a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. However, the total carbon number upper limit of L ^b9 and L ^b10 is 20.
L ^b11 and L ^b12 represent a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. However, the upper limit of the total carbon number of L ^b11 , L ^b12 and L ^b13 is 19.
L ^b14 and L ^b15 each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms.
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. However, the upper limit of the total carbon number of L ^b14 , L ^b15 and L ^b16 is 21.

Among them, L ^b1 is preferably any one of formula (b1-1) to formula (b1-4), more preferably formula (b1-1) or formula (b1-2), and still more preferably formula (b1-1). And particularly preferably a divalent group represented by the formula (b1-1) in which L ^b2 is a single bond or —CH ₂ —.

Examples of the divalent group represented by the formula (b1-1) include the following.

Examples of the divalent group represented by the formula (b1-2) include the following.

Examples of the divalent group represented by the formula (b1-3) include the following.

Examples of the divalent group represented by the formula (b1-4) include the following.

Examples of the divalent group represented by the formula (b1-5) include the following.

Examples of the divalent group represented by the formula (b1-6) include the following.

Examples of the divalent group represented by the formula (b1-7) include the following.

Specific examples when the hydrogen atom contained in the aliphatic saturated hydrocarbon group of L ^b1 is substituted with a fluorine atom or a hydroxy group include the following.

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y26).

  Especially, it is preferably a group represented by any one of formulas (Y1) to (Y19), more preferably represented by formula (Y11), formula (Y14), formula (Y15) or formula (Y19). And more preferably a group represented by formula (Y11) or formula (Y14).

Examples of the substituent for the alicyclic hydrocarbon group in Y include a halogen atom, a hydroxy group, an oxo group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 to 3 carbon atoms. 16 alicyclic hydrocarbon groups, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, aralkyl groups having 7 to 21 carbon atoms, acyl groups having 2 to 4 carbon atoms, glycidyloxy Group or — (CH ₂ ) _j2 —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or 6 to 6 carbon atoms). 18 represents an aromatic hydrocarbon group, and j2 represents an integer of 0 to 4.
The alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aralkyl group, and the like, which are substituents for Y, may further have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxy group, and an oxo group.

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the aromatic hydrocarbon group include those similar to the above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of Y include the following.

  Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably a substituent (for example, an oxo group, a hydroxy group, etc.). An adamantyl group, more preferably an adamantyl group, a hydroxyadamantyl group, or an oxoadamantyl group.

The sulfonate anion in the salt represented by the formula (B1) is preferably an anion represented by the formula (b1-1-1) to the formula (b1-1-9). In the following formulas, the definitions of the symbols have the same meaning as described above, and the substituents R ^b2 and R ^b3 each independently represent an alkyl group having 1 to 4 carbon atoms (preferably a methyl group).
Specific examples of the sulfonate anion in the salt represented by the formula (B1) include the anions described in JP 2010-204646 A.

Examples of the cation (Z ⁺ ) contained in the acid generator (B) include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation. , An organic sulfonium cation or an organic iodonium cation, and more preferably an arylsulfonium cation.

Z ⁺ in formula (B1) is preferably represented by any of formula (b2-1) to formula (b2-4).

In formula (b2-1) to formula (b2-4),
Each of R ^{b4 to} R ^b6 independently represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms; , R ^b4 and R ^b5 may together form a ring which may have a sulfur atom. The aliphatic hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms.

R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5. When m2 is 2 or more, the plurality of P ^b7 are the same or different, and when n2 is 2 or more, the plurality of P ^b8 are the same or different.
R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or R ^b9 and R ^{b10 taken} together May be bonded to each other together with a sulfur atom to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring).
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The aromatic hydrocarbon group is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyl having 1 to 12 carbon atoms. It may be substituted with an oxy group.
R ^b11 and R ^b12 may be combined to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with —CH—CO— to which they are bonded.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, multiple R ^b13 are the same or different, when p2 is 2 or more, multiple R ^b14 are the same or different, and when q2 is 2 or more, multiple R ^b15 are the same or different , When r2 is 2 or more, a plurality of R ^b16 are the same or different, when s2 is 2 or more, a plurality of R ^b17 are the same or different, and when t2 is 2 or more, a plurality of R ^b18 are the same or different Different.

Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. Is mentioned. In particular, the alkyl group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
Examples of the aliphatic hydrocarbon group in which a hydrogen atom is substituted with an alicyclic hydrocarbon group include a 1- (adamantan-1-yl) alkane-1-yl group.

