CN112987497A

CN112987497A - Resist composition and resist pattern forming method

Info

Publication number: CN112987497A
Application number: CN202011474716.7A
Authority: CN
Inventors: 平野智之; 米村幸治; 中川裕介
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2019-12-17
Filing date: 2020-12-14
Publication date: 2021-06-18
Also published as: KR20210077614A; JP2021096353A; JP7479142B2

Abstract

A negative resist composition comprising: a polymer compound (A1) having a structural unit (a10) containing a phenolic hydroxyl group, an acid generator (B0) represented by the following general formula (B0-1), a crosslinking agent (C), and an aromatic compound (Z) (wherein Rb is an aromatic compound having 1 or 2 phenolic hydroxyl groups in the molecule and having no carboxyl group) (wherein Rb is¹Is an organic radical, Rb²Is a group represented by the following general formula (b0-r-1) or the following general formula (b 0-r-2). [ formula 1]

Description

Resist composition and resist pattern forming method

Technical Field

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

The present application claims priority based on japanese patent application No. 2019-227234, filed in japan on 12/17/2019, and the contents thereof are incorporated herein.

Background

In recent years, in the manufacture of semiconductor devices and liquid crystal display devices, the miniaturization of patterns has been rapidly advanced due to the progress of photolithography. As a method for miniaturization, generally, the exposure light source is shortened in wavelength (increased in energy).

The resist material is required to have lithographic characteristics such as sensitivity to these exposure light sources and resolution with which a pattern of a fine size can be reproduced.

As a resist material satisfying such a demand, a chemically amplified resist composition containing a base component whose solubility in a developer changes by the action of an acid and an acid generator component which generates an acid upon exposure has been conventionally used.

For example, when the developer is an alkaline developer (alkaline developing process), a composition containing a resin component (base resin) whose solubility in the alkaline developer is increased by the action of an acid and an acid generator component is generally used as a positive chemically amplified resist composition. When a resist film formed using the resist composition is selectively exposed to light during formation of a resist pattern, an acid is generated from an acid generator component in an exposed portion, the polarity of a matrix resin is increased by the action of the acid, and the exposed portion of the resist film becomes soluble in an alkaline developer. Therefore, by performing the alkali development, a positive pattern in which an unexposed portion of the resist film remains as a pattern is formed.

Further, as a resist material, a chemically amplified resist composition containing a base material component (alkali-soluble base material component) soluble in an alkali developer, an acid generator component generating an acid upon exposure, and a crosslinking agent component has been used. When an acid is generated from the acid generator component by exposure, for example, the acid acts to crosslink the alkali-soluble base material component and the crosslinking agent component, and as a result, the solubility in an alkaline developer is reduced. Therefore, in the formation of a resist pattern, when a resist film obtained by applying the chemically amplified resist composition to a support is selectively exposed to light, the exposed portion of the resist film is rendered insoluble to an alkaline developer, while the unexposed portion of the resist film remains insoluble to the alkaline developer.

For example, patent document 1 describes a negative chemically amplified resist composition containing an alkali-soluble polyhydroxystyrene resin, an acid-crosslinkable substance, a specific photoacid generator, and a dissolution promoter.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 3655030

Disclosure of Invention

Technical problem to be solved by the invention

As a result of the studies by the present inventors, when a resist pattern is formed using a negative resist composition using an alkali-soluble polyhydroxystyrene resin as a base component, the etching resistance may be insufficient when a thick resist film of a micron order is formed by utilizing the wet etching resistance, and further, when a resist pattern is formed and etched.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist composition capable of forming a resist pattern having excellent etching resistance, and a method for forming a resist pattern using the same.

Solution for solving the above technical problem

In order to solve the above-described problems, the present invention adopts the following configuration.

That is, the 1 st aspect of the present invention is a negative resist composition comprising: a polymer compound (A1) having a structural unit (a10) represented by the following general formula (a10-1), an acid generator (B0) represented by the following general formula (B0-1), a crosslinking agent (C), and an aromatic compound (Z) having 1 or 2 phenolic hydroxyl groups in the molecule and no carboxyl group.

[ solution 1]

[ wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. Ya^x1Is a single bond or a 2-valent linking group. Wa^x1Is an aromatic hydrocarbon group which may have a substituent. n is_ax1Is an integer of 1 or more.]

[ solution 2]

[ in the formula, Rb¹Is an organic group. Rb²Is a group represented by the following general formula (b0-r-1) or the following general formula (b 0-r-2).]

[ solution 3]

[ formula (b0-r-1) wherein Rb is²⁰¹And Rb²⁰²Each independently is an organic group. Denotes a bond. In formula (b0-r-2), Xb is a group that forms a cyclic group having a cyclic imide structure together with- (O ═ C — N — C (═ O) -. Denotes a bond.]

The invention according to claim 2 is a resist pattern forming method including: forming a resist film on a support using the resist composition according to claim 1; exposing the resist film; and forming a resist pattern by developing the exposed resist film.

Effects of the invention

According to the present invention, a resist composition capable of forming a resist pattern having excellent etching resistance and a method for forming a resist pattern using the same can be provided.

Detailed Description

In the present specification and claims, "aliphatic" refers to a relative concept with respect to aromatic groups, and is defined to mean groups, compounds, and the like that do not have aromatic properties.

Unless otherwise specified, "alkyl" includes straight-chain, branched-chain and cyclic 1-valent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.

Unless otherwise specified, "alkylene" includes linear, branched and cyclic 2-valent saturated hydrocarbon groups.

Examples of the "halogen atom" may include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The "structural unit" refers to a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).

When "may have a substituent" is described, the case where a hydrogen atom (-H) is substituted with a group having a valence of 1 and the case where a methylene group (-CH) is substituted are included₂-) two cases substituted with a 2-valent group.

"exposure" refers to a concept including irradiation of all radiation.

The "acid-decomposable group" is a group having an acid-decomposability in which at least a part of the bonds in the structure of the acid-decomposable group are cleavable by an acid.

Examples of the acid-decomposable group whose polarity is increased by the action of an acid include groups which are decomposed by the action of an acid to generate a polar group.

Examples of the polar group include a carboxyl group, a hydroxyl group, an amino group and a sulfonic acid group (-SO)₃H) And the like.

More specifically, the acid-decomposable group may be a group in which the polar group is protected with an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).

The "acid-dissociable group" refers to both of the following: (i) an acid-dissociable group having a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group that can be cleaved by the action of an acid; or (ii) a group in which a part of the bond is cleaved by the action of an acid and then decarboxylation is further caused, whereby the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved.

The acid-dissociable group constituting the acid-dissociable group must be a group having a polarity lower than that of the polar group generated by dissociation of the acid-dissociable group, and thus when the acid-dissociable group is dissociated by the action of an acid, a polar group having a polarity higher than that of the acid-dissociable group is generated and the polarity increases. As a result, the polarity of the entire component (a1) increases. The increase in polarity relatively changes the solubility in the developer, and the solubility increases when the developer is an alkaline developer, and decreases when the developer is an organic developer.

The "substrate component" refers to an organic compound having film-forming ability. Organic compounds used as a component of the substrate are roughly classified into non-polymers and polymers. As the non-polymer, a non-polymer having a molecular weight of 500 or more and less than 4000 is generally used. Hereinafter, in the case where "low molecular compound" is mentioned, it means a non-polymer having a molecular weight of 500 or more and less than 4000. As the polymer, a polymer having a molecular weight of 1000 or more is generally used. Hereinafter, when "resin", "high molecular compound" or "polymer" is referred to, it means a polymer having a molecular weight of 1000 or more. As the molecular weight of the polymer, a mass average molecular weight in terms of polystyrene based on GPC (gel permeation chromatography) was used.

The "derived structural unit" refers to a structural unit formed by cleavage of multiple bonds between carbon atoms, for example, an olefinic double bond.

The hydrogen atom bonded to the carbon atom in the α -position of the "acrylate" may be substituted with a substituent. A substituent (R) for substituting the hydrogen atom bonded to the carbon atom at the alpha position^αx) Is an atom or group other than a hydrogen atom. In addition, the compound also comprises a substituent (R)^αx) Itaconate diester substituted with a substituent comprising an ester bond, substituent (R)^αx) Substituted by hydroxyalkyl groups or groups modifying the hydroxy groupsThe alpha hydroxy acrylate of (1). Unless otherwise specified, the carbon atom at the α -position of the acrylate refers to a carbon atom to which a carbonyl group of acrylic acid is bonded.

Hereinafter, an acrylate in which a hydrogen atom bonded to a carbon atom at the α -position is substituted with a substituent may be referred to as an α -substituted acrylate.

The term "derivative" is intended to include a compound in which the hydrogen atom at the α -position of the target compound is substituted with another substituent such as an alkyl group or a haloalkyl group, and a concept of derivatives thereof. Examples of the derivatives thereof include compounds in which a hydrogen atom at the α -position is substituted with a substituent, and a hydrogen atom of a hydroxyl group of the subject compound is substituted with an organic group; and compounds in which a substituent other than a hydroxyl group is bonded to a target compound in which a hydrogen atom at the α -position may be substituted with a substituent. In addition, the α position means the 1 st carbon atom adjacent to the functional group unless otherwise specified.

Examples of the substituent for substituting the hydrogen atom at the α -position of hydroxystyrene include the group represented by formula (I) and (II)^αxThe same groups.

In the present specification and claims, depending on the structure represented by the formula, there exists a structure of asymmetric carbon, and there may exist a structure of enantiomer (enatiomer) or diastereomer (diasteromer). In this case, these isomers are represented representatively by a chemical formula. These isomers may be used alone or as a mixture.

(resist composition)

The resist composition of claim 1 of the present invention is a negative resist composition.

An embodiment of the resist composition may include a resist composition containing a base component (a) (hereinafter, also referred to as "component a") whose solubility in a developer changes by the action of an acid, an acid generator component (B) (hereinafter, also referred to as "component B") which generates an acid upon exposure, a crosslinking agent (C) (hereinafter, also referred to as "component C"), and an aromatic compound (Z) (hereinafter, also referred to as "component Z") having 1 or 2 phenolic hydroxyl groups in the molecule and no carboxyl group.

In the resist composition of the present embodiment, the component (a) contains a polymer compound (a1) (hereinafter referred to as a "component (a 1)") having a structural unit (a10) represented by the general formula (a10-1), and the component (B) contains an acid generator (B0) (hereinafter referred to as a "component (B0)") represented by the general formula (B0-1).

When a resist film is formed using the resist composition of the present embodiment and the resist film is selectively exposed, an acid is generated in an exposed portion of the resist film, and the solubility of the component (a) in the developer changes due to the action of the acid, while the solubility of the component (a) in the developer does not change in an unexposed portion of the resist film, so that a difference in solubility in the developer occurs between the exposed portion and the unexposed portion of the resist film. Therefore, when the resist film is subjected to alkali development, unexposed portions of the resist film are dissolved and removed to form a negative resist pattern.

In this specification, a resist composition in which exposed portions of a resist film are dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist composition in which unexposed portions of a resist film are dissolved and removed to form a negative resist pattern is referred to as a negative resist composition. The resist composition of the present embodiment is a negative resist composition.

< ingredient (A) >

(A) The component is a base component whose solubility in the developer changes by the action of an acid.

In the present invention, the "base material component" is an organic compound having a film-forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, film formation ability is improved, and a resist pattern of a nanometer order is easily formed.

Organic compounds used as a component of the substrate are roughly classified into non-polymers and polymers.

As the non-polymer, a non-polymer having a molecular weight of 500 or more and less than 4000 is generally used. Hereinafter, in the case where "low molecular compound" is mentioned, it means a non-polymer having a molecular weight of 500 or more and less than 4000. As the polymer, a polymer having a molecular weight of 1000 or more is generally used. Hereinafter, when "resin", "high molecular compound" or "polymer" is referred to, it means a polymer having a molecular weight of 1000 or more. As the molecular weight of the polymer, a weight average molecular weight in terms of polystyrene based on GPC (gel permeation chromatography) was used.

In the resist composition of the present embodiment, at least the polymer compound (a1) having the structural unit (a10) represented by the general formula (a0-1) is used as the component (a), and a polymer compound and/or a low-molecular compound other than the component (a1) may be used in combination.

When a resist film is formed using a resist composition containing at least the component (a1) and the resist film is selectively exposed, for example, when the resist composition contains the component (B), acid is generated from the component (B), and crosslinking occurs between the component (a10) and the component (a1) via the crosslinkable structural unit by the action of the acid in the exposed portion of the resist film, resulting in a decrease in the solubility of the exposed portion of the resist film in an alkaline developer. Therefore, in the formation of a resist pattern, when a resist film obtained by applying the resist composition of the present embodiment to a support is selectively exposed to light, the exposed portion of the resist film is rendered insoluble to an alkaline developer, while the unexposed portion of the resist film remains insoluble to the alkaline developer.

With respect to the (A1) component

(A1) Component (b) is a polymer compound having a structural unit (a10) represented by the general formula (a 0-1).

As the component (a1), a copolymer having a structural unit (a11) in addition to the structural unit (a10), in which the structural unit (a11) includes an aromatic ring (not including an aromatic ring bonded to a hydroxyl group) in a side chain, is preferable.

The component (a1) may have other structural units in addition to the structural unit (a10) and the structural unit (a 11).

With respect to structural unit (a 10):

the structural unit (a10) is a structural unit represented by the following general formula (a 10-1).

[ solution 4]

In the formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.

The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, it may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group or a neopentyl group.

The haloalkyl group having 1 to 5 carbon atoms in R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. The halogen atom is particularly preferably a fluorine atom.

R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group or a trifluoromethyl group, further preferably a hydrogen atom or a methyl group, particularly preferably a methyl group, from the viewpoint of easy industrial availability.

In the formula (a10-1), Ya^x1Is a single bond or a 2-valent linking group.

In the chemical formula, as Ya^x1The linking group having a valence of 2 in (A) is not particularly limited, and may have a substituentAs the preferable linking group, a 2-valent hydrocarbon group of the group, a 2-valent linking group containing a hetero atom, and the like are preferable.

A 2-valent hydrocarbon group which may have a substituent:

at Ya^x1When the hydrocarbon group is a 2-valent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

··Ya^x1Aliphatic hydrocarbon group of (1)

The aliphatic hydrocarbon group means a hydrocarbon group having no aromatic character. The aliphatic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. Examples of the aliphatic hydrocarbon group include a straight-chain or branched-chain aliphatic hydrocarbon group, and an aliphatic hydrocarbon group having a ring in the structure.

Linear or branched aliphatic hydrocarbon radical

The number of carbon atoms of the straight-chain aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and most preferably 1 to 3.

The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specifically, it may, for example, be methylene [ -CH ]₂-]Ethylene [ - (CH)₂)₂-]Propylene [ - (CH)₂)₃-]Butylene [ - (CH)₂)₄-]- (CH) pentylene [ - (CH)₂)₅-]And the like.

The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically may, for example, be-CH (CH)₃)-、-CH(CH₂CH₃)-、-C(CH₃)₂-、-C(CH₃)(CH₂CH₃)-、-C(CH₃)(CH₂CH₂CH₃)-、-C(CH₂CH₃)₂-isoalkylmethylene; -CH (CH)₃)CH₂-、-CH(CH₃)CH(CH₃)-、-C(CH₃)₂CH₂-、-CH(CH₂CH₃)CH₂-、-C(CH₂CH₃)₂-CH₂-isoalkylethylene; -CH (CH)₃)CH₂CH₂-、-CH₂CH(CH₃)CH₂-isoalkylpropylene; -CH (CH)₃)CH₂CH₂CH₂-、-CH₂CH(CH₃)CH₂CH₂An alkylalkylene group such as an alkylbutylene group, etc. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

The linear or branched aliphatic hydrocarbon group may have a substituent or may have no substituent. Examples of the substituent include a fluorine atom, a fluoroalkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.

Aliphatic hydrocarbon groups containing rings in the structure

Examples of the cyclic aliphatic hydrocarbon group having a ring in its structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing 2 hydrogen atoms from an aliphatic hydrocarbon ring) which may have a substituent and which has a hetero atom in a ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to an end of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups. Examples of the linear or branched aliphatic hydrocarbon group may include the same aliphatic hydrocarbon groups as described above.

The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a monocyclic hydrocarbon. The monocyclic hydrocarbon is preferably a monocyclic hydrocarbon having 3 to 6 carbon atoms, and specifically, cyclopentane, cyclohexane, or the like may be mentioned. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a C7-12 polycycloalkane, and specifically includes adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and a carbonyl group.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a tert-butoxy group, and yet more preferably a methoxy group or an ethoxy group.

The halogen atom as the substituent is preferably a fluorine atom.

Examples of the "haloalkyl" group as the substituent may include a group in which a part or all of hydrogen atoms of the alkyl group are substituted with the halogen atom.

The cyclic aliphatic hydrocarbon group may be partially substituted with a heteroatom-containing substituent. The heteroatom-containing substituent is preferably-O-, -C (═ O) -O-, -S-, -S (═ O)₂-、-S(＝O)₂-O-。

··Ya^x1Aromatic hydrocarbon radical in (1)

The aromatic hydrocarbon group is a hydrocarbon group having at least 1 aromatic ring.

The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Wherein the number of carbons does not include the number of carbons in the substituent.

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

Specific examples of the aromatic hydrocarbon group include a group (arylene group or heteroarylene group) obtained by removing 2 hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring; a group obtained by removing 2 hydrogen atoms from an aromatic compound (for example, biphenyl, fluorene, or the like) containing 2 or more aromatic rings; and a group (aryl or heteroaryl) obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring or the aromatic heterocyclic ring, wherein 1 hydrogen atom is substituted with an alkylene group (for example, a group obtained by removing 1 hydrogen atom from an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), and the like. The number of carbon atoms of the alkylene group bonded to the aryl or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the above aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted by a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, and a hydroxyl group.

Examples of the "alkoxy" and "halogen" and "haloalkyl" as the substituent include those exemplified as substituents for substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.

Heteroatom-containing 2-valent linking groups:

at Ya^x1In the case of a heteroatom-containing 2-valent linking group, examples of the linking group include-O-, -C (═ O) -O-, -O-C (═ O) -, -O-C (═ O) -O-, -C (═ O) -NH-, -NH-C (═ NH) - (H may be substituted with a substituent such as alkyl or acyl), -S-, -S (═ O)₂-、-S(＝O)₂-O-, of the formula-Y²¹-O-Y²²-、-Y²¹-O-、-Y²¹-C(＝O)-O-、-C(＝O)-O-Y²¹-、-[Y²¹-C(＝O)-O]_m”-Y²²-、-Y²¹-O-C(＝O)-Y²²-or-Y²¹-S(＝O)₂-O-Y²²A group represented by (wherein Y is)²¹And Y²²Each independently is a 2-valent hydrocarbon group which may have a substituent, O is an oxygen atom, and m' is an integer of 0 to 3]Etc. as preferred groups.

In the case where the heteroatom-containing 2-valent linking group is — C (═ O) -NH-, -C (═ O) -NH-C (═ O) -, -NH-C (═ NH) -, H thereof may be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms of the substituent (such as alkyl group or acyl group) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

General formula-Y²¹-O-Y²²-、-Y²¹-O-、-Y²¹-C(＝O)-O-、-C(＝O)-O-Y²¹-、-[Y²¹-C(＝O)-O]_m”-Y²²-、-Y²¹-O-C(＝O)-Y²²-or-Y²¹-S(＝O)₂-O-Y²²In (Y)²¹And Y²²Each independently is a 2-valent hydrocarbon group which may have a substituent. The 2-valent hydrocarbon group may, for example, be the group represented by the formula Ya^x1The same groups as those exemplified in the description of the linking group having a valence of 2 (a 2-valent hydrocarbon group which may have a substituent) are mentioned.

As Y²¹The aliphatic hydrocarbon group is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.

As Y²²The aliphatic hydrocarbon group is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

Is represented by the formula- [ Y ]²¹-C(＝O)-O]_m”-Y²²In the group represented by (A), m' is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as represented by the formula- [ Y ]²¹-C(＝O)-O]_m”-Y²²A group represented by the formula-Y is particularly preferred²¹-C(＝O)-O-Y²²-a group represented by (a). Among them, the formula- (CH) is preferred₂)_a’-C(＝O)-O-(CH₂)_b’-a group represented by (a). In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

Among the above, as Ya^x1Preferably a single bond, an ester bond [ -C (═ O) -O-, -O-C (═ O) -]An ether bond (-O-), a linear or branched alkylene group, or a combination thereof, and more preferably a single bond or an ester bond (-C (-O) -O-, -O-C (-O) -)]。

In the formula (a10-1), Wa^x1Is an aromatic hydrocarbon group which may have a substituent.

As Wa^x1The aromatic hydrocarbon group in (1) may be a group obtained by removing (n) from an optionally substituted aromatic ring_ax1+1) hydrogen atoms. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; and an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

Further, as Wa^x1The aromatic hydrocarbon group in (1) may be obtained by removing (n) from an aromatic compound containing 2 or more optionally substituted aromatic rings (e.g., biphenyl, fluorene, etc.)_ax1+1) hydrogen atoms.

Among the above, as Wa^x1Preferably from benzene, naphthalene, anthracene or biphenyl (n)_ax1A group having +1) hydrogen atoms, more preferably (n) is removed from benzene or naphthalene_ax1A group having +1) hydrogen atoms, and (n) is more preferably removed from benzene_ax1+1) hydrogen atoms.

Wa^x1The aromatic hydrocarbon group in (1) may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a haloalkyl group. Examples of the "alkyl", "alkoxy", "halogen atom" and "haloalkyl" as said substituent may include Ya and^x1the same groups as those exemplified for the substituents of the cyclic aliphatic hydrocarbon group in (1) are exemplified. The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Wa^x1The aromatic hydrocarbon group in (1) preferably has no substituent.

In the formula (a10-1), n_ax1Is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1, 2 or 3, and particularly preferably 1 or 2.

Specific examples of the structural unit (a10) represented by the above formula (a10-1) are shown below.

In the following formulae, R^αRepresents a hydrogen atom, a methyl group or a trifluoromethyl group.

[ solution 5]

[ solution 6]

[ solution 7]

[ solution 8]

(A1) The constituent unit (a10) of component (a) may be 1 or 2 or more.

(A1) The proportion of the structural unit (a10) in the component (a1) is preferably 70 to 99 mol%, more preferably 75 to 99 mol%, further preferably 80 to 99 mol%, and particularly preferably 85 to 95 mol%, based on the total (100 mol%) of all the structural units constituting the component (a 1).

By setting the ratio of the structural unit (a10) to the lower limit or more, the development characteristics and the lithography characteristics are further improved. On the other hand, when the upper limit value is not more than the upper limit value, balance with other constituent units is easily obtained.

With respect to structural unit (a 11):

(A1) component (b) is preferably a copolymer having a structural unit (a11) in addition to the structural unit (a10), the structural unit (a11) being a structural unit derived from a compound containing an aromatic ring (excluding an aromatic ring bonded to a hydroxyl group) in a side chain.

Examples of the compound having an aromatic ring (excluding an aromatic ring bonded to a hydroxyl group) in the side chain thereof may preferably include compounds represented by the following general formula (a 11-1).

[ solution 9]

[ in the formula (a11-1), Ra^x2Is a group containing a polymerizable group. Wa^x2Is (n)_ax2+1) a valent aromatic hydrocarbon radical. Wherein, Ra may be substituted^x2And Wa^x2Forming a fused ring structure. Ra^x02Is substituted to form Wa^x2A substituent of a hydrogen atom of (aromatic hydrocarbon group). n is_ax2Is an integer of 0 to 3. n is_ax2In the case of 2 or more, a plurality of Ra^x02May be bonded to each other to form a ring structure.]

In the formula (a11-1), Ra^x2Is a group containing a polymerizable group.

Ra^x2The "polymerizable group" in (1) means a compound having a polymerizable group which can be polymerized by a radical polymerization or the likeThe polymeric group is, for example, a group containing multiple bonds between carbon atoms such as ethylenic double bonds.

Examples of the polymerizable group include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a trifluoroallyl group, a perfluoroallyl group, a trifluoromethylacryloyl group, a nonylfluorobutylacryloyl group, a vinyl ether group, a fluorine-containing vinyl ether group, an allyl ether group, a fluorine-containing allyl ether group, a styryl group, a vinylnaphthyl group, a fluorine-containing styryl group, a fluorine-containing vinylnaphthyl group, a norbornyl group, a fluorine-containing norbornyl group, and a silyl group.

The polymerizable group-containing group may be a group composed of only a polymerizable group, or may be a group composed of a polymerizable group and a group other than the polymerizable group. Examples of the other groups than the polymerizable group include a substituted 2-valent hydrocarbon group, a heteroatom-containing 2-valent linking group, and the like.

As Ra^x2For example, the following compounds represented by the formula: CH (CH)₂＝C(R)-Ya^x0-a group represented by (a). In the chemical formula, R is hydrogen atom, alkyl group with 1-5 carbon atoms or halogenated alkyl group with 1-5 carbon atoms, Ya^x0Is a linking group having a valence of 2.

In the formula (a11-1), Wa^x2Is (n)_ax2+1) valent aromatic hydrocarbon group, which may be exemplified by Wa in the above-mentioned (a10-1)^x1The same groups.

Wherein, Ra may be substituted^x2And Wa^x2Forming a fused ring structure.

In the reaction of Ra^x2And Wa^x2In the case of forming a condensed ring structure, a condensed ring structure containing a condensed ring derived from Wa^x2An aromatic ring of (2). Furthermore, derived from Ra^x2The multiple bonds between carbon atoms of the polymerizable group (A) are cleaved to form the main chain of the component (A1). That is, a part of the carbon atoms constituting the condensed ring constitutes the main chain of component (a 1).

In the formula (a11-1), Ra^x02Is substituted to form Wa^x2A substituent of a hydrogen atom of (aromatic hydrocarbon group).

As Ra^x02Examples of the substituent in (3) include an alkyl group, an alkoxy group, and an acyloxy group.

As Ra^x02The alkyl group as the substituent(s) in (1) is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

As Ra^x02The alkoxy group as the substituent(s) in (1) is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group or a tert-butoxy group, and particularly preferably a methoxy group or an ethoxy group.

As Ra^x02The carbon number of the acyloxy group as a substituent in (1) is preferably 2 to 6, more preferably CH₃C (═ O) -O- (acetoxy), C₂H₅C (═ O) -O-, particularly preferably CH₃C (═ O) -O- (acetoxy).

In the formula (a11-1), n_ax2Is an integer of 0 to 3, preferably 0, 1 or 2, more preferably 0 or 1.

n_ax2In the case of 2 or more, a plurality of Ra^x02May be bonded to each other to form a ring structure. The ring structure formed here may be a hydrocarbon ring or a heterocyclic ring. For example, Wa^x22 Ra bonded to the same aromatic ring^x02And the 2 Ra^x02Bonded aromatic ring (Wa)^x2) A ring structure formed on one side (bonding between carbon atoms).

As the above-mentioned structural unit (a11), for example, structural units represented by the following general formulae (a11-u1-1) to (a11-u1-6) are preferable.