The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. And cycloalkyl groups such as cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.
In particular, the alicyclic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group, and an isobornyl group. Can be mentioned.
As an aromatic hydrocarbon group, phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-methoxyphenyl group And aryl groups such as p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenylyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
Examples of the alkyl group in which a hydrogen atom is substituted with an aromatic hydrocarbon group, that is, an aralkyl group, include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.
When the aromatic hydrocarbon group includes an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, the aliphatic hydrocarbon group having 1 to 18 carbon atoms and the alicyclic hydrocarbon having 3 to 18 carbon atoms Groups are preferred.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
As an aromatic hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 4-methoxyphenyl group etc. are mentioned, for example.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

The ring formed by combining R ^b4 and R ^b5 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings, and a sulfur atom As long as it contains one or more, one or more oxygen atoms may be further contained.

Examples of the ring formed by R ^b9 and R ^b10 include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring.
^Examples of the ring formed by R ^b11 and R ^b12 include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among the cation (b2-1) to cation (b2-4), the cation (b2-1) is preferable, the cation represented by the formula (b2-1-1) is more preferable, and the cation (b2-1) is more preferable. Are triphenylsulfonium cations (in formula (b2-1-1), v2 = w2 = x2 = 0), diphenyltolylsulfonium cations (in formula (b2-1-1), v2 = w2 = 0, x2 = 1 And R ^b21 is a methyl group.) Or a tolylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl. Group.)

In formula (b2-1-1),
R ^b19 , R ^b20 and R ^b21 each independently represent a halogen atom (more preferably a fluorine atom) hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or 3 carbon atoms. Represents an alicyclic hydrocarbon group of -18, and the alkyl group, alkoxy group and alicyclic hydrocarbon group are a halogen atom, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 18 carbon atoms. It may be substituted with a hydrocarbon group, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. Two ^members selected from R ^b19 , R ^b20 and R ^b21 may be combined to form a ring containing a sulfur atom.
v2, w2 and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1). When v2 is 2 or more, the plurality of R ^b19 are the same or different, when w2 is 2 or more, the plurality of R ^b20 are the same or different, and when x2 is 2 or more, the plurality of R ^b21 are the same or different. .

Among them, R ^b19 , R ^b20 and R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a carbon number of 1 to 12 Of the alkoxy group.
The ring formed by combining two ^members selected from R ^b19 , R ^b20 and R ^b21 may be any of monocyclic, polycyclic, aromatic and non-aromatic rings, and sulfur. As long as it contains one or more atoms, it may further contain one or more oxygen atoms.

  Specific examples of the cation include those described in JP2010-204646A.

  The acid generator (B1) is a combination of the above-described sulfonate anion and organic cation. The above-mentioned anion and cation can be arbitrarily combined, and preferably a combination of any one of anion (b1-1-1) to anion (b1-1-9) and cation (b2-1-1), and A combination of any one of anions (b1-1-3) to (b1-1-5) and a cation (b2-3) may be mentioned.

  As an acid generator (B1), Preferably, what is each represented by Formula (B1-1)-Formula (B1-20) is mentioned. Among them, those containing an arylsulfonium cation are preferable, and the formula (B1-1), formula (B1-2), formula (B1-3, formula (B1-6), formula (B1-7), formula (B1-11) A salt represented by formula (B1-12), formula (B1-13), formula (B1-14), formula (B1-18), formula (B1-19) or formula (B1-20), preferable.

The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less).
In the resist composition of the present invention, the acid generator (B) may contain one kind of acid generator alone or may contain plural kinds of acid generators.

<Compound represented by formula (II)>
The compound represented by the formula (II) is usually used as a quencher.
[In the formula (II),
Ring W ¹ represents a saturated heterocyclic ring having 2 to 36 carbon atoms.
R ³ represents a hydrocarbon group having 1 to 30 carbon atoms, and one or more —CH ₂ — contained in the hydrocarbon group is replaced with —O— or —CO—. ]

The saturated heterocyclic ring in the ring W ¹ may have one or more of a nitrogen atom, an oxygen atom or a sulfur atom in addition to the nitrogen atom bonded to R ^{3 as} long as it is a ring having at least one nitrogen atom. Examples of such a saturated heterocyclic ring include the following groups. Especially, group represented by a formula (W1), a formula (W2), or a formula (W3) is preferable.

The hydrocarbon group for R ³ includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain, a ring, and a combination thereof. Is included.
The aliphatic hydrocarbon group is preferably an alkyl group, and the alicyclic hydrocarbon group includes monocyclic and polycyclic alicyclic hydrocarbon groups. Of these, a saturated hydrocarbon group is preferable.

Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, 1-methylethyl group (isopropyl group), n-butyl group, 1,1-dimethylethyl group (tert-butyl group), 2, 2-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, n-hexyl group, 1-propylbutyl group, pentyl group, 1-methylpentyl group, 1,4-dimethylhexyl group, heptyl group, 1-methylheptyl group, octyl group, etc. Of the alkyl group.
Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.
Examples of the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are combined include a 1- (adamantan-1-yl) alkane-1-yl group.

R ³ is, for example, H—A ²¹ — * (A ²¹ represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and one or more methylene groups contained in the hydrocarbon group are an oxygen atom or a carbonyl group. (* Represents a bond with N).

As the hydrocarbon group in which one or more —CH ₂ — of the hydrocarbon group of R ³ is replaced by —O— or —CO—, a group represented by the formula (R ³ -1), a formula (R ³ — 2), a group represented by the formula (R ³ -3), and a group represented by the formula (R ³ -4). Among them, the formula a group represented by (R ³ -1), preferably a group represented by the formula group and the formula represented by ^{(R 3 -2) (R 3} -3), especially the formula (R ³ The group represented by -1) is preferred.
[In the formula (R ³ -1),
A ²⁰ represents a divalent hydrocarbon group having 1 to 29 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
* Represents a bond with N. ]
[In the formula (R ³ -2),
A ³⁰ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Ring W ² represents a lactone ring having 2 to 10 carbon atoms which may have a substituent.
* Represents a bond with N. ]

[In the formula (R ³ -3),
A ⁴⁰ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and one or more methylene groups contained in the hydrocarbon group are replaced with an oxygen atom or a carbonyl group.
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
* Represents a bond with N. ]
[In the formula (R ³ -4),
A ⁵⁰ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Ring W ³ represents an ether ring having 2 to 10 carbon atoms, and a methylene group contained in the ether ring may be replaced with a carbonyl group. However, ring W ³ has no ester bond.
* Represents a bond with N. ]
Here, a C2-C10 ether ring represents a C2-C10 cyclic ether ring.

The group represented by the formula (R ³ -1), the group represented by the formula (R ³ -2), the group represented by the formula (R ³ -3) and the formula (R ³ -4). In the group, examples of the divalent hydrocarbon group include an alkanediyl group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1, Linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group;
Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4- Branched alkanediyl groups such as diyl groups;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic hydrocarbon group;
Polycyclic divalent alicyclic hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group and the like Etc.
In addition, as the divalent aromatic hydrocarbon group, phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group , A group in which one hydrogen atom is removed from an aryl group such as mesityl group, biphenylyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.

Examples of the group in which the methylene group contained in the divalent hydrocarbon group is replaced with an oxygen atom or a carbonyl group include any of the formulas (L1-1) to (L1-4), preferably the formula (L1- 1) to any one of formulas (L1-4), more preferably formula (L1-1), formula (L1-2) or formula (L1-3), and even more preferably formula (L1-1) or formula (L1). -2). In formula (L1-1) ~ formula (L1-4), 2 single bond hands represented by each *, the left and right have been described in conjunction with Formula (II), with the ring W ¹ on the right Join. The same applies to specific examples of the following formulas (L1-1) to (L1-4).

Where
L ^a and L ^e each independently represent a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms. Among these it is preferable L ^a and L ^e is a single bond.
L ^c and L ^g each independently represent a single bond or a divalent hydrocarbon group having 1 to 17 carbon atoms. Of these, L ^c and L ^g are preferably a single bond.
L ^b represents a divalent hydrocarbon group having 1 to 19 carbon atoms. Among these, a divalent group in which L ^b is — (CH ₂ ) ₄ —, — (CH ₂ ) ₈ — or — (CH ₂ ) ₁₂ — is preferable.
L ^d and L ^h each independently represent a divalent hydrocarbon group having 1 to 18 carbon atoms. Of these, a divalent group in which L ^d and L ^h are —CH ₂ — is preferable.
L ^f represents a divalent hydrocarbon group having 1 to 4 carbon atoms. Among these, a divalent group in which L ^f is represented by — (CH ₂ ) ₂ — or — (CH ₂ ) ₃ — is preferable.
n represents an integer of 2 to 4.
The divalent hydrocarbon group in L ^a , L ^b , L ^c , L ^d , L ^e , L ^g and L ^h is preferably a divalent saturated hydrocarbon group.
In each of the formula (L1-1) ~ formula ^{(L1-4), L a, L} b, L c, L d, L e, the number of carbon atoms of the divalent hydrocarbon group for L ^g and L ^h and oxygen The total number of atoms (—O—) and carbonyl groups is 29 or less at A ^{20 and 20} or less at A ³⁰ , A ⁴⁰ and A ⁵⁰ .