[ solution 10]

[ in the formula, R^αIs hydrogen atom, methyl or trifluoromethyl. R^βIs alkyl, alkoxy or acyloxy. n is_ax2Is an integer of 0 to 3. n is_ax2In the case of 2 or more, a plurality of R^βMay be bonded to each other to form a ring structure. n is₂₁、n₂₂、n₂₄And n₂₅Each independently is 0 or 1. n is₂₃And n₂₆Independently of each other 1 or 2.]

In the formulas (a11-u1-1) to (a11-u1-6), R^βWherein the alkyl group, alkoxy group and acyloxy group in (a) are each independently substituted with Ra in the formula (a11-1)^x02The same applies to the alkyl group, alkoxy group and acyloxy group as examples of the substituent(s) in (1).

Specific examples of the structural unit derived from the compound represented by the general formula (a11-1) (structural unit (a11)) are shown below.

[ solution 11]

[ solution 12]

[ solution 13]

[ solution 14]

[ solution 15]

Among the above examples, the structural unit (a11) is preferably at least one selected from the group consisting of structural units represented by general formulae (a11-u1-1) to (a11-u1-3), and more preferably a structural unit represented by general formula (a11-u 1-1).

Among these structural units, the structural unit (a11) is preferably a structural unit represented by any one of the chemical formulae (a11-u1-11), (a11-u1-21) or (a11-u 1-31).

(A1) The constituent unit (a11) of component (a) may be 1 or 2 or more.

When the component (a1) has the structural unit (a11), the proportion of the structural unit (a11) in the component (a1) is preferably 1 to 30 mol%, more preferably 1 to 25 mol%, still more preferably 1 to 20 mol%, and particularly preferably 5 to 15 mol% based on the total (100 mol%) of all the structural units constituting the component (a 1).

By setting the ratio of the structural unit (a11) to the lower limit or more, the etching resistance and the lithographic characteristics are further improved. On the other hand, when the upper limit value is not more than the upper limit value, balance with other constituent units is easily obtained.

Other structural units

(A1) Component (c) may have other structural units in addition to the structural unit (a10) and the structural unit (a 11).

Examples of the compound from which the other structural unit is derived include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, and the like; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated dienes such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; epoxy group-containing polymerizable compounds, and the like.

In the resist composition of the present embodiment, the component (a) contains a polymer compound (a1) having a structural unit (a10) (component (a 1)).

The preferable component (a1) is a polymer compound having at least a structural unit (a 10). Specifically, the following are preferable: a polymer compound having a repeating structure of the structural unit (a10) (a homopolymer composed of the structural unit (a 10)); a polymer compound having a repeating structure of the structural unit (a10) and the structural unit (a 11).

(A1) The weight average molecular weight (Mw) of the component (B) is not particularly limited, but is preferably 500 to 50000, more preferably 1000 to 30000, and further preferably 2000 to 20000 (in terms of polystyrene equivalent by Gel Permeation Chromatography (GPC)).

If the Mw of the component (a1) is not more than the preferable upper limit of the range, the solubility in a resist solvent is sufficient for use as a resist, and if the Mw of the component is not less than the preferable lower limit of the range, the dry etching resistance and the cross-sectional shape of a resist pattern are further improved.

(A1) The molecular weight distribution coefficient (Mw/Mn) of the component (B) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.5. In addition, Mn represents a number average molecular weight.

The component (a1) can be produced by: the monomer from which each structural unit is derived is dissolved in a polymerization solvent, and a radical polymerization initiator such as Azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) is added thereto to carry out polymerization.

Alternatively, the component (a1) can be produced by: the monomer from which the structural unit (a10) is derived and the monomer from which the structural unit other than the structural unit (a10) is derived, which is used as needed, are dissolved in a polymerization solvent, and the above-mentioned radical polymerization initiator is added thereto to carry out polymerization, followed by deprotection reaction.

In addition, at the time of polymerization,for example, by using HS-CH in combination₂-CH₂-CH₂-C(CF₃)₂A chain transfer agent such as-OH to introduce-C (CF) at the terminal₃)₂-OH groups. Thus, the copolymer of the hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with the fluorine atom is effective in reducing development defects and LER (line edge roughness: uneven line side wall).

With respect to the (A2) component

The resist composition of the present embodiment may use, as the component (a), a base material component (hereinafter referred to as a "component (a 2)") which is not the component (a1) and whose solubility in a developer changes due to the action of an acid.

The component (a2) is not particularly limited, and may be used by arbitrarily selecting from a variety of components known as substrate components for chemically amplified resist compositions.

(A2) The component (C) may be 1 kind of a high molecular compound or a low molecular compound, or 2 or more kinds thereof may be used in combination.

The proportion of the component (a1) in the component (a) is preferably 25% by mass or more, more preferably 50% by mass or more, further preferably 75% by mass or more, and may be 100% by mass, relative to the total mass of the component (a). When the ratio is 25% by mass or more, a resist pattern having excellent lithographic characteristics such as high sensitivity, resolution, and roughness can be easily formed.

The content of the component (a) in the resist composition of the present embodiment may be adjusted according to the thickness of a resist film to be formed.

< ingredient (B) >

With respect to the (B0) component

(B) The component (C) is an acid generator component which generates an acid by exposure. In the resist composition of the present embodiment, the component (B) contains at least the acid generator (B0) ((B0) component) represented by the following general formula (B0-1).

[ solution 16]

[ solution 17]

In the present embodiment, the component (B0) is not particularly limited as long as it is a compound represented by the above formula (B0-1), and examples thereof include at least one compound selected from the group consisting of the following general formulae (B0-1-1) to (B0-1-6).

[ solution 18]

[ in the formula, Rb¹¹And Rb²¹Each independently is a non-aromatic group.]

[ solution 19]

[ in the formula, Rb¹²Is alkyl or haloalkyl. Rb²²Is an aromatic group.]

[ solution 20]

[ in the formula, Rb¹³Is a hydrocarbon group which may have a substituent. nb3 is 2 or 3. Ab is 2-or 3-valentAn organic group.]

[ solution 21]

[ in the formula, Rb¹⁴Is a group of an aromatic polycyclic hydrocarbon group, a saturated or unsaturated non-aromatic polycyclic hydrocarbon group or a substituted derivative thereof. Rb²⁴Are inert organic groups.]

[ solution 22]

[ in the formula, Rb¹⁵Is a substituted or unsubstituted 1-valent saturated hydrocarbon group, unsaturated hydrocarbon group or aromatic group. Xb⁵Is a group which forms a cyclic group having a cyclic imide structure together with- (O ═ C — N — C (═ O) -.]

[ solution 23]

[ in the formula, Rb¹⁶Is an alkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. Rb²⁶¹～Rb²⁶³Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. nb6 is an integer of 0 to 5.]

In the above formula (b0-1-1), Rb is the number¹¹And Rb¹²Examples of the non-aromatic group in (2) include an alkyl group, a haloalkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a cycloalkoxy group, and an adamantyl group.

As Rb¹¹And Rb¹²The alkyl group in (1) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-octyl group, and an n-dodecyl group.

For Rb¹¹And Rb¹²The number of halogen atoms in the haloalkyl group in (1) is not particularly limited, and 1 or more may be introduced. The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The haloalkyl group is preferably a haloalkyl group having 1 to 4 carbon atoms, such as chloromethyl, trichloromethyl, trifluoromethyl, and 2-bromopropyl.

As Rb¹¹And Rb¹²The alkenyl group in (1) is preferably a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, a vinyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, or the like.

As Rb¹¹And Rb¹²The cycloalkyl group in (1) is preferably a cycloalkyl group having 5 to 12 carbon atoms, for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, etc., and the cycloalkenyl group is preferably a cycloalkenyl group having 4 to 8 carbon atoms, for example, a 1-cyclobutenyl group, a 1-cyclopentenyl group, a 1-cyclohexenyl group, a 1-cycloheptenyl group, a 1-cyclooctenyl group, etc.

As Rb¹¹And Rb¹²The alkoxy group in (1) is preferably an alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, or the like.

As Rb¹¹And Rb¹²As the cycloalkoxy group in (1), preferred is a cycloalkoxy group having 5 to 8 carbon atoms, for example, cyclopentyloxy group, cyclohexyloxy group and the like.

In said formula (b0-1-1), as Rb¹¹Alkyl, haloalkyl and cycloalkyl groups are preferred, and alkyl groups are particularly preferred. As Rb²¹Alkyl, cycloalkyl and cycloalkenyl groups are preferred, and cycloalkenyl groups are particularly preferred. Among them, Rb is more preferable¹¹Is alkyl with 1-4 carbon atoms, Rb²¹Is cyclopentenyl.

Specific examples of the compound represented by the formula (b0-1-1) include α - (methylsulfonoxyimino) -1-cyclopentenylacetonitrile, α - (methylsulfonoxyimino) -1-cyclohexenylacetonitrile, α - (methylsulfonoxyimino) -1-cycloheptenylacetonitrile, α - (methylsulfonoxyimino) -1-cyclooctenylacetonitrile, α - (trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α - (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α - (ethylsulfonyloxyimino) -ethylacetonitrile, α - (propylsulfonyloxyimino) -propylacetonitrile, α - (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, and mixtures thereof, α - (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α - (cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α - (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α - (isopropylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α - (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α - (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α - (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α - (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile and the like.

In the formula (b0-1-2), as Rb¹²Examples of the alkyl group in (3) include straight-chain or branched alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

As Rb¹²Examples of the haloalkyl group in (1) to (4) include haloalkyl groups having 1 to 4 carbon atoms such as chloromethyl group, trichloromethyl group, trifluoromethyl group and 2-bromopropyl group.

In the formula (b0-1-2), Rb is²²The aromatic group in (1) is a group showing physical and chemical properties peculiar to an aromatic compound, and examples thereof include a phenyl group, a naphthyl group, a furyl group, and a thienyl group. Rb²²In the aromatic group in (2), a part of hydrogen atoms of the aromatic ring constituting the aromatic group may be substituted with a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and a nitro group.

As the compound represented by the above formula (b0-1-2), specifically, examples thereof include α - (methylsulfonoxyimino) -phenylacetonitrile, α - (methylsulfonoxyimino) -4-methoxyphenylacetonitrile, α - (methylsulfonoxyimino) -4-methylphenylacetonitrile, α - (trifluoromethylsulfonyloxyimino) -phenylacetonitrile, α - (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α - (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α - (propylsulfonyloxyimino) -4-methylphenylacetonitrile and α - (methylsulfonoxyimino) -4-bromophenylacetonitrile.

In said formula (b0-1-3), as Rb¹³Examples of the hydrocarbon group in (2) include an aromatic group and a non-aromatic hydrocarbon group. The aromatic group is preferably an aromatic group having 6 to 14 carbon atoms, and examples thereof include an aromatic hydrocarbon group such as a phenyl group, a tolyl group, a methoxyphenyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, and a heterocyclic group such as a furyl group, a pyridyl group, and a quinolyl group. The non-aromatic hydrocarbon group includes hydrocarbon groups having no aromatic ring such as benzene ring, naphthalene ring, furan ring, thiophene ring, and pyridine ring, for example, aliphatic hydrocarbon groups and alicyclic hydrocarbon groups, including, for example, alkyl groups, alkenyl groups, cycloalkyl groups, and cycloalkenyl groups. The alkyl group and the alkenyl group may be either straight or branched, preferably having 1 to 12 carbon atoms, and the cycloalkyl group and the cycloalkenyl group preferably having 4 to 12 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-octyl group, and an n-dodecyl group, examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a butadienyl group, a hexenyl group, and an octadienyl group, examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and an cyclododecyl group, and examples of the cycloalkenyl group include a 1-cyclobutenyl group, a 1-cyclopentenyl group, a 1-cyclohexenyl group, a 1-cycloheptenyl group, and a 1-cyclooctenyl.

In the formula (b0-1-3), Rb is¹³The hydrocarbon group in (1) may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, and an acyl group.

In the formula (b0-1-3), the organic group having a valence of 2 or 3 in Ab may, for example, be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having a valence of 2 or 3.

Specific examples of the compound represented by the above formula (b0-1-3) are shown below.

[ solution 24]

[ solution 25]

In the formula (b0-1-4), as Rb¹⁴Examples of the aromatic polycyclic hydrocarbon group in (2) include aromatic condensed polycyclic hydrocarbon groups such as 2-indenyl, 1-naphthyl, 2-naphthyl and 2-anthryl, and aromatic non-condensed polycyclic hydrocarbon groups such as biphenyl and terphenyl. Examples of the substituted derivative group include those wherein the aromatic ring is substituted with a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, a nitro group, an amino group, a hydroxyl group, an alkyl group, an alkoxy group or the like, and examples thereof include a 5-hydroxy-1-naphthyl group and a 4-amino-1-naphthyl group.

In the formula (b0-1-4), as Rb¹⁴Examples of the saturated or unsaturated nonaromatic polycyclic hydrocarbon group in (1) include a polycyclic terpene residue and an adamantyl group, and a polycyclic terpene residue is preferable. Examples of the substituted derivative group include those having a suitable substituent such as a halogen atom (e.g., a chlorine atom, a bromine atom or an iodine atom), a nitro group, an amino group, a hydroxyl group, an oxo group, an alkyl group or an alkoxy group in the ring. As examples of such groups, there are camphor-3-yl, camphor-8-yl, camphor-10-yl, 3-bromocamphor-10-yl and the like.

As the Rb¹⁴Naphthyl and camphor-10-yl are preferable, and 1-naphthyl is particularly preferable because of its excellent resolution.

In the formula (b0-1-4), Rb is²⁴The inert organic group in (b) is an organic group inert to the coexisting components under the conditions of use, and is not particularly limited, but an aromatic group is preferable from the viewpoint of sensitivity to an alignment molecule laser, an electron beam, and an X-ray. Examples of the aromatic group include a phenyl group, a naphthyl group, a furyl group, and a thienyl group. These aromatic groups may have an inert substituent such as a halogen atom (e.g., chlorine atom, bromine atom, iodine atom), an alkyl group, an alkoxy group, a nitro group, etcAnd (4) generation of base.

Specific examples of the compound represented by the above formula (b0-1-4) include α - (1-naphthylsulfonyloxyimino) -4-methoxybenzyl cyanide, α - (2-naphthylsulfonyloxyimino) -4-methoxybenzyl cyanide, α - (1-naphthylsulfonyloxyimino) benzyl cyanide, α - (2-naphthylsulfonyloxyimino) benzyl cyanide, α - (10-camphorsulfonyloxyimino) -4-methoxybenzyl cyanide, α - (10-camphorsulfonyloxyimino) benzyl cyanide, α - (3-camphorsulfonyloxyimino) -4-methoxybenzyl cyanide, α - (3-bromo-10-camphorsulfonyloxyimino) -4-methoxybenzyl cyanide, and the like.

In said formula (b0-1-5), as Rb¹⁵Examples of the substituted or unsubstituted 1-valent saturated or unsaturated hydrocarbon group in (1) include linear or branched saturated or unsaturated hydrocarbon groups having 1 to 8 carbon atoms and groups obtained by substituting these groups with a halogen atom, a nitro group, an acetylamino group, a lower alkoxy group, a monocyclic aryl group, etc., and particularly preferred are groups having a substituent such as a halogen atom, a lower alkoxy group, etc. Further, as Rb¹⁵Examples of the substituted or unsubstituted 1-valent aromatic group in (1) include monocyclic or bicyclic groups, and particularly preferred is a group in which a benzene ring is substituted with a vinyl group, an alkyl group, an alkoxy group, a halogen atom, or the like.

In the formula (b0-1-5), as Xb⁵Examples of the cyclic group having a cyclic imide structure which is formed together with- (O ═ C-N-C (═ O) -, include a succinimide ring, a maleimide ring, a glutarimide ring, a phthalimide ring, and a1, 8-naphthalenediimide ring. Xb⁵The cyclic group having a cyclic imide structure, which is formed together with- (O ═ C-N-C (═ O) -, may have a substituent. Examples of the substituent include a halogen atom, a nitro group, an acetylamino group, an alkoxy group, and a monocyclic aryl group.

Specific examples of the compound represented by the above formula (b0-1-5) include N-methylsulfonyloxy succinimide, N-isopropylsulfonyloxy succinimide, N-chloroethylsulfonyloxy succinimide, N- (p-methoxyphenyl) sulfonyloxy succinimide, N- (p-vinylphenyl) sulfonyloxy succinimide, N-naphthalenesulfonyloxy succinimide, N-phenylsulfonyloxy succinimide, N- (2, 4, 6-trimethylphenyl) sulfonyloxy succinimide, N-methylsulfonyloxy maleimide, N-isopropylsulfonyloxy maleimide, N-chloroethylsulfonyloxy maleimide, N- (p-methoxyphenyl) sulfonyloxy maleimide, N-isopropylsulfonyloxy maleimide, N-sulfonyloxy maleimide, N-isopropylsulfonyloxy maleimide, N, N- (p-vinylphenyl) sulfonyloxy maleimide, N-naphthalenesulfonyloxy maleimide, N-phenylsulfonyloxy maleimide, N- (2, 4, 6-trimethylphenyl) sulfonyloxy maleimide, N-methylsulfonyloxyphthalimide, N-isopropylsulfonyloxyphthalimide, N-chloroethylsulfonyloxyphthalimide, n- (p-methoxyphenyl) sulfonyloxyphthalimide, N- (p-vinylphenyl) sulfonyloxyphthalimide, N-naphthalenesulfonyloxyphthalimide, N-phenylsulfonyloxyphthalimide, N- (2, 4, 6-trimethylphenyl) sulfonyloxyphthalimide, compounds described in paragraphs [0089] to 0091] of Japanese patent laid-open publication No. H10-097075, and the like.

In said formula (b0-1-6), as Rb¹⁶The alkyl group in (3) is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2, 4, 4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl and the like.

Wherein, as Rb¹⁶The alkyl group in (1) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 5 carbon atoms.

Rb¹⁶The alkyl group in (1) may have a substituent. Examples of the substituent include a halogen atom, a haloalkyl group, CN and NO₂Phenyl, alkoxy, carboxyl, carbonyl, sulfonyl, amino and the like.

In the formula (b0-1-6), as Rb¹⁶The aromatic hydrocarbon group in (1) may, for example, be a phenyl group, a naphthyl group or a phenanthryl groupAnthracenyl, heteroaryl, and the like. Rb¹⁶The aromatic hydrocarbon group in (1) may have a substituent. Examples of the substituent include a halogen atom, a haloalkyl group, CN and NO₂Phenyl, alkoxy, carboxyl, carbonyl, sulfonyl, amino and the like.

Specific examples of the compound represented by the formula (b0-1-6) include a compound represented by the following chemical formula (b0-1-61), and compounds of examples 25 to 40 and 53 of JP 2002-508774A.

[ solution 26]

Other specific examples of the component (B0) include compounds described in paragraphs [0056], [0058], [0060] and [0063] of Japanese patent No. 4110392, and compounds described in paragraphs [0053], [0054], [0056], [0058], [0060] and [0062] of Japanese patent No. 4000469.

Among them, as the component (B1), at least 1 selected from the group consisting of the compound represented by the formula (B0-1-2), the compound represented by the formula (B0-1-3), the compound represented by the formula (B0-1-5) and the compound represented by the formula (B0-1-6) is preferable, and at least one selected from the group consisting of the compound represented by the formula (B0-1-2), the compound represented by the formula (B0-1-3) and the compound represented by the formula (B0-1-6) is more preferable.

Preferable specific examples of the component (B0) are described below.

[ solution 27]

The component (B0) contained in the resist composition of the present embodiment may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

In the resist composition of the present embodiment, the content of the component (B0) is preferably 50 parts by mass or less, more preferably 0.1 to 40 parts by mass, still more preferably 0.1 to 30 parts by mass, and particularly preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the component (a).

When the content of the component (B) is in the above range, the pattern formation can be sufficiently performed.

With respect to the (B1) component

The resist composition of the present embodiment may further contain an acid generator (hereinafter referred to as "(B1) component") other than the (B0) component as the (B) component.

The component (B1) is not particularly limited, and acid generators proposed heretofore as acid generators for use in chemically amplified resist compositions can be used.

Examples of such an acid generator include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators; diazomethane acid generators such as dialkyl or bisarylsulfonyl diazomethane and poly (bissulfonyl) diazomethane; nitrobenzyl sulfonate acid generators, disulfone acid generators, and the like.

Examples of the onium salt-type acid generator include a compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), a compound represented by the following general formula (b-2) (hereinafter also referred to as "component (b-2)"), and a compound represented by the following general formula (b-3) (hereinafter also referred to as "component (b-3)").

[ solution 28]

[ in the formula, R¹⁰¹、R¹⁰⁴～R¹⁰⁸Each independently represents a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent. R¹⁰⁴、R¹⁰⁵May be bonded to each other to form a ring. R¹⁰²Is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. Y is¹⁰¹Is a single bond or a 2-valent linking group comprising an oxygen atom. V¹⁰¹～V¹⁰³Each independently a single bond, alkylene, or fluoroalkylene. L is¹⁰¹～L¹⁰²Each independently being a single bond or an oxy groupAnd (4) adding the active ingredients. L is¹⁰³～L¹⁰⁵Each independently of the other being a single bond, -CO-or-SO₂-. M is an integer of 1 or more, M'^m+Is an onium cation having a valence of m.]

{ anion portion }

The anion part of component (b-1)

In the formula (b-1), R¹⁰¹The alkyl group may be a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent.

A cyclic group which may have a substituent:

the cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromatic character. The aliphatic hydrocarbon group may be saturated or unsaturated, and is preferably saturated.

R¹⁰¹The aromatic hydrocarbon group in (1) is a hydrocarbon group having an aromatic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. Wherein the number of carbons does not include the number of carbons in the substituent.

As R¹⁰¹The aromatic ring of the aromatic hydrocarbon group in (3) may, specifically, be benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocycle in which a part of carbon atoms constituting the aromatic ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.

As R¹⁰¹Specific examples of the aromatic hydrocarbon group in (1) include a group obtained by removing 1 hydrogen atom from the aromatic ring (an aryl group: e.g., a phenyl group or a naphthyl group), and a group obtained by substituting 1 hydrogen atom of the aromatic ring with an alkylene group (e.g., an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group or a 2-naphthylethyl group). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

R¹⁰¹Examples of the cyclic aliphatic hydrocarbon group includeAliphatic hydrocarbon groups containing rings in the structure.

Examples of the aliphatic hydrocarbon group having a ring in its structure include an alicyclic hydrocarbon group (a group obtained by removing 1 hydrogen atom from an aliphatic hydrocarbon ring), a group obtained by bonding an alicyclic hydrocarbon group to the end of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups.

The alicyclic hydrocarbon group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.

The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing 1 or more hydrogen atoms from a monocyclic hydrocarbon. The monocyclic hydrocarbon is preferably a monocyclic hydrocarbon having 3 to 6 carbon atoms, and specifically, cyclopentane, cyclohexane, or the like may be mentioned. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing 1 or more hydrogen atoms from a cycloalkane, and the polycycloalkane is preferably a C7-30 polycycloalkane. Among these, as the polycyclic alkane, polycyclic alkanes having a polycyclic skeleton with a crosslinked ring, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, are more preferable; polycyclic alkanes having a polycyclic skeleton of condensed rings, such as cyclic groups having a steroid skeleton.

Wherein, as R¹⁰¹The cyclic aliphatic hydrocarbon group in (2) is preferably a group obtained by removing 1 or more hydrogen atoms from a monocycloparaffin or a polycycloalkane, more preferably a group obtained by removing 1 hydrogen atom from a polycycloalkane, particularly preferably an adamantyl group, a norbornyl group, or a cyclic group having a steroid skeleton, and most preferably an adamantyl group or a cyclic group having a steroid skeleton.

The straight or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

Furthermore, R¹⁰¹The cyclic hydrocarbon group in (2) may contain a hetero atom like a heterocycle and the like. Specifically, examples thereof include lactone ring-containing groups represented by the general formulae (a2-r-1) to (a2-r-7) and-SO-containing groups represented by the general formulae (a5-r-1) to (a5-r-4)₂A cyclic group and other heterocyclic groups represented by the following chemical formulae (r-hr-1) to (r-hr-16).

[ solution 29]

As R¹⁰¹Examples of the substituent in the cyclic group (b) include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, or an n-butyl groupA tert-butyl group.

The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.

Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the haloalkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, for example, groups in which some or all of hydrogen atoms such as methyl, ethyl, propyl, n-butyl, and tert-butyl are substituted with the above-mentioned halogen atom.

The carbonyl group as the substituent is a methylene group (-CH) substituted for the cyclic hydrocarbon group₂-) of (a) a group of (b).

Chain alkyl group which may have a substituent:

as R¹⁰¹The chain alkyl group of (b) may be either linear or branched.

The straight-chain alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl and docosyl.

The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples thereof include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl and 4-methylpentyl.

Chain alkenyl group which may have a substituent:

as R¹⁰¹The chain alkenyl group (C) may be either straight or branched, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, and further more preferablyThe one-step is preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylethenyl group, a 2-methylethenyl group, a 1-methylpropenyl group and a 2-methylpropenyl group.

Among the above, the linear alkenyl group is preferably a linear alkenyl group, more preferably an ethenyl group or a propenyl group, and particularly preferably an ethenyl group.

As R¹⁰¹Examples of the substituent in the linear alkyl group or the linear alkenyl group of (3) include an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above-mentioned R¹⁰¹Cyclic group in (1), and the like.

Wherein R is¹⁰¹The cyclic group may have a substituent, and more preferably a cyclic hydrocarbon group may have a substituent. More specifically, a group obtained by removing 1 or more hydrogen atoms from a phenyl group, a naphthyl group, or a polycyclic alkane is preferable; lactone ring-containing groups represented by the general formulae (a2-r-1), (a2-r-3) to (a2-r-7), respectively; containing-SO represented by the general formulae (a5-r-1) to (a5-r-4) respectively₂-cyclic groups, etc.

In the formula (b-1), Y¹⁰¹Is a single bond or a 2-valent linking group comprising an oxygen atom.

At Y¹⁰¹In the case of a 2-valent linking group containing an oxygen atom, Y¹⁰¹Atoms other than oxygen atoms may be contained. Examples of the atom other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.

Examples of the linking group having a valence of 2 and containing an oxygen atom may include linking groups represented by the general formulae (y-al-1) to (y-al-8) described above.

As Y¹⁰¹The linking group having a valence of 2 and containing an ester bond or the linking group having a valence of 2 and containing an ether bond are preferable, and the linking groups represented by the general formulae (y-al-1) to (y-al-5) are more preferable.

In the formula (b-1), V¹⁰¹Is a single bond, alkylene or fluoroalkylene. V¹⁰¹The carbon number of the alkylene group or fluoroalkylene group in (1) is preferably1 to 4. As V¹⁰¹The fluoroalkylene group in (1) may, for example, be V¹⁰¹Wherein a part or all of hydrogen atoms of the alkylene group in (1) are substituted by fluorine atoms. Wherein, V¹⁰¹Preferably a single bond or a C1-4 fluoroalkylene group.

In the formula (b-1), R¹⁰²Is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. R¹⁰²Preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

Specific examples of the anion portion of the component (b-1) include, for example, those in Y¹⁰¹Examples of the "single bond" may include fluoroalkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutane sulfonate anion; at Y¹⁰¹In the case of a linking group having a valence of 2 and containing an oxygen atom, an anion represented by any one of the following formulae (an-1) to (an-3) may be mentioned.