Examples of the divalent group represented by the formula (L1-1) include the following.

Examples of the divalent group represented by the formula (L1-2) include the following.

Examples of the divalent group represented by the formula (L1-3) include the following.

Examples of the divalent group represented by the formula (L1-4) include the following.

Examples of the lactone ring of the ring W ² include monocyclic and polycyclic lactone rings, and specific examples thereof include the following groups.

Examples of the substituent of the lactone ring of the ring W ² include a hydrocarbon group in which a cyano group and a methylene group may be replaced with an oxygen atom or a carbonyl group, and examples thereof include an alkoxy group having 1 to 6 carbon atoms and 2 carbon atoms. An acyl group having 18 to 18 carbon atoms, an acyloxy group having 2 to 18 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Can be mentioned.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
Examples of the alkylcarbonyl group include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, sec-butylcarbonyl group, tert-butylcarbonyl group, pentylcarbonyl group, hexylcarbonyl. Group, octylcarbonyl group, 2-ethylhexylcarbonyl group and the like.
Examples of the aliphatic hydrocarbon group and the alicyclic hydrocarbon group include the same as R ³ .

Examples of the alkyl group for R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, 2,2-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group. Group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, n-hexyl group, 1 Examples include -propylbutyl group, pentyl group, 1-methylpentyl group, 1,4-dimethylhexyl group, heptyl group, 1-methylheptyl group, octyl group and the like.

Examples of the alicyclic hydrocarbon group include a cyclohexyl group, an adamantyl group, and the following groups.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenylyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.

Examples of the ether ring of ring W ³ include the following groups.
The ether ring of the ring W ³ may have a substituent. Examples of the substituent include the same substituents as those on the lactone ring of ring W ² .

Examples of the group represented by the formula (R ³ -2) include the following.

Examples of the group represented by the formula (R ³ -4) include groups represented by the formula (R ³ -4-1) and the formula (R ³ -4-2).

In the formula (R ³ -4-1) and the formula (R ³ -4-2),
A ³³ and A ⁵⁵ each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—. Good.
Ring W ²⁰ represents a monocyclic or polycyclic ether ring having 2 to 10 carbon atoms. At least one —CH ₂ — contained in the ether ring is replaced by —CO—. However, ring W ²⁰ is not a lactone ring. The ether ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 18 carbon atoms, and carbon. Examples thereof include an acyloxy group having 2 to 18 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an alicyclic hydrocarbon group having 3 to 20 carbon atoms. The number of substituents is preferably 6 or less.
Ring W ³⁰ represents an ether ring having 2 to 10 carbon atoms.

Examples of the group represented by the formula (R ³ -4) include the following.

Examples of the compound in which R ³ is a group represented by the formula (R ³ -1) include the following compounds.

Examples of the compound in which R ³ is a group represented by the formula (R ³ -2) include the following compounds.

Examples of the compound in which R ³ is a group represented by the formula (R ³ -3) include the following compounds.

Examples of the compound in which R ³ is a group represented by the formula (R ³ -4) include the following compounds.

Of the compounds represented by formula (II), the compound represented by formula (II-1) is preferred.
[In the formula (II-1),
Ring W ¹ represents the same meaning as described above.
A ²⁰ represents a divalent hydrocarbon group having 1 to 29 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

In particular, the ring W ¹ is preferably a morpholine ring.
Among the compounds represented by the formula (II-1), the compound represented by the formula (II-2) is more preferable.
[In the formula (II-1),
Z ¹ is an alkanediyl group having 7 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an alkanediyl group having 1 to 6 carbon atoms and a divalent fat having 3 to 20 carbon atoms. A group in combination with a cyclic hydrocarbon group is represented. ]

  The alkanediyl group may be linear or branched. For example, a methylene group, ethylene group, propane-1,3-diyl group, tetramethylene group, pentamethylene group, hexamethylene group, heptane-1,7- Diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane- 1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl Group, propane-1,1-diyl group, propane-2,2-diyl group and the like.

Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cycloalkanediyl group having 3 to 20 carbon atoms and a group represented by the following.
Z ¹ is preferably an alkanediyl group having 7 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an alkanediyl group having 7 to 12 carbon atoms or 6 to 20 carbon atoms. The divalent alicyclic hydrocarbon group is more preferably an alkanediyl group having 7 to 12 carbon atoms or a cycloalkanediyl group having 6 to 20 carbon atoms.
Particularly preferable examples of the compound represented by the formula (II) include those represented by the above-described compound represented by the formula (II-1-1) to the formula (II-1-30).
The compounds represented by formula (II) may be used alone or in combination of two or more.