[ solution 30]

[ in the formula, R "¹⁰¹Is an alicyclic ring group which may have a substituent, a 1-valent heterocyclic group represented by the above chemical formulae (r-hr-1) to (r-hr-6), or a chain alkyl group which may have a substituent. R'¹⁰²Is an aliphatic cyclic group which may have a substituent, a lactone-containing cyclic group represented by the general formulae (a2-r-1), (a2-r-3) to (a2-r-7), or an-SO-containing cyclic group represented by the general formulae (a5-r-1) to (a5-r-4)₂-a cyclic group. R'¹⁰³The group is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. V'¹⁰¹Is a single bond, an alkylene group having 1 to 4 carbon atoms or a fluoroalkylene group having 1 to 4 carbon atoms. R¹⁰²Is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. v ' is an integer of 0 to 3, q ' is an integer of 1 to 20, and n ' is 0 or 1.]

R”¹⁰¹、R”¹⁰²And R "¹⁰³May have a substituent(s)The radical of formula (II) is preferably as said R¹⁰¹The cyclic aliphatic hydrocarbon group in (1) is exemplified. The substituent may, for example, be represented by the formula¹⁰¹The same groups as those mentioned above as the substituents which may be substituted for the cyclic aliphatic hydrocarbon group.

R”¹⁰³The aromatic cyclic group which may have a substituent(s) in (1) is preferably the R¹⁰¹Examples of the aromatic hydrocarbon group in the cyclic hydrocarbon group in (1) are given. The substituent may, for example, be represented by the formula¹⁰¹The same groups as those in (1) may be substituted for the aromatic hydrocarbon group.

R”¹⁰¹The chain alkyl group which may have a substituent(s) in (1) is preferably the R group¹⁰¹The chain alkyl group in (1) above. R'¹⁰⁴The optionally substituted chain alkenyl group in (1) is preferably the R group¹⁰¹The chain alkenyl group in (1) is exemplified.

V”¹⁰¹Preferably a single bond or a fluoroalkylene group, and more preferably a single bond or a fluoroalkylene group having 1 to 3 carbon atoms. At V'¹⁰¹In the case of fluoroalkylene radicals, -V "¹⁰¹-C(F)(R”¹⁰²)-SO₃ ^-V in (1) "¹⁰¹preferably-CF₂-、-CHF-、-CF₂CF₂-、-CHFCF₂-、-CF(CF₃)CF₂-、-CH(CF₃)CF₂-, more preferably-CF₂-、-CHF-。

R¹⁰²Is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. R¹⁰²Preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

v' is an integer of 0 to 3, preferably 0 or 1. q' is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1, 2 or 3, and particularly preferably 1 or 2. n "is 0 or 1.

Anion part of component (b-2)

In the formula (b-2), R¹⁰⁴、R¹⁰⁵Each of which is independently a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent, are exemplified byR in the formula (b-1)¹⁰¹The same groups. Wherein R is¹⁰⁴、R¹⁰⁵May be bonded to each other to form a ring.

R¹⁰⁴、R¹⁰⁵The alkyl group is preferably a chain alkyl group which may have a substituent, more preferably a linear or branched alkyl group or a linear or branched fluoroalkyl group.

The number of carbon atoms of the chain alkyl group is preferably 1 to 10, more preferably 1 to 7, and further preferably 1 to 3. R is also good in solubility in a solvent for a resist, and the like¹⁰⁴、R¹⁰⁵The number of carbons of the chain alkyl group(s) is preferably as small as possible within the above-mentioned range of carbon numbers. Furthermore, R¹⁰⁴、R¹⁰⁵The chain alkyl group (2) is preferred because the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength. The proportion of fluorine atoms in the chain alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

In the formula (b-2), V¹⁰²、V¹⁰³Each independently represents a single bond, an alkylene group or a fluoroalkylene group, and is exemplified by V in the formula (b-1)¹⁰¹The same groups.

In the formula (b-2), L¹⁰¹、L¹⁰²Each independently a single bond or an oxygen atom.

The anion part of component (b-3)

In the formula (b-3), R¹⁰⁶～R¹⁰⁸Each of which is independently a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent, is exemplified by R in the formula (b-1)¹⁰¹The same groups.

L¹⁰³～L¹⁰⁵Each independently of the other being a single bond, -CO-or-SO₂-。

{ cation portion }

In the formulae (b-1), (b-2) and (b-3), M is an integer of 1 or more, M'^m+As the onium cation having a valence of m, sulfonium cation and iodonium cation can be preferably mentioned, and examples thereof include organic cations represented by the general formulae (ca-1) to (ca-4)A cation.

[ solution 31]

[ in the formula, R²⁰¹～R²⁰⁷And R²¹¹～R²¹²Each independently represents an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. R²⁰¹～R²⁰³、R²⁰⁶～R²⁰⁷、R²¹¹～R²¹²May be bonded to each other to form a ring together with the sulfur atom in the formula. R²⁰⁸～R²⁰⁹Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or may be bonded to each other to form a ring together with the sulfur atom in the formula. R²¹⁰Is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a-SO-containing group which may have a substituent₂-a cyclic group. L is²⁰¹represents-C (═ O) -or-C (═ O) -O-. Plural of Y²⁰¹Each independently represents an arylene group, an alkylene group or an alkenylene group. x is 1 or 2. W²⁰¹Represents a (x +1) -valent linking group.]

As R²⁰¹～R²⁰⁷And R²¹¹～R²¹²Examples of the aryl group in (1) include aryl groups having 6 to 20 carbon atoms, and phenyl and naphthyl groups are preferable.

As R²⁰¹～R²⁰⁷And R²¹¹～R²¹²The alkyl group in (1) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

As R²⁰¹～R²⁰⁷And R²¹¹～R²¹²The alkenyl group in (1) preferably has 2 to 10 carbon atoms.

As R²⁰¹～R²⁰⁷And R²¹¹～R²¹²Examples of the substituent which may be present include an alkyl group, a halogen atom, a haloalkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulae (ca-r-1) to (ca-r-7).

[ solution 32]

[ wherein R'²⁰¹Each independently represents a hydrogen atom, a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent.]

R’²⁰¹Examples of the cyclic group which may have a substituent, the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent include R in the formula (b-1) described later¹⁰¹Examples of the same group other than the above-mentioned groups include the same groups as the acid-dissociable group represented by the above-mentioned formula (a1-r-2), as a cyclic group which may have a substituent or a chain alkyl group which may have a substituent.

At R²⁰¹～R²⁰³、R²⁰⁶～R²⁰⁷、R²¹¹～R²¹²When they are bonded to each other to form a ring together with the sulfur atom in the formula, they may be bonded to each other via a heteroatom such as a sulfur atom, an oxygen atom, a nitrogen atom or the like, a carbonyl group, -SO-, -SO₂-、-SO₃-, -COO-, -CONH-or-N (R)_N) - (the R)_NAlkyl group having 1 to 5 carbon atoms) and the like. The ring to be formed is preferably a three-to ten-membered ring in which 1 ring including the sulfur atom in the formula in the ring skeleton includes a sulfur atom, and particularly preferably a five-to seven-membered ring. Specific examples of the ring to be formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

R²⁰⁸～R²⁰⁹Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, in R²⁰⁸～R²⁰⁹In the case of an alkyl group, they may be bonded to each other to form a ring.

R²¹⁰Is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent-containing group which may have a substituent-SO₂-a cyclic group.

As R²¹⁰Examples of the aryl group in (1) include unsubstituted aryl groups having 6 to 20 carbon atoms, and phenyl and naphthyl are preferable.

As R²¹⁰The alkyl group in (1) is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

As R²¹⁰The alkenyl group in (1) is preferably an alkenyl group having 2 to 10 carbon atoms. As R²¹⁰Wherein the-SO-containing group may have a substituent₂-cyclic radicals, preferably "containing-SO₂A polycyclic group ", more preferably a group represented by the general formula (a 5-r-1).

Y²⁰¹Each independently represents an arylene group, an alkylene group or an alkenylene group.

Y²⁰¹The arylene group in (A) is exemplified by R in the formula (b-1)¹⁰¹The aromatic hydrocarbon group in (1) is a group obtained by removing 1 hydrogen atom from an aryl group.

Y²⁰¹Examples of the "alkylene" and "alkenylene" may include R in the formula (b-1)¹⁰¹The group (b) in (a) is a group obtained by removing 1 hydrogen atom from the group exemplified as the chain alkyl group or the chain alkenyl group.

In the formula (ca-4), x is 1 or 2.

W²⁰¹Is a linking group having a valence of (x +1), i.e., 2 or 3.

As W²⁰¹The 2-valent linking group in (a) is preferably a 2-valent hydrocarbon group which may have a substituent(s), and may be exemplified by the group corresponding to Ya in the above-mentioned general formula (a2-1)²¹The same 2-valent hydrocarbon group which may have a substituent. W²⁰¹The 2-valent linking group in (b) may be linear, branched or cyclic, and is preferably cyclic. Among these, a group in which 2 carbonyl groups are combined at both ends of an arylene group is preferable. The arylene group may, for example, be a phenylene group or a naphthylene group, and a phenylene group is particularly preferable.

As W²⁰¹The linking group having a valence of 3 in (1) may, for example, be represented by the formula W²⁰¹Wherein 1 hydrogen atom is removed from the 2-valent linking group, and the 2-valent linking group is bonded to the 2-valent linking groupGroups, and the like. As W²⁰¹The linking group having a valence of 3 in (1) is preferably a group in which 2 carbonyl groups are bonded to an arylene group.

Specific examples of the preferable cation represented by the formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149).

In the following chemical formula, g1 represents the number of repetitions, and g1 is an integer of 1 to 5. g2 represents the number of repeats, and g2 is an integer of 0 to 20. g3 represents the number of repeats, and g3 is an integer of 0 to 20.

[ solution 33]

[ chemical 34]

[ solution 35]

[ solution 36]

[ solution 37]

[ solution 38]

[ solution 39]

[ solution 40]

[ solution 41]

[ solution 42]

[ in the formula, R "²⁰¹Is a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned R²⁰¹～R²⁰⁷And R²¹¹～R²¹²Examples of the substituent(s) include alkyl groups, halogen atoms, haloalkyl groups, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by the general formulae (ca-r-1) to (ca-r-7).]

Specific examples of the preferable cation represented by the formula (ca-2) include cations represented by the following formulae (ca-2-1) to (ca-2-3), a diphenyliodonium cation, and a bis (4-tert-butylphenyl) iodonium cation.

[ solution 43]

Specific examples of the preferable cation represented by the formula (ca-3) include cations represented by the following formulae (ca-3-1) to (ca-3-7).

[ solution 44]

Specific examples of the preferable cation represented by the formula (ca-4) include cations represented by the following formulae (ca-4-1) to (ca-4-2).

[ solution 45]

Of the above, the cation portion ((M)^m+)_1/m) The cation represented by the general formula (ca-1) or (ca-2) is preferable, and the cations represented by the formulae (ca-1-1) to (ca-1-78), (ca-1-101) to (ca-1-149) and (ca-2-1) to (ca-2-3) are more preferable.

In the resist composition of the present embodiment, 1 kind of the component (B1) may be used alone, or 2 or more kinds may be used in combination.

When the resist composition contains the component (B1), the content of the component (B1) in the resist composition is preferably 50 parts by mass or less, more preferably 0.1 to 40 parts by mass, still more preferably 0.1 to 30 parts by mass, and particularly preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the component (a).

< ingredient (C) >

(C) The ingredient is a crosslinking agent. The component (C) is not particularly limited, and can be arbitrarily selected from known crosslinking agents for negative resist compositions. Examples of the acid-crosslinkable substance include amino resins having a hydroxyl group or an alkoxy group, such as melamine resins, urea resins, guanamine resins, acetoguanamine resins, benzoguanamine resins, glycoluril-formaldehyde resins, succinamide-formaldehyde resins, and ethyleneurea-formaldehyde resins. The acid-crosslinkable substance can be easily obtained by methylolating melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluril, succinamide, or ethylene urea by reacting the compound with formalin in boiling water, or by alkoxylating the compound by further reacting the compound with a lower alcohol. From the practical viewpoint, they can be obtained as melamine resins such as Nikalac (ニカラツク, registered trademark) MX-750, NikalacMW-30 and NikalacMW100LM, and urea resins such as NikalacMX-290 (manufactured by Sanwa chemical Co., Ltd.). Benzoguanamine resins such as CYMEL1123 and CYMEL1128 (manufactured by Mitsui Cyanamid co., ltd.) are also available as commercially available products.

Further, as the component (C), benzene compounds having an alkoxy group such as 1, 3, 5-tris (methoxymethoxy) benzene, 1, 2, 4-tris (isopropoxymethoxy) benzene, 1, 4-bis (sec-butoxymethoxy) benzene; and phenol compounds having a hydroxyl group or an alkoxy group such as 2, 6-dimethylol-p-tert-butylphenol.

Among them, component (C) preferably contains-NCH₂-OCH₃The compound of (B) is more preferably a compound represented by the following formula (c1-1) or (c1-2), and still more preferably a compound having a melamine skeleton represented by the following formula (c1-1) or (c 1-2).

[ solution 46]

[ in the formula, nc1 and nc2 are each independently an integer of 1 to 3. ]

(C) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

In the resist composition of the present embodiment, the content of the component (C) is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, still more preferably 3 to 30 parts by mass, and most preferably 5 to 25 parts by mass, based on 100 parts by mass of the component (a).

When the content of the component (C) is not less than the lower limit, crosslinking formation proceeds sufficiently, and the resolution performance and the lithographic characteristics are further improved. Further, a good resist pattern with less swelling can be obtained. If the amount is less than the upper limit, the storage stability of the resist composition is good, and deterioration of sensitivity with time is easily suppressed.