  The content of the compound represented by the formula (II) is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less in the solid content of the composition. It is 01 mass% or more, More preferably, it is 0.05 mass% or more.

<Solvent (E)>
The content of the solvent (E) is, for example, 90% by mass or more in the resist composition, preferably 92% by mass or more, more preferably 94% by mass or more, for example 99.9% by mass or less, preferably 99% by mass or less. It is. The content rate of a solvent (E) can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (E) may contain 1 type independently, and may contain 2 or more types.

<Basic compound (hereinafter sometimes referred to as “basic compound (C)”)>
The resist composition of the present invention may contain a basic compound (C) that acts as a quencher.
The basic compound (C) is preferably a basic nitrogen-containing organic compound, and examples thereof include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines. The basic compound (C) is preferably a compound represented by any one of the formulas (C1) to (C8) and (C1-1), more preferably represented by the formula (C1-1). The compound which is made is mentioned.

[In formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 represents an aromatic hydrocarbon group, and the hydrogen atom contained in the alkyl group and the alicyclic hydrocarbon group may be substituted with a hydroxy group, an amino group or an alkoxy group having 1 to 6 carbon atoms, The hydrogen atom contained in the aromatic hydrocarbon group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. It may be substituted with a group hydrocarbon group. ]

[In Formula (C1-1), R ^c2 and R ^c3 represent the same meaning as described above.
R ^c4 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
m3 represents an integer of 0 to 3, and when m3 is 2 or more, the plurality of R ^c4 are the same or different. ]

[In Formula (C2), Formula (C3) and Formula (C4), R ^c5 , R ^c6 , R ^c7 and R ^c8 each independently represent the same meaning as R ^c1 .
R ^c9 represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms.
n3 represents an integer of 0 to 8, and when n3 is 2 or more, the plurality of R ^c9 are the same or different. ]

[In Formula (C5) and Formula (C6), R ^c10 , R ^c11 , R ^c12 , R ^c13 and R ^c16 each independently represent the same meaning as R ^c1 .
R ^c14 , R ^c15 and R ^c17 each independently represent the same meaning as R ^c4 .
o3 and p3 each independently represents an integer of 0 to 3, and when o3 is 2 or more, the plurality of R ^c14 are the same or different, and when p3 is 2 or more, the plurality of R ^c15 are the same or Different.
L ^c1 represents an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

Wherein (C7) and formula ^{(C8), R c18, R} c19 and R ^c20 in each occurrence independently represent the same meaning as R ^c4.
q3, r3 and s3 each independently represent an integer of 0 to 3, and when q3 is 2 or more, the plurality of R ^c18 are the same or different, and when r3 is 2 or more, the plurality of R ^c19 are the same. Or when different and when s3 is 2 or more, the plurality of R ^c20 are the same or different.
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

In formula (C1) to formula (C8) and formula (C1-1), the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, alkanediyl group are the same as those described above. Is mentioned.
Examples of the alkanoyl group include acetyl group, 2-methylacetyl group, 2,2-dimethylacetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, and 2,2-dimethylpropionyl group.

  Examples of the compound represented by the formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N- Dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tri Pentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyl Hexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonyl Amine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2- Examples include diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and preferably diisopropyl. Piruanirin. Particularly preferred include 2,6-diisopropylaniline.

Examples of the compound represented by the formula (C2) include piperazine.
Examples of the compound represented by the formula (C3) include morpholine.
Examples of the compound represented by the formula (C4) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575.
Examples of the compound represented by the formula (C5) include 2,2′-methylenebisaniline.
Examples of the compound represented by the formula (C6) include imidazole and 4-methylimidazole.
Examples of the compound represented by the formula (C7) include pyridine and 4-methylpyridine.
Examples of the compound represented by the formula (C8) include 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1, 2-di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipiconylamine, bipyridine and the like.

  As ammonium salts, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

  The content of the basic compound (C) in the solid content of the resist composition is preferably about 0.01 to 5% by mass, more preferably about 0.01 to 3% by mass, and particularly preferably 0. About 0.01 to 1% by mass.

<Other components (hereinafter sometimes referred to as “other components (F)”)>
The resist composition of this invention may contain the other component (F) as needed. The other component (F) is not particularly limited, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, and the like can be used.

<Preparation of resist composition>
The resist composition of the present invention comprises a resin (A), an acid generator (B) and a compound (II), and a solvent (E), a basic compound (C) and other components (F) used as necessary. Etc. can be prepared by mixing them. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature range from the range of 10-40 degreeC according to the kind etc. of resin, the solubility with respect to solvent (E), such as resin. An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) A step of applying the resist composition of the present invention on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) The process of heating the composition layer after exposure, (5) The process of developing the composition layer after a heating is included.