< ingredient (Z) >

The component (Z) is not particularly limited as long as it is an aromatic compound having 1 or 2 phenolic hydroxyl groups in the molecule and no carboxyl group.

The component (Z) preferably contains at least one compound selected from the group consisting of a compound represented by the following general formula (Z1-1) and a compound represented by the following general formula (Z2-1).

[ solution 47]

[ in the formula (z1-1), V_z ¹Is a 2-valent linking group having no hydroxyl group and no carboxyl group. In the formula (z2-1), Rz²Is a hydrocarbyl group. n1 is 1 or 2. n2 is an integer of 2 to 5. Wherein n1+ n2 is less than or equal to 6.]

In the formula (z1-1), as V_z ¹The 2-valent linking group in (1) which does not have a hydroxyl group or a carboxyl group may, for example, be Ya in the above formula (a10-1)^x1The 2-valent linking group in (2) does not have a 2-valent linking group of a hydroxyl group and a carboxyl group. Further, as V_z ¹The linking group having a valence of 2 in (a) may, for example, be Ya in the above general formula (a10-1)^x1In the 2-valent linking group, a part of hydrogen atoms of the linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group.

The "group obtained by substituting a part of hydrogen atoms constituting the linear or branched aliphatic hydrocarbon group with an aromatic hydrocarbon group" as the linear or branched aliphatic hydrocarbon group may, for example, be a methylene group [ -CH₂-]Ethylene [ - (CH)₂)₂-]、-CH(CH₃)-、-CH(CH₂CH₃)-、-C(CH₃)₂-、-C(CH₃)(CH₂CH₃)-、-C(CH₃)(CH₂CH₂CH₃)-、-C(CH₂CH₃)₂An isoalkylmethylene group and the like.

The aromatic hydrocarbon group in the "group in which a part of hydrogen atoms constituting the linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group" may, for example, be a group obtained by removing one hydrogen atom from an aromatic ring such as benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or the like.

The aromatic hydrocarbon group in the "group in which a part of hydrogen atoms constituting the linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group" may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and an arylalkyl group.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

Examples of the "alkoxy", "halogen" and "haloalkyl" related to the above-mentioned substituent may include Ya in the above-mentioned general formula (a10-1)^x1Among the 2-valent linking groups in (2), those exemplified as substituents for substituting hydrogen atoms of the cyclic aliphatic hydrocarbon group are exemplified.

Examples of the arylalkyl group as the substituent include benzyl, phenethyl, phenyl-tert-butyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl and 2-naphthylethyl. The arylalkyl group may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, or an arylalkyl group.

As the compound represented by the above formula (z1-1), a compound represented by the following general formula (z1-1-1) is preferable.

[ solution 48]

[ in the formula, R_z ¹¹And R_z ¹²Each independently a hydrogen atom or a hydrocarbon group which may have a substituent. R_z ¹¹And R_z ¹²May be bonded to each other to form a ring.]

In the formula (z1-1-1), as R_z ¹¹And R_z ¹²Examples of the hydrocarbon group of (b) include a linear or branched alkyl group, an aromatic hydrocarbon group which may have a substituent, and the like.

The number of carbon atoms of the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and further preferably 1 or 2. Specifically, the alkyl group may include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like. Among them, methyl, ethyl or n-butyl is preferable, and methyl or ethyl is more preferable.

The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, the alkyl group may include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1-diethylpropyl, and 2, 2-dimethylbutyl, with isopropyl being preferred.

As R_z ¹¹And R_z ¹²The aromatic hydrocarbon group in (1) may, for example, be a group obtained by removing 1 hydrogen atom from an aromatic ring such as benzene, fluorene, naphthalene, anthracene, phenanthrene or biphenyl.

R_z ¹¹And R_z ¹²The aromatic hydrocarbon group in (1) may have a substituent. The substituent may be the same as the substituent that the aromatic hydrocarbon group in the above-mentioned "group in which a part of hydrogen atoms constituting the linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group".

In the formula (z1-1-1), R_z ¹¹And R_z ¹²May be bonded to each other to form a ring. Examples of the ring to be formed include aliphatic rings such as cyclopentane, cyclohexane, and cycloheptane rings.

In the formula (z1-1-1), R_z ¹¹And R_z ¹²Preferably a linear alkyl group or an aromatic hydrocarbon group having a substituent group and having 1 to 5 carbon atoms, or R_z ¹¹And R_z ¹²Bonded to each other to form an alicyclic ring, more preferably methyl, phenyl or 4- (4-hydroxyphenyl-t-butyl) phenyl, or R_z ¹¹And R_z ¹²Bonded to each other to form a cyclohexane ring.

In the above formula (z2-1), Rz is²As the hydrocarbon group in (1), there may be mentioned R in the above-mentioned formula (z1-1-1)_z ¹¹And R_z ¹²The hydrocarbon group of (1) is exemplified. Wherein as Rz²An aromatic hydrocarbon group is preferable, a phenyl group or a benzyl group is more preferable, and a phenyl group is further preferable.

In the formula (z1-2), n1 is preferably 1. n2 is preferably 2 or 3, more preferably 2.

As the compound represented by the above formula (z1-2), a compound represented by the following general formula (z1-2-1) is preferable.

[ solution 49]

[ wherein Rz²¹And Rz²²Each independently is an aromatic hydrocarbon group.]

In the formula (z1-2-1), Rz is²As the hydrocarbon group of (2), there may be mentioned Rz in the formula (z1-1-1)¹¹And Rz¹²The hydrocarbon group of (1) is exemplified. Wherein as Rz²Preferably phenyl or benzyl, more preferably phenyl.

Specific examples of the component (Z) are shown below.

[ solution 50]

The mass average molecular weight (Mw) of the component (Z) is preferably 1000 or less, more preferably 100 to 950, and still more preferably 150 to 900.

When the mass average molecular weight of the component (Z) is equal to or less than the upper limit of the above preferable range, the substrate adhesion performance can be easily improved, and the wet etching resistance can be easily improved.

The component (Z) contained in the resist composition of the present embodiment may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

In the resist composition of the present embodiment, the content of the component (Z) is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and still more preferably 3 to 20 parts by mass, based on 100 parts by mass of the component (a).

When the proportion of the component (Z) is within the above-described preferable range, the etching resistance is good and a pattern having a good shape can be easily formed.

< optional Components >

(D) component

The resist composition of the present embodiment may contain an acid diffusion controller component (hereinafter referred to as "component (D)") in addition to the components (a), (B), (C) and (Z). (D) The component (a) is a component that functions as a quencher (acid diffusion controller) for trapping an acid generated by exposure in the resist composition.

Examples of the component (D) include a nitrogen-containing organic compound (D1) (hereinafter referred to as a "component (D1)"), and a photodegradable base (D2) (hereinafter referred to as a "component (D2)") which does not belong to the component (D1) and loses its acid diffusion controllability by decomposition by exposure to light.

When a resist pattern is formed, the contrast between the exposed portion and the unexposed portion of the resist film can be further improved by the resist composition containing the component (D).

With respect to the (D1) component

(D1) The component (B) is an alkali component, and is a nitrogen-containing organic compound component which functions as an acid diffusion controller in the resist composition.

The component (D1) is not particularly limited as long as it functions as an acid diffusion-controlling agent, and examples thereof include aliphatic amines and aromatic amines.

Among the aliphatic amines, secondary aliphatic amines and tertiary aliphatic amines are preferable.

The aliphatic amine is an amine having 1 or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.

The aliphatic amine may, for example, be ammonia NH₃An amine (alkylamine or alkylol amine) or a cyclic amine obtained by substituting at least 1 hydrogen atom of (a) a C12 or less alkyl group or hydroxyalkyl group.

Specific examples of the alkylamine and the alkylol amine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine and tri-n-octanolamine. Among these, trialkylamines having 5 to 10 carbon atoms are more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine).

Specific examples of the alicyclic monocyclic amine include piperidine and piperazine. The aliphatic polycyclic amine is preferably one having 6 to 10 carbon atoms, and specifically, it may, for example, be 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo [5.4.0] -7-undecene, hexamethylenetetramine or 1, 4-diazabicyclo [2.2.2] octane.

Examples of the other aliphatic amine include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl } amine, tris {2- (2-methoxyethoxymethoxy) ethyl } amine, tris {2- (1-methoxyethoxy) ethyl } amine, tris {2- (1-ethoxyethoxy) ethyl } amine, tris {2- (1-ethoxypropoxy) ethyl } amine, tris [2- {2- (2-hydroxyethoxy) ethoxy } ethyl ] amine, and triethanolamine triacetate is preferable.

Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, aniline compounds, and n-tert-butoxycarbonylpyrrolidine.

(D1) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among the above, the component (D1) is preferably an aromatic amine, and more preferably an aniline compound. Examples of the aniline compound include 2, 6-diisopropylaniline, N-dimethylaniline, N-dibutylaniline and N, N-dihexylaniline.

With respect to the (D2) component

The component (D2) is not particularly limited as long as it is a component which loses acid diffusion controllability by decomposition by exposure to light, and is preferably 1 or more compounds selected from the group consisting of a compound represented by the following general formula (D2-1) (hereinafter referred to as a "D2-1 component"), a compound represented by the following general formula (D2-2) (hereinafter referred to as a "D2-2 component"), and a compound represented by the following general formula (D2-3) (hereinafter referred to as a "D2-3 component").

The components (d2-1) to (d2-3) decompose in the exposed portion of the resist film and lose the acid diffusion controllability (basicity), and thus cannot function as a quencher, but function as a quencher in the unexposed portion of the resist film.

[ solution 51]

[ in the formula, Rd¹～Rd⁴The alkyl group may be a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent. Wherein Rd in the general formula (d2-2)²To the carbon atom adjacent to the S atom in (1) is not bonded with a fluorine atom. Yd¹Is a single bond or a 2-valent linking group. M is an integer of 1 or more, M'^m+Each independently an m-valent onium cation.]

{ (d2-1) composition }

An anionic moiety

In the formula (d2-1), Rd¹Examples of the "R" in the formula (b-1) and the "R" in the formula (b-1) may include a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, and a linear alkenyl group which may have a substituent¹⁰¹And the like.

Among these, as Rd¹Preferred is an aromatic hydrocarbon group which may have a substituent, an alicyclic group which may have a substituent, or a chain alkyl group which may have a substituent. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluoroalkyl group, lactone ring-containing groups represented by the general formulae (a2-r-1) to (a2-r-7), ether bonds, ester bonds, and combinations thereof. In the case where an ether bond or an ester bond is contained as a substituent, the substituent in this case may be a substituent via an alkylene groupPreferred are linking groups represented by the above formulae (y-al-1) to (y-al-5).

The aromatic hydrocarbon group may preferably be a polycyclic structure having a phenyl group, a naphthyl group or a bicyclooctane skeleton (for example, a polycyclic structure composed of a ring structure of the bicyclooctane skeleton and other ring structures).

The alicyclic group is more preferably a group obtained by removing 1 or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like.

The chain alkyl group is preferably a linear alkyl group having 1 to 10 carbon atoms, and specifically, it may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, or the like; branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl and 4-methylpentyl.

When the chain alkyl group is a fluoroalkyl group having a fluorine atom or a fluoroalkyl group as a substituent, the number of carbon atoms in the fluoroalkyl group is preferably 1 to 11, more preferably 1 to 8, and still more preferably 1 to 4. The fluoroalkyl group may contain an atom other than a fluorine atom. Examples of the atom other than the fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

As Rd¹The fluoroalkyl group is preferably a fluoroalkyl group in which a part or all of the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms, and particularly preferably a fluoroalkyl group (linear perfluoroalkyl group) in which all of the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms.

Preferred specific examples of the anion portion of the component (d2-1) are shown below.

[ solution 52]

Cationic moiety

M 'of formula (d 2-1)'^m+Is an onium cation having a valence of m.

As M'^m+The onium cation of (2) may preferably be the same cation as the cations represented by the general formulae (ca-1) to (ca-4), more preferably the cation represented by the general formula (ca-1), and even more preferably the cations represented by the formulae (ca-1-1) to (ca-1-78), (ca-1-101) to (ca-1-149).

The component (d2-1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

{ (d2-2) composition }

An anionic moiety

In the formula (d2-2), Rd²Examples of the "R" in the formula (b-1) include a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, and a linear alkenyl group which may have a substituent¹⁰¹And the like.

Wherein, Rd²The carbon atom adjacent to the S atom in (1) is not bonded with a fluorine atom (fluorine-free substitution). Thus, the anion of the component (D2-2) becomes a moderately weak acid anion, and the quenching ability as the component (D2) is improved.

As Rd²Preferred is a chain alkyl group which may have a substituent, or an alicyclic group which may have a substituent. The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms. More preferred examples of the alicyclic group include groups (which may have a substituent) obtained by removing 1 or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like; a group obtained by removing 1 or more hydrogen atoms from camphor or the like.

Rd²The hydrocarbon group (C) may have a substituent, and examples of the substituent include Rd of the formula (d2-1)¹The hydrocarbon group (aromatic hydrocarbon group, alicyclic group, or chain alkyl group) in (1) may have the same substituent.

Preferred specific examples of the anion portion of the component (d2-2) are shown below.

[ Hua 53]

Cationic moiety

M 'of formula (d 2-2)'^m+Is an M-valent onium cation, with M 'in the formula (d 2-1)'^m+Are the same onium cations.

The component (d2-2) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

{ (d2-3) composition }

An anionic moiety

In the formula (d2-3), Rd³Examples of the "R" in the formula (b-1) may include a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, and a linear alkenyl group which may have a substituent¹⁰¹The same group is preferably a cyclic group, a linear alkyl group or a linear alkenyl group containing a fluorine atom. Among them, fluoroalkyl group is preferable, and Rd is more preferable¹The fluoroalkyl group of (a) is the same fluoroalkyl group.

In the formula (d2-3), Rd⁴Examples of the "R" in the formula (b-1) include a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, and a linear alkenyl group which may have a substituent¹⁰¹And the like.

Among them, preferred are alkyl groups, alkoxy groups, alkenyl groups, and cyclic groups which may have a substituent.

Rd⁴The alkyl group in (b) is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, it may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group or a neopentyl group. Rd⁴A part of the hydrogen atoms of the alkyl group in (b) may be substituted by a hydroxyl group, a cyano group or the like.

Rd⁴The alkoxy group in (3) is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group and a tert-butoxy group. Among them, methoxy group and ethoxy group are preferable.

Rd⁴The alkenyl group in (b) is exemplified by the same as R in the formula (b-1)¹⁰¹And the like, in the case of,vinyl, propenyl (allyl), 1-methylpropenyl and 2-methylpropenyl are preferred. These groups may further have an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms as a substituent.

Rd⁴Examples of the cyclic group in (b) include the group represented by R in the formula (b-1)¹⁰¹The same groups are preferably alicyclic groups obtained by removing 1 or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane, or aromatic groups such as phenyl and naphthyl. At Rd⁴In the case of an alicyclic group, the resist composition is favorably dissolved in an organic solvent, whereby the lithographic characteristics are favorable.

In the formula (d2-3), Yd¹Is a single bond or a 2-valent linking group.

As Yd¹The 2-valent linking group in (2) is not particularly limited, and examples thereof include a 2-valent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) having a substituent, a 2-valent linking group containing a heteroatom, and the like. These are exemplified by Ya in the formula (a10-1) above^x1The same groups as those exemplified for the 2-valent hydrocarbon group which may have a substituent and the heteroatom-containing 2-valent linking group in the description of the 2-valent linking group in (1).

As Yd¹Preferably a carbonyl group, ester linkage, amide linkage, alkylene group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and still more preferably a methylene group or an ethylene group.

Preferred specific examples of the anion portion of the component (d2-3) are shown below.

[ solution 54]

[ solution 55]

Cationic moiety

M 'of formula (d 2-3)'^m+Is an M-valent onium cation, with M 'in the formula (d 2-1)'^m+Are the same onium cations.

The component (d2-3) may be used alone in 1 kind or in combination of 2 or more kinds.

(D2) The component (c) may be any of the above-mentioned components (d2-1) to (d2-3), or 2 or more thereof may be used in combination.

When the resist composition contains the component (D2), the content of the component (D2) in the resist composition is preferably 0.5 to 35 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 2 to 20 parts by mass, and particularly preferably 3 to 15 parts by mass, relative to 100 parts by mass of the component (A).

When the content of the (D2) component is equal to or greater than the preferable lower limit, particularly good lithographic characteristics and resist pattern shape can be easily obtained. On the other hand, if the upper limit value is less than or equal to the upper limit value, balance with other components can be obtained, and various lithographic characteristics can be improved.

(D2) The method for producing the component (A):

the method for producing the component (d2-1) or the component (d2-2) is not particularly limited, and the component (d2-1) can be produced by a known method.

The method for producing the component (d2-3) is not particularly limited, and the component (d2-3) can be produced, for example, in the same manner as the method described in U.S. Pat. No. 2012-0149916.

(E) component: at least 1 compound selected from the group consisting of organic carboxylic acid and phosphorus oxyacid and its derivative

The resist composition of the present embodiment may contain at least 1 compound (E) (hereinafter referred to as "component (E)") selected from the group consisting of organic carboxylic acids, phosphorus oxyacids and derivatives thereof as an optional component for the purpose of preventing sensitivity deterioration, improving resist pattern shape, stability with standing, and the like.

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

The oxyacid of phosphorus may, for example, be phosphoric acid, phosphonic acid or phosphinic acid, and among these, phosphonic acid is particularly preferred.

Examples of the derivative of an oxyacid of phosphorus include esters obtained by substituting a hydrogen atom of the oxyacid with a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 15 carbon atoms.

Examples of the phosphoric acid derivative include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.

Examples of the phosphonic acid derivative include phosphonic acid esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate.

The phosphinic acid derivative may, for example, be a phosphinic acid ester or phenylphosphinic acid.

In the resist composition of the present embodiment, 1 kind of the component (E) may be used alone, or 2 or more kinds may be used in combination.

When the resist composition contains the component (E), the content of the component (E) is usually 0.01 to 5 parts by mass relative to 100 parts by mass of the component (a).

Component (F): fluorine additive ingredient

The resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") in order to impart water repellency to the resist film or to improve lithographic characteristics.

As the component (F), for example, fluorine-containing polymer compounds described in Japanese patent application laid-open Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569 and 2011-128226 can be used.

More specifically, the component (F) may be a polymer having a structural unit (F1) represented by the following formula (F1-1). The polymer is preferably a polymer (homopolymer) composed only of a structural unit (f1) represented by the following formula (f 1-1); a copolymer of the structural unit (f1) and the structural unit (a 1); the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and a copolymer of the structural unit (a 1). The structural unit (a1) copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate or a structural unit derived from 1-methyl-1-adamantyl (meth) acrylate.

[ solution 56]

[ wherein R is the same as described above, Rf¹⁰²And Rf¹⁰³Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms, Rf¹⁰²And Rf¹⁰³May be the same or different. nf¹Is an integer of 1 to 5, Rf¹⁰¹Is an organic group containing a fluorine atom.]

In the formula (f1-1), R bonded to the carbon atom at the α -position is the same as described above. R is preferably a hydrogen atom or a methyl group.

In the formula (f1-1), as Rf¹⁰²And Rf¹⁰³Examples of the halogen atom of (b) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable. As Rf¹⁰²And Rf¹⁰³Examples of the alkyl group having 1 to 5 carbon atoms of (b) include the same ones as those of the alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferable. As Rf¹⁰²And Rf¹⁰³The haloalkyl group having 1 to 5 carbon atoms in (b) may specifically be a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is particularly preferable. Wherein as Rf¹⁰²And Rf¹⁰³The alkyl group is preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, and is preferably a hydrogen atom, a fluorine atom, a methyl group or an ethyl group.

In the formula (f1-1), nf¹Is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2.

In the formula (f1-1), Rf¹⁰¹Is an organic group containing a fluorine atom, preferably containing fluorineAn atomic hydrocarbon group.

The hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms.

The hydrocarbon group containing a fluorine atom is preferably fluorinated in an amount of 25% or more, more preferably 50% or more, of the hydrogen atoms in the hydrocarbon group, and is particularly preferably fluorinated in an amount of 60% or more, since the hydrophobicity of the resist film at the time of immersion exposure is improved.

Wherein, as Rf¹⁰¹More preferred is a C1-6 fluorinated hydrocarbon group, and particularly preferred is a trifluoromethyl group, -CH₂-CF₃、-CH₂-CF₂-CF₃、-CH(CF₃)₂、-CH₂-CH₂-CF₃、-CH₂-CH₂-CF₂-CF₂-CF₂-CF₃。

(F) The mass average molecular weight (Mw) of the component (A) is preferably 1000 to 50000, more preferably 5000 to 40000, and most preferably 10000 to 30000 (in terms of polystyrene equivalent by gel permeation chromatography). If the upper limit of the range is less than or equal to the upper limit, the solubility in a solvent for a resist sufficient for use as a resist is obtained, and if the lower limit of the range is more than or equal to the lower limit, the water repellency of the resist film is good.

(F) The molecular weight distribution coefficient (Mw/Mn) of the component (B) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.

In the resist composition of the present embodiment, 1 kind of the component (F) may be used alone, or 2 or more kinds may be used in combination.

When the resist composition contains the component (F), the component (F) is usually used in an amount of 0.5 to 10 parts by mass per 100 parts by mass of the component (a).

(S) component: organic solvent composition

The resist composition of the present embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as "component (S)").

The component (S) is not particularly limited as long as it can dissolve each component used to form a uniform solution, and any component may be appropriately selected from those conventionally known as solvents for chemically amplified resist compositions.

For example, the component (S) may include lactones such as γ -butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; derivatives of polyhydric alcohols such as compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, and compounds having an ether bond such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and the like of the polyhydric alcohols or the compounds having an ester bond [ among these, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Ether (PGME) ]; esters such as cyclic ethers like dioxane, methyl lactate, Ethyl Lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, methyltolyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropyltoluene, mesitylene, and the like; dimethylsulfoxide (DMSO), and the like.

In the resist composition of the present embodiment, the component (S) may be used alone in 1 kind, or may be used as a mixed solvent of 2 or more kinds.

Among them, PGMEA, PGME, gamma-butyrolactone, EL, and cyclohexanone are preferable.

In addition, a mixed solvent obtained by mixing PGMEA with a polar solvent is also preferable. The blending ratio (mass ratio) thereof may be determined as appropriate in consideration of the compatibility of the PGMEA with the polar solvent, and is preferably in the range of 1: 9 to 9: 1, more preferably in the range of 2: 8 to 8: 2.

More specifically, in the case of blending EL or cyclohexanone as the polar solvent, the mass ratio of PGMEA to EL or cyclohexanone is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. In addition, when PGME is blended as the polar solvent, the mass ratio of PGMEA to PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and further preferably 3: 7 to 7: 3. Further, a mixed solvent of PGMEA and PGME with cyclohexanone is also preferable.

In addition to the (S) component, a mixed solvent of γ -butyrolactone and at least 1 selected from PGMEA and EL is also preferable. In this case, the mixing ratio of the former to the latter is preferably 70: 30 to 95: 5 by mass.

The amount of the component (S) used is not particularly limited, and is appropriately set according to the coating film thickness at a concentration at which the component (S) can be applied to a substrate or the like. Generally, the (S) component is used so that the solid content concentration of the resist composition is in the range of 0.1 to 50 mass%, preferably 10 to 50 mass%.

The resist composition of the present embodiment may further contain additives having miscibility, for example, additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like, as appropriate according to the purpose.

The resist composition of the present embodiment may be used for removing impurities and the like by using a polyimide porous membrane, a polyamide-imide porous membrane, and the like after dissolving the resist material in the (S) component. For example, the filtration of the resist composition can be performed using a filter composed of a polyimide porous membrane, a filter composed of a polyamideimide porous membrane, a filter composed of a polyimide porous membrane and a polyamideimide porous membrane, or the like. Examples of the polyimide porous film and the polyamideimide porous film include those described in Japanese patent laid-open publication No. 2016-155121.

The negative resist composition of the present embodiment contains a polymer compound (a1), an acid generator (B0), a crosslinking agent (C), and an aromatic compound (Z) having 1 or 2 phenolic hydroxyl groups in the molecule and no carboxyl groups.

As a result of the studies by the present inventors, when a resist pattern is formed using a negative resist composition using an alkali-soluble polyhydroxystyrene resin as a base component, the etching resistance may be insufficient when a thick resist film of a micron order is formed by utilizing the wet etching resistance, and further, when a resist pattern is formed and etched. This is presumably because the adhesion between the resist film formed using the negative resist composition and the substrate interface is insufficient.

In the resist composition of the present embodiment described above, it is presumed that the (Z) component segregates in the lower layer of the resist film, contributing to the improvement of the substrate adhesion. Therefore, it is presumed that the resist pattern formed using the negative resist composition of the present embodiment has good etching resistance.

(resist Pattern Forming method)

The invention of claim 2 is a resist pattern forming method, comprising: a step (i) of forming a resist film on a support using the resist composition according to claim 1; a step (ii) of exposing the resist film; and (iii) developing the exposed resist film to form a resist pattern.

As an embodiment of the above-described resist pattern forming method, for example, a resist pattern forming method performed as described below can be exemplified.

Step (i):

first, the resist composition of the above embodiment is applied to a support by a spin coater or the like, and is subjected to a baking (pre-Bake (PAB)) treatment at a temperature of 80 to 160 ℃ for 40 to 200 seconds, preferably 60 to 150 seconds, to form a resist film.

Step (ii):

then, the resist film is selectively exposed to light through a mask (mask pattern) having a predetermined pattern formed thereon by using an Exposure apparatus such as a KrF Exposure apparatus, and then subjected to baking (Post Exposure Bake) treatment for 40 to 150 seconds, preferably 60 to 120 seconds, at a temperature of 80 to 150 ℃.

Step (iii):

next, the resist film is subjected to a development process. The development treatment is performed using an alkaline developer in the case of an alkaline development process, and is performed using an organic solvent-containing developer (organic developer) in the case of a solvent development process.

After the development treatment, a rinsing treatment is preferably performed. The rinsing treatment is preferably a water rinsing using pure water in the case of an alkaline development process, and a rinsing liquid containing an organic solvent in the case of a solvent development process.

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

Drying is performed after the development treatment or after the rinsing treatment. Further, a baking treatment (post-baking) may be performed after the above-described developing treatment according to circumstances. Here, the baking treatment (post-baking) is performed, for example, at a temperature of 80 ℃ or higher, preferably 90 to 120 ℃ for 10 to 120 seconds, preferably 30 to 90 seconds.

As described above, a resist pattern can be formed.

The support is not particularly limited, and conventionally known supports may be used, and examples thereof include a substrate for electronic components, a support having a predetermined wiring pattern formed thereon, and the like. More specifically, the substrate may be a silicon wafer, a substrate made of metal such as copper, chromium, iron, or aluminum, or a glass substrate. As a material of the wiring pattern, for example, copper, aluminum, nickel, gold, or the like can be used.

The support may be one in which an inorganic and/or organic film is provided on the substrate as described above. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) may be mentioned. Examples of the organic film include organic films such as an organic anti-reflection film (organic BARC) and an underlying organic film in a multilayer resist method.

Here, the multilayer resist method is a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are provided on a substrate, and patterning of the lower organic film is performed using a resist pattern formed on the upper resist film as a mask, and it is considered that a pattern with a high aspect ratio can be formed. That is, according to the multilayer resist method, a desired thickness can be secured by the lower organic film, and therefore, the resist film can be thinned, and a fine pattern with a high aspect ratio can be formed.