  Application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be washed or an antireflection film or the like may be formed.

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking) or using a decompression device to form a composition layer from which the solvent has been removed. The temperature in this case is preferably about 50 to 200 ° C., for example. The pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) Using various lasers such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do.

  The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection group reaction. As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., and the development time is preferably 5 to 300 seconds.

When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline). The alkali developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern.

In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention is a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly a liquid. It is suitable as a resist composition for immersion exposure and useful for fine processing of semiconductors.

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The structure of the compound was confirmed by MASS (LC: Agilent 1100 type, MASS: Agilent LC / MSD type or LC / MSD TOF type).
The weight average molecular weight of the resin is a value determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

Synthesis Example 1 [Synthesis of Monomer (M-K)]
33.48 parts of the compound represented by the formula (K-1), 23.93 parts of dicyclohexylcarbodiimide and 40 parts of methylene chloride were charged into a reactor and mixed. After cooling the obtained mixture to about 0 ° C., 18.83 parts of the compound represented by the formula (K-2) was added, and the mixture was stirred for about 1 hour while maintaining about 0 ° C. The temperature was raised to 23 ° C. and the mixture was further stirred for 30 minutes. Insoluble matters were removed by filtration, and the obtained filtrate was concentrated to obtain 44.28 parts of a compound represented by the formula (K-3).

A reactor was charged with 19.42 parts of the compound represented by the formula (K-3) obtained as described above, 18.22 parts of the compound represented by the formula (K-4) and 200 parts of acetonitrile. Mixed. The resulting mixture was stirred at 50 ° C. for 3 hours. The obtained mixture was concentrated, 300 parts of chloroform and 150 parts of ion-exchanged water were added, and then the organic layer was recovered by a liquid separation operation. The recovered organic layer was washed with 150 parts of ion exchange water, and then the organic layer was concentrated. The concentrate is subjected to column fractionation (column fractionation conditions stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd. developing solvent: ethyl acetate) to obtain 12.89 parts of a compound represented by the formula (M-K). It was.
MS (mass spectrometry): 308.1 (molecular ion peak)

Synthesis Example 2 [Synthesis of Compound D1]
50 parts of compound (D1-a) and 10 parts of compound (D1-b) were mixed, heated to 80 ° C., and stirred for 6 hours. The resulting mixture was cooled to room temperature and 40 parts of ion exchange water was added. The resulting mixture was extracted with 120 parts of ethyl acetate, and the organic layer was washed 5 times with 40 parts of ion-exchanged water. The organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated to obtain 9 parts of compound (D1) as a yellow liquid.
MS (mass spectrometry): 215.2 (molecular ion peak)

Synthesis Example 3 [Synthesis of Compound D2]
120 parts of compound (D2-a) and 24 parts of compound (D2-b) were mixed, heated to 40 ° C., and stirred for 4 hours. After cooling to room temperature, 96 parts of ion exchange water was added. Extraction was performed with 288 parts of ethyl acetate, and the organic layer was washed 5 times with 96 parts of ion-exchanged water. The organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated to obtain 22 parts of compound (D2) as a milky white solid.
MS (mass spectrometry): 271.3 (molecular ion peak)

Synthesis Example 4 [Synthesis of Compound D3]

47 parts of the compound (D3-a), 50 parts of the compound (D3-b) and 28 parts of ion-exchanged water were mixed, heated to 97 ° C., and stirred for 2 hours. The resulting mixture was cooled to room temperature and 448 parts of a saturated aqueous sodium hydroxide solution was added. The resulting mixture was extracted with 186 parts of methyl-tert-butyl ether, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated. The obtained liquid was distilled under reduced pressure to obtain 63 parts of a basic compound (D3) as a colorless liquid.
MS (mass spectrometry): 185.1 (molecular ion peak)

Synthesis Example 5: Synthesis of salt represented by formula (B1-5)
50.49 parts of the salt represented by the formula (B1-5-a) and 252.44 parts of chloroform are charged into a reactor, stirred at 23 ° C. for 30 minutes, and then represented by the formula (B1-5-b). 16.27 parts of the compound was added dropwise and stirred at 23 ° C. for 1 hour to obtain a solution containing a salt represented by the formula (B1-5-c). To the obtained solution containing the salt represented by the formula (B1-5-c), 48.80 parts of the salt represented by the formula (B1-5-d) and 84.15 parts of ion-exchanged water are added, The mixture was stirred at 23 ° C. for 12 hours. Since the resulting reaction solution was separated into two layers, the chloroform layer was separated and removed, and 84.15 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. To the obtained chloroform layer, 3.88 parts of activated carbon was added and stirred, followed by filtration. The collected filtrate was concentrated, 125.87 parts of acetonitrile was added to the resulting residue, and the mixture was stirred and concentrated. To the obtained residue, 20.62 parts of acetonitrile and 309.30 parts of tert-butyl methyl ether were added and stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated. To the obtained residue, 200 parts of n-heptane was added, stirred at 23 ° C. for 30 minutes, and then filtered to obtain 61.54 parts of a salt represented by the formula (B1-5).
MASS (ESI (+) Spectrum): M ⁺ 375.2
MASS (ESI (−) Spectrum): M ^- 339.1