Among the multilayer resist methods, there is basically a method (2-layer resist method) which adopts a two-layer structure of an upper resist film and a lower organic film; and a method (3-layer resist method) using a multilayer structure of three or more layers in which one or more intermediate layers (such as a metal thin film) are provided between an upper resist film and a lower organic film.

The resist pattern forming method according to the embodiment is a method useful for forming a thick resist film. The resist film formed in the step (i) can form a resist pattern stably in a good shape even if the film thickness is, for example, 1 to 10 μm.

The wavelength used for the exposure is not particularly limited, and ultraviolet rays such as g-ray and i-ray, ArF excimer laser, KrF excimer laser, and F can be used₂Excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, and the like.

The resist composition of claim 1 is highly useful for g-ray, i-ray, and other ultraviolet rays, KrF excimer laser, ArF excimer laser, EB and EUV, more useful for g-ray, i-ray, and other ultraviolet rays, KrF excimer laser, and ArF excimer laser, and particularly useful for g-ray, i-ray, and other ultraviolet rays, KrF excimer laser. The method of forming a resist pattern according to claim 2 is particularly preferable when ultraviolet rays such as g-rays and i-rays, or KrF excimer laser light is irradiated on the resist film in the step (ii).

The resist film may be exposed to normal light in an inert gas such as air or nitrogen (dry exposure) or may be subjected to Liquid Immersion exposure (Liquid Immersion Lithography).

The liquid immersion exposure is an exposure method in which a space between a resist film and a lens at the lowermost position of an exposure apparatus is filled with a solvent (liquid immersion medium) having a refractive index larger than that of air in advance, and exposure is performed in this state (immersion exposure).

The liquid immersion medium is preferably a solvent having a refractive index higher than that of air and lower than that of the resist film to be exposed. The refractive index of the solvent is not particularly limited within the above range.

Examples of the solvent having a refractive index higher than that of air and lower than that of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.

Specific example of the fluorine-based inert liquid is C₃HCl₂F₅、C₄F₉OCH₃、C₄F₉OC₂H₅、C₅H₃F₇And liquids containing a fluorine-based compound as a main component, preferably a liquid having a boiling point of 70 to 180 ℃, and more preferably a liquid having a boiling point of 80 to 160 ℃. When the fluorine-based inert liquid has a boiling point in the above range, it is preferable because the medium used for the immersion liquid can be removed by a simple method after the exposure is completed.

The fluorine-based inert liquid is particularly preferably a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group have been replaced with fluorine atoms. The perfluoroalkyl compound may specifically be a perfluoroalkyl ether compound or a perfluoroalkyl amine compound.

More specifically, the perfluoroalkyl ether compound may, for example, be perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ℃ C.), and the perfluoroalkyl amine compound may, for example, be perfluorotributylamine (boiling point: 174 ℃ C.).

As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility, and the like.

The alkaline developer used for the development treatment in the alkaline development process may, for example, be a 0.1 to 10 mass% aqueous tetramethylammonium hydroxide (TMAH) solution.

The organic solvent contained in the organic developer used for the development treatment in the solvent development process may be selected from known organic solvents as long as it is an organic solvent capable of dissolving the component (a) (component (a) before exposure). Specifically, the solvent may include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents and hydrocarbon solvents.

The ketone solvent is an organic solvent containing C — C (═ O) -C in the structure. The ester solvent is an organic solvent containing C — C (═ O) -O — C in the structure. The alcohol solvent is an organic solvent containing alcoholic hydroxyl groups in the structure. "alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile solvents are organic solvents that contain nitrile groups in the structure. The amide-based solvent is an organic solvent containing an amide group in the structure. The ether solvent is an organic solvent containing C-O-C in the structure.

Among the organic solvents, there are also organic solvents having a structure containing a plurality of functional groups having the characteristics of each of the above solvents, and in this case, the organic solvents are classified into all kinds of solvents having the functional groups at the same time. For example, diethylene glycol monomethyl ether is classified into any of the alcohol solvents and ether solvents in the above classification.

The hydrocarbon solvent is a hydrocarbon solvent composed of a halogenated hydrocarbon and having no substituent other than a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a fluorine atom.

Among the above, the organic solvent contained in the organic developer is preferably a polar solvent, and is preferably a ketone solvent, an ester solvent, a nitrile solvent, or the like.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethyl ketone, methylisobutyl ketone, acetylacetone, diacetone, ionone, diacetone alcohol, acetyl methanol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, γ -butyrolactone, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, methyl acetate, ethyl methoxybutyl acetate, butyl acetate, n-butyl acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl carbonate, butyl carbonate, methyl pyruvate, methyl acetate, ethyl formate, butyl formate, ethyl lactate, butyl acetate, ethyl formate, butyl formate, methyl pyruvate, ethyl, Ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like. Among these, butyl acetate is preferable as the ester solvent.

Examples of the nitrile solvent include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

The organic developer may be blended with known additives as needed. Examples of the additive include surfactants. The surfactant is not particularly limited, and, for example, an ionic or nonionic fluorine-based and/or silicon-based surfactant can be used. The surfactant is preferably a nonionic surfactant, more preferably a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant.

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

The developing treatment may be carried out by a known developing method, and examples thereof include a method of immersing the support in a developer for a certain period of time (immersion method), a method of supporting the developer on the surface of the support by surface tension and standing for a certain period of time (stirring (paddle) method), a method of spraying the developer on the surface of the support (spray method), and a method of continuously discharging the developer onto the support rotating at a certain speed while scanning a developer discharge nozzle at a certain speed (dynamic dispensing method).

As the organic solvent contained in the rinse liquid used in the rinse treatment after the development treatment in the solvent development process, for example, an organic solvent that is difficult to dissolve the resist pattern among the organic solvents exemplified as the organic solvents used in the organic developer can be appropriately selected and used. At least 1 solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is generally used. Among these, at least 1 kind selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferable, at least 1 kind selected from alcohol solvents and ester solvents is more preferable, and alcohol solvents are particularly preferable.

The alcoholic solvent used in the rinse liquid is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specifically, it may, for example, be 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol or benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, and 1-hexanol and 2-hexanol are more preferred.

These organic solvents may be used alone, or 2 or more kinds may be used in combination. Further, the solvent may be used in combination with an organic solvent or water other than those mentioned above. However, in consideration of the developing property, the amount of water to be added to the rinse liquid is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on the total amount of the rinse liquid.

The rinse liquid may be mixed with known additives as needed. Examples of the additive include surfactants. Examples of the surfactant include the same surfactants as described above, preferably nonionic surfactants, more preferably nonionic fluorine surfactants, or nonionic silicon surfactants.

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

The rinsing process (cleaning process) using the rinsing liquid can be performed by a known rinsing method. Examples of the rinsing treatment include a method of continuously discharging a rinsing liquid onto a support rotating at a constant speed (spin coating method), a method of immersing the support in a rinsing liquid for a constant time (immersion method), and a method of spraying a rinsing liquid onto the surface of the support (spray method).

In the resist pattern forming method of the present embodiment described above, it is presumed that a resist pattern having excellent etching resistance can be obtained by using the resist composition according to claim 1.

[ examples ] A method for producing a compound

The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples.

< preparation of resist composition >

Examples 1 to 12 and comparative examples 1 to 5

The components shown in tables 1 to 2 were mixed and dissolved to prepare resist compositions of respective examples.

[ TABLE 1]

[ TABLE 2]

In tables 1 and 2, the abbreviations have the following meanings. [] The numerical values in (b) are amounts (parts by mass) to be blended.

(A) -1: a polymer compound represented by the following chemical formula (A-1). The polymer compound (A-1) is obtained by radical polymerization using monomers from which the structural units constituting the polymer compound are derived at a predetermined molar ratio. The polymer compound (A-1) had a weight average molecular weight (Mw) of 2500 in terms of polystyrene standard as determined by GPC measurement and a molecular weight distribution coefficient (Mw/Mn) of 1.2. By passing¹³The copolymerization composition ratio (the ratio of the respective structural units in the structural formula (molar ratio)) determined by C-NMR was 90/10 (l/m).

[ solution 57]

(A) -2: a polymer compound (homopolymer) represented by the following chemical formula (A-2). The polymer compound (A-2) is obtained by radical polymerization of a monomer (hydroxystyrene) from which a structural unit constituting the polymer compound is derived. The polymer compound (A-2) had a mass average molecular weight (Mw) of 2500 and a molecular weight distribution (Mw/Mn) of 1.2 in terms of polystyrene standards, which were determined by GPC measurement.

[ solution 58]

(B) -1 to (B) -3: an acid generator comprising compounds represented by the following chemical formulas (B-1) to (B-3).

[ chemical 59]

(C) -1: a crosslinking agent comprising a compound represented by the following chemical formula (C-1).

(D) -1: a nitrogen-containing organic compound composed of a compound represented by the following chemical formula (D-1).

[ solution 60]

(Z) -1: a compound represented by the following chemical formula (Z-1). The mass-average molecular weight (Mw) was 268.36.

(Z) -2: a compound represented by the following chemical formula (Z-2). The mass-average molecular weight (Mw) was 352.43.

(Z) -3: a compound represented by the following chemical formula (Z-3). The mass-average molecular weight (Mw) was 246.31.

(Z) -11: a compound represented by the following chemical formula (Z-11). The mass-average molecular weight (Mw) was 230.22.

(Z) -12: a compound represented by the following chemical formula (Z-12). The mass-average molecular weight (Mw) was 278.22.

(Z) -13: a compound represented by the following chemical formula (Z-13). The mass-average molecular weight (Mw) was 286.33.

(S) -1: propylene glycol monomethyl ether acetate

[ solution 61]

< method for Forming resist Pattern >

Step (i):

the resist compositions of the respective examples were applied to silicon substrates subjected to Hexamethyldisilazane (HMDS) treatment using a spin coater, and Prebaked (PAB) treatment was performed on a hot plate at 90 ℃ for 90 seconds, followed by drying, thereby forming a resist film having a thickness of 3 μm.

Step (ii):

next, the resist film was selectively irradiated with a high-pressure mercury lamp (365nm) through a mask pattern by an i-ray stepper (reduction projection exposure apparatus: NSR-2205i14E (manufactured by nikon corporation; NA (numerical aperture) ═ 0.57, σ ═ 0.67)).

Then, a post-exposure heating (PEB) treatment was performed at 110 ℃ for 60 seconds.

Step (iii):

next, alkaline development was carried out at 23 ℃ for 60 seconds using 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution "NMD-3" (trade name, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a developer.

Then, baking treatment (post-baking) was performed at 100 ℃ for 60 seconds.

As a result, an isolated line pattern (hereinafter referred to as "IS pattern") having an interval width of 600nm was formed.

< evaluation of undercut >

The cross-sectional shape of the IS pattern formed in the < method for forming a resist pattern > was observed with a scanning electron microscope (product name: S4500; manufactured by Hitachi Ltd.) and undercut (cut of the resist itself at the bottom of the resist pattern formed on the substrate) (nm) was evaluated. The results are shown in tables 3 and 4.

< evaluation of Wet etching >

A part of the substrate on which the IS pattern was formed by the resist pattern formation method was cut out and immersed in 23% buffered hydrofluoric acid for 12 minutes.

The cross-sectional shape of the immersed IS pattern was observed with a scanning electron microscope (product name: S4500; manufactured by Hitachi Ltd.) to evaluate the side etching (the cut due to etching at the interface between the resist film and the substrate) (μm). The results are shown in tables 3 and 4.

[ TABLE 3]

[ TABLE 4]

From the results shown in tables 3 and 4, the following were confirmed: resist patterns formed using the resist compositions of examples 1 to 12 were excellent in dry etching resistance and wet etching resistance.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the invention. The invention is not to be limited by the foregoing description but is only limited by the scope of the appended claims.

Claims

1. A negative resist composition, comprising:

a polymer compound (A1) having a structural unit (a10) represented by the following general formula (a10-1),

An acid generator (B0) represented by the following general formula (B0-1),

A crosslinking agent (C),

An aromatic compound (Z) having 1 or 2 phenolic hydroxyl groups in the molecule and having no carboxyl group,

[ solution 1]

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, Ya^x1Is a single bond or a 2-valent linking group, Wa^x1Is an optionally substituted aromatic hydrocarbon group, n_ax1Is an integer of 1 or more, and is,

[ solution 2]

In the formula, Rb¹Is an organic radical, Rb²Is a group represented by the following general formula (b0-r-1) or the following general formula (b0-r-2),

[ solution 3]

In the formula (b0-r-1), Rb is²⁰¹And Rb²⁰²Each independently represents an organic group, and Xb in formula (b0-r-2) is a group which forms a cyclic group having a cyclic imide structure together with- (O ═ C-N-C (═ O) -, and represents a bond.

2. The negative resist composition of claim 1, wherein the aromatic compound (Z) comprises at least one compound selected from the group consisting of a compound represented by the following general formula (Z1-1) and a compound represented by the following general formula (Z2-1),

[ solution 4]

In the formula (z1-1), V_z ¹Is a 2-valent linking group having no hydroxyl group or carboxyl group, in the formula (z2-1), Rz²Is alkyl, n1 is 1 or 2, n2 is an integer of 2-5, wherein n1+ n2 is less than or equal to 6.

3. The resist composition according to claim 1, wherein the aromatic compound (Z) is contained in an amount of 0.5 to 30 parts by mass based on 100 parts by mass of the polymer compound (a 1).

4. A method for forming a resist pattern, comprising a step of forming a resist film on a support using the resist composition according to any one of claims 1 to 3, a step of exposing the resist film to light, and a step of developing the exposed resist film to form a resist pattern.