Synthesis of Resin (A) Compounds (monomers) used in the synthesis of resin (A) are shown below.
Hereinafter, these monomers are referred to as “monomer (MA)” to “monomer (ML)” depending on the reference numerals.

Synthesis Example 6 [Synthesis of Resin A1]
As a monomer, a monomer (MG), a monomer (ME), a monomer (MB), a monomer (M-H), and a monomer (M-K) are used, and the molar ratio [monomer (MG) : Monomer (ME): monomer (MB): monomer (M-H): monomer (M-K)] to be 32: 7: 8: 43: 10 1.5 mass times dioxane was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.6. A × 10 ³ resin A1 (copolymer) was obtained in a yield of 80%. This resin A1 has the following structural units.

Synthesis Example 7 [Synthesis of Resin A2]
As a monomer, a monomer (MF), a monomer (M-I), a monomer (M-J), a monomer (MD), and a monomer (M-K) are used, and the molar ratio [monomer (MF) : Monomer (M-I): monomer (M-J): monomer (M-D): monomer (M-K)] is mixed to be 45: 14: 2.5: 22.5: 16, Dioxane of 1.5 mass times the total monomer amount was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 8.8. A × 10 ³ resin A2 (copolymer) was obtained with a yield of 71%. This resin A2 has the following structural units.

Synthesis Example 8 [Synthesis of Resin A3]
As a monomer, a monomer (M−F), a monomer (M−I), a monomer (M−J), a monomer (M−D), a monomer (M−H), and a monomer (M−K) are used, and a molar ratio thereof. [Monomer (MF): Monomer (M-I): Monomer (M-J): Monomer (MD): Monomer (M-H): Monomer (M-K)] 45: 14: 2. It mixed so that it might become 5: 17.5: 5: 16, and the dioxane of 1.5 mass times the total monomer amount was added, and it was set as the solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 8.3. A × 10 ³ resin A3 (copolymer) was obtained in a yield of 69%. This resin A3 has the following structural units.

Synthesis Example 9 [Synthesis of Resin A4]
As a monomer, a monomer (MF), a monomer (ML), a monomer (MJ), a monomer (MD), and a monomer (MK) are used, and the molar ratio [monomer (MF) : Monomer (ML): monomer (M-J): monomer (MD): monomer (M-K)] is mixed to be 45: 14: 2.5: 22.5: 16, A solution was prepared by adding propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by reprecipitation operation of filtering the resin twice. Resin A4 (copolymer) having a molecular weight of 8.2 × 10 ³ was obtained in a yield of 66%. This resin A4 has the following structural units.

Synthesis Example 10 [Synthesis of Resin A5]
As a monomer, a monomer (MG), a monomer (ML), a monomer (MB), a monomer (M-H), and a monomer (M-K) are used, and the molar ratio [monomer (MG) : Monomer (ML): monomer (MB): monomer (M-H): monomer (M-K)] to be 32: 7: 8: 43: 10 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by reprecipitation operation of filtering the resin twice. Resin A5 (copolymer) having a molecular weight of 7.9 × 10 ³ was obtained in a yield of 82%. This resin A5 has the following structural units.

Synthesis Example 11 [Synthesis of Resin H1]
Monomer (MA) and monomer (MC) are used as monomers and mixed so that the molar ratio [monomer (MA): monomer (MC)] is 40:60. An amount of 1.5 mass times dioxane was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.4 mol% and 4.2 mol%, respectively, based on the total monomer amount, and these were added at 70 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and the reprecipitation operation of filtering the resin was performed twice, and the weight average molecular weight was 5.0. A × 10 ³ resin H1 (copolymer) was obtained in a yield of 92%. This resin H1 has the following structural units.

<Preparation of resist composition>
Each of the components shown below was dissolved in a solvent in parts by mass shown in Table 1, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

<Resin>
A1 to A5, H1: Resin A1 to Resin A5, Resin H1
<Acid generator>
B1-3: synthesized according to the example of JP 2010-152341 A
B1-5:
B2: Triphenylsulfonium triflate (manufactured by TPS-105 Midori Chemical Co., Ltd.)
<Compound represented by formula (II)>
D1:
D2:
D3:

<Basic compound: Quencher>
C1: 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent>
Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts

Examples 1 to 12 and Comparative Examples 1 and 2
<Manufacture of negative resist pattern>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer, and baked under the conditions of 205 ° C. and 60 seconds, whereby an organic layer having a thickness of 78 nm. An antireflection film was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (pre-baking) was 100 nm. After coating, the composition layer was formed on the silicon wafer by pre-baking on a direct hot plate for 60 seconds at the temperature described in the “PB” column of Table 1.
An ArF excimer laser stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized illumination) is applied to a silicon wafer on which the composition layer has been formed. Using a mask for forming a pitch of 90 nm / line of 45 nm, exposure was performed by changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 1. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured. In the obtained resist pattern, an exposure amount at which the line width and space width of the line and space pattern were 1: 1 was defined as effective sensitivity.

<Pattern collapse evaluation (PCM) evaluation>
When the obtained resist pattern was observed with a scanning electron microscope and the pattern pattern disappeared due to falling or peeling was not observed in the line pattern formed with an exposure amount less than the effective sensitivity, it was formed with an exposure amount greater than the effective sensitivity. The case where pattern disappearance due to falling or peeling was observed also in the line pattern was marked as x. The results are shown in Table 2. The line width of the line pattern becomes narrower as the exposure amount is smaller, and the pattern disappears more easily. The numbers in parentheses indicate the minimum line width (nm) of the resist pattern in which no pattern disappearance is observed.

Examples 13 to 24 and Comparative Examples 3 to 4
Except for changing the developer to 2-heptanone (manufactured by Kyowa Hakko Co., Ltd.), the same operation as above was performed to produce a negative resist pattern, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

  From the above results, it can be seen that according to the resist composition of the present invention, a negative resist pattern can be produced with excellent pattern collapse resistance (PCM).

<Preparation of resist composition>
Each of the components shown below was dissolved in the following solvent in the parts by mass shown in Table 4 and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

Examples 25-27 and Comparative Examples 3-4
<Manufacture of resist pattern>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 78 nm. An organic antireflection film was formed. Next, the above resist composition was spin-coated on the organic antireflection film so that the film thickness after drying was 85 nm.
The obtained silicon wafer was pre-baked (PB) for 60 seconds on a direct hot plate at the temperature described in the “PB” column of Table 4. Using the ArF excimer stepper for immersion exposure [XT: 1900Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light] on the wafer on which the resist composition film is formed in this manner, the exposure amount is stepwise. The line and space pattern was subjected to immersion exposure. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking (PEB) was performed for 60 seconds on a hot plate at the temperature described in the “PEB” column of Table 4, and then with an aqueous 2.38 mass% tetramethylammonium hydroxide solution for 60 seconds. Paddle development was performed.

<Pattern collapse evaluation (PCM) evaluation>
Using a line-and-space pattern mask reduced from the line width of 45 nm to every 1 nm, the line-and-space pattern of each line width is exposed at an exposure amount that can be resolved, and when the line-and-space pattern is obtained, the pattern of the resist pattern collapses Or the presence or absence of pattern peeling (presence or absence of pattern disappearance) was observed. The case where pattern disappearance due to falling or peeling was not observed even when the line width was thinner than 38 nm was designated as “◯”, and the case where pattern disappearance due to falling or peeling was observed with a line width of 38 nm or more was designated as “X”. The results are shown in Table 5. The numerical value in the parenthesis indicates the line width (nm).

  Since the resist composition of the present invention can produce a resist pattern having excellent pattern collapse resistance (PCM), it is useful for fine processing of semiconductors.

Claims (3)

A resist composition comprising a resin comprising a structural unit represented by formula (I) and a structural unit having an acid labile group, an acid generator, and a compound represented by formula (II-1) .
[In the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —O—, ^* —A ² —CO—O—, ^* —A ² —CO—O—A ³ —CO—O—, or ^* —A ² —O—CO. -A ³ represents a -O-.
* Represents a bond with -O-.
A ² and A ³ each independently represents an alkanediyl group having 1 to 6 carbon atoms. ]
[In the formula (II-1),
Ring W ¹ represents a saturated heterocyclic ring having 2 to 36 carbon atoms.
A ²⁰ represents a divalent hydrocarbon group having 1 to 29 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ] A resist composition according to claim 1 Symbol mounting contains a solvent. (1) The process of apply | coating the resist composition of Claim 1 or 2 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: