JP2020086439A - Resist composition and method for forming resist pattern - Google Patents

Abstract

To provide a resist composition from which a pattern having good etching durability and a good profile can be formed, and a method for forming a resist pattern using the resist composition.SOLUTION: The resist composition comprises a base component (A) the solubility of which with a developer changes by an action of an acid, and a dissolution inhibitor (Z) that suppresses dissolution with a developer. The dissolution inhibitor (Z) comprises a compound (Z1) having a mass average molecular weight of 3000 or less and having a phenolic hydroxyl group or a carboxyl group in the molecule, and a compound (Z2) having a mass average molecular weight of 3000 or less and represented by general formula (z2) below. In the formula, Ris an acid dissociable group; Ris a hydrogen atom or an organic group; n1 is an integer of 1 to 6; and n2 is an integer of 0 to 5, where n1+n2=6.SELECTED DRAWING: None

Description

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

In the lithographic technique, for example, a resist film made of a resist material is formed on a substrate, the resist film is selectively exposed, and a development process is performed to form a resist pattern having a predetermined shape on the resist film. The process of doing is performed. A resist material in which the exposed portion of the resist film changes to a characteristic that dissolves in a developing solution is called a positive type, and a resist material in which the exposed portion of the resist film changes to a characteristic that does not dissolve in a developing solution is called a negative type.
2. Description of the Related Art In recent years, in the manufacture of semiconductor devices and liquid crystal display devices, pattern miniaturization is rapidly progressing due to advances in lithography technology. As a method of miniaturization, generally, the wavelength of the exposure light source is shortened (increased in energy). Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but nowadays, mass production of semiconductor devices using KrF excimer laser light or ArF excimer laser light is being carried out. .. Further, EUV (extreme ultraviolet ray), EB (electron beam), X-ray, etc. having a shorter wavelength (high energy) than these excimer laser beams are also being studied.

The resist material is required to have lithographic characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern having a fine dimension.
As a resist material satisfying such requirements, conventionally, a chemically amplified resist composition containing a base material component whose solubility in a developing solution is changed by the action of an acid and an acid generator component which generates an acid upon exposure to light. Is used.
For example, when the developing solution is an alkaline developing solution (alkali developing process), as a positive chemically amplified resist composition, a resin component (base resin) whose solubility in an alkaline developing solution increases due to the action of an acid and an acid generation Those containing a drug component are generally used. When a resist film formed using such a resist composition is selectively exposed at the time of forming a resist pattern, an acid is generated from the acid generator component in the exposed portion, and the action of the acid increases the polarity of the base resin. Then, the exposed portion of the resist film becomes soluble in the alkali developing solution. Therefore, the alkali development forms a positive pattern in which the unexposed portion of the resist film remains as a pattern.
On the other hand, when such a chemically amplified resist composition is applied to a solvent developing process using a developing solution containing an organic solvent (organic developing solution), when the polarity of the base resin is increased, the organic developing method is relatively performed. Since the solubility in the liquid is lowered, the unexposed portion of the resist film is dissolved and removed by the organic developing solution to form a negative resist pattern in which the exposed portion of the resist film remains as a pattern. The solvent developing process for forming a negative resist pattern in this way is sometimes referred to as a negative developing process.

In the above chemically amplified resist composition, in order to suppress the film loss of the resist film at the time of forming the resist pattern and improve the solubility difference (dissolution contrast) between the exposed portion and the unexposed portion of the resist film, a developing solution is used. It is known to add a dissolution inhibitor that suppresses the solubility of the above (see, for example, Patent Documents 1 to 3).

In recent years, photofabrication has become the mainstream of precision microfabrication technology. Photofabrication refers to the chemically amplified resist composition, which is applied to the surface of an object to be processed to form a resist film, and a resist pattern having a predetermined shape is formed on the resist film, which is used as a mask for chemical etching. This refers to a processing technique for producing various precision parts by performing electrolytic forming or electroforming mainly including electroplating.

JP, 2006-328241, A JP, 2007-206425, A JP, 2008-122932, A

In such photofabrication, depending on the application, etc., when a thick resist film having a film thickness of, for example, a micron order is formed on the surface of the workpiece, a resist pattern is formed, and etching is performed. There is. For example, in the development of a three-dimensional structure device (three-dimensional NAND), the capacity of the memory is increased by vertically stacking several tens of cells manufactured using a thick film resist pattern.
As a result of examination by the present inventors, when a chemically amplified resist composition containing a conventional dissolution inhibitor is used to form a thick film resist film of micron order, and a resist pattern is formed to perform etching. In some cases, the etching resistance was insufficient. On the other hand, when a thick resist film is formed using a chemically amplified resist composition containing no dissolution inhibitor and a resist pattern is formed, the resist film is reduced during the formation of the resist pattern, and In some cases, a pattern having a shape cannot be formed.

The present invention has been made in view of the above circumstances, and provides a resist composition having good etching resistance and capable of forming a pattern having a good shape, and a resist pattern forming method using the resist composition. The task is to do.

In order to solve the above problems, the present invention adopts the following configurations.
That is, the first aspect of the present invention is a resist composition which generates an acid upon exposure and whose solubility in a developing solution changes by the action of an acid, wherein the solubility in a developing solution changes by the action of an acid. And a dissolution inhibitor (Z) that suppresses solubility in a developing solution, wherein the dissolution inhibitor (Z) has a mass average molecular weight of 3,000 or less, and A resist composition comprising a compound (Z1) having a phenolic hydroxyl group or a carboxyl group and a compound (Z2) having a mass average molecular weight of 3000 or less and represented by the following general formula (z2).

［式中、Ｒ_ｚ ^２０は酸解離性基である。Ｒ_ｚ ^３０は水素原子又は有機基である。ｎ１は１〜６の整数であり、ｎ２は０〜５の整数である。ただし、ｎ１＋ｎ２＝６である。］

[In the formula, R _z ²⁰ is an acid dissociable group. R _z ³⁰ is a hydrogen atom or an organic group. n1 is an integer of 1 to 6, and n2 is an integer of 0 to 5. However, n1+n2=6. ]

A second aspect of the present invention is to provide a step (i) of forming a resist film on the support using the resist composition, a step (ii) of exposing the resist film, and a resist film after the exposure. A method of forming a resist pattern, which comprises a step (iii) of developing to form a resist pattern.

According to the present invention, it is possible to provide a resist composition having good etching resistance and capable of forming a pattern having a good shape, and a resist pattern forming method using the resist composition.

In the present specification and claims, the term “aliphatic” is defined as a relative concept to aromatic and means a group, compound or the like having no aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the “alkylene group” includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The “halogenated alkyl group” is a group in which a part or all of hydrogen atoms of an alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which some or all of the hydrogen atoms of the alkyl group or alkylene group are substituted with fluorine atoms.
The “structural unit” means a monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer).
When describing that "may have a substituent" or "may have a substituent", a hydrogen atom (-H) may be substituted with a monovalent group, and a methylene group (-CH ₂ Both the case where -) is substituted with a divalent group are included.
“Exposure” is a concept that includes all radiation irradiation.

The “structural unit derived from an acrylic ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylic ester.
The term "acrylate ester" is a compound in which the hydrogen atom of the carboxyl group terminal of acrylic acid _(CH 2 = CH-COOH) has been substituted with an organic group.
In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α0 ) for substituting the hydrogen atom bonded to the carbon atom at the α-position is an atom or a group other than a hydrogen atom, and is, for example, an alkyl group having 1 to 5 carbon atoms or a halogenated group having 1 to 5 carbon atoms. An alkyl group etc. are mentioned. In addition, itaconic acid diesters in which the substituent (R ^α0 ) is substituted with a substituent containing an ester bond, and α-hydroxy acrylic esters in which the substituent (R ^α0 ) is substituted with a hydroxyalkyl group or a group modified with its hydroxyl group are also included. Shall be included. The α-position carbon atom of the acrylic ester is the carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified.
Hereinafter, an acrylic acid ester 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 acrylic acid ester. In addition, the acrylic ester and the α-substituted acrylic ester may be collectively referred to as “(α-substituted) acrylic ester”.

“A structural unit derived from acrylamide” means a structural unit formed by cleavage of an ethylenic double bond of acrylamide.
In acrylamide, a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, and one or both hydrogen atoms of an amino group of acrylamide may be substituted with a substituent. The carbon atom at the α-position of acrylamide is the carbon atom to which the carbonyl group of acrylamide is bound, unless otherwise specified.
As the substituent for substituting the hydrogen atom bonded to the carbon atom at the α-position of acrylamide, the same substituents as those described above as the α-substituent in the α-substituted acrylate (substituent (R ^α0 )) can be used. Can be mentioned.

The “structural unit derived from hydroxystyrene” means a structural unit formed by cleavage of the ethylenic double bond of hydroxystyrene. The “structural unit derived from a hydroxystyrene derivative” means a structural unit formed by cleavage of the ethylenic double bond of the hydroxystyrene derivative.
The term "hydroxystyrene derivative" is intended to include hydroxystyrene in which the hydrogen atom at the α-position is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. As the derivatives thereof, those obtained by substituting the hydrogen atom of the hydroxyl group of hydroxystyrene, which may be substituted with a hydrogen atom at the α-position, with an organic group; Examples thereof include those in which a substituent other than a hydroxyl group is bonded to the benzene ring of good hydroxystyrene. The α-position (carbon atom at the α-position) means the carbon atom to which the benzene ring is bonded, unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same ones as the substituents at the α-position in the above α-substituted acrylate ester.

The “constituent unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative” means a constituent unit formed by cleavage of the ethylenic double bond of vinylbenzoic acid or a vinylbenzoic acid derivative.
The term “vinyl benzoic acid derivative” includes vinyl benzoic acid in which the α-position hydrogen atom is substituted with another substituent such as an alkyl group and a halogenated alkyl group, and a derivative thereof. Those derivatives include those obtained by substituting the hydrogen atom of the carboxy group of vinylbenzoic acid, which may have a hydrogen atom at the α-position, with an organic group; the hydrogen atom at the α-position being substituted with a substituent. The benzene ring of vinyl benzoic acid which may be substituted with a substituent other than a hydroxyl group and a carboxy group and the like. The α-position (carbon atom at the α-position) means the carbon atom to which the benzene ring is bonded, unless otherwise specified.

The “styrene derivative” is a concept including styrene in which the hydrogen atom at the α-position is substituted with another substituent such as an alkyl group and a halogenated alkyl group, and derivatives thereof. Examples of these derivatives include those in which a substituent is bonded to the benzene ring of hydroxystyrene in which the hydrogen atom at the α-position may be substituted. The α-position (carbon atom at the α-position) means the carbon atom to which the benzene ring is bonded, unless otherwise specified.
The "structural unit derived from styrene" and "structural unit derived from styrene derivative" mean a structural unit formed by cleavage of the ethylenic double bond of styrene or a styrene derivative.

The alkyl group as the α-position substituent is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
The halogenated alkyl group as the α-position substituent is specifically a group in which a part or all of the hydrogen atoms of the above-mentioned “alkyl group as the α-position substituent” is replaced with a halogen atom. Be done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as the α-position substituent include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the α-position substituent” are substituted with hydroxyl groups. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.

In the present specification and claims, depending on the structure represented by the chemical formula, an asymmetric carbon atom may exist, and enantiomers (enantiomers) and diastereoisomers (diastereomers) may exist. In that case, one chemical formula represents these isomers. Those isomers may be used alone or as a mixture.

(Resist composition)
The resist composition according to the first aspect of the present invention is a resist composition in which an acid is generated by exposure and the solubility in a developing solution is changed by the action of the acid.
As one embodiment of such a resist composition, a base component (A) whose solubility in a developing solution is changed by the action of an acid (hereinafter also referred to as “(A) component”) and a dissolution that suppresses the solubility in a developing solution Examples include resist compositions containing an inhibitor (Z) (hereinafter also referred to as “(Z) component”) and an organic solvent component (S) (hereinafter also referred to as “(S) component”).

The resist composition of the present embodiment is suitable for forming a resist pattern by performing exposure using an exposure light source such as an ultraviolet ray such as a g-ray or an i-ray or a KrF excimer laser.
Further, the resist composition of the present embodiment is suitable for forming a resist film having a thickness of, for example, 1 to 10 μm on a support, and particularly, a resist pattern formed by forming a thick resist film. It is suitable for formation. The thick film here means a film having a thickness of 3 μm or more. The resist composition of the present embodiment preferably has a thickness of 3 μm or more, and is suitable for forming a resist film having a thickness of 3.5 μm or more, and further having a thickness of 4 μm or more within this range. Is.

When a resist film is formed using such a resist composition and the resist film is selectively exposed, an acid is generated in the exposed portion of the resist film, and the action of the acid causes the developer of the component (A) to develop. While the solubility of the component (A) in the unexposed portion of the resist film does not change in the unexposed portion of the resist film, there is a difference in solubility in the developing solution between the exposed portion and the unexposed portion. Occurs. Therefore, when the resist film is developed, when the resist composition is a positive type, the exposed portion of the resist film is dissolved and removed to form a positive type resist pattern, and when the resist composition is a negative type, the resist film is not formed. The exposed portion is dissolved and removed to form a negative resist pattern.
In this specification, a resist composition in which an exposed portion of the resist film is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and an unexposed portion of the resist film is dissolved and removed to form a negative resist pattern. The resist composition thus prepared is referred to as a negative resist composition.
The resist composition of this embodiment may be a positive resist composition or a negative resist composition.
Further, the resist composition of this embodiment may be for an alkali developing process using an alkali developing solution for the developing treatment at the time of forming a resist pattern, and a developing solution containing an organic solvent (organic developing solution) may be used for the developing treatment. It may be for the solvent development process used.

The resist composition of the present embodiment has an acid generating ability to generate an acid upon exposure to light, and the component (A) may generate an acid upon exposure to light, and an additive compounded separately from the component (A). The component may generate an acid upon exposure.
Specifically, the resist composition of this embodiment may include (1) an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as “(B) component”), ( 2) The component (A) may be a component that generates an acid upon exposure, (3) The component (A) is a component that generates an acid upon exposure, and further contains a component (B). It may be.
That is, in the cases of the above (2) and (3), the component (A) becomes "a base material component which generates an acid upon exposure and whose solubility in a developing solution is changed by the action of the acid". When the component (A) is a base material component that generates an acid upon exposure to light and the solubility of the developer changes by the action of the acid, the component (A1) described below generates an acid upon exposure to light, and A polymer compound whose solubility in a developing solution is changed by the action of an acid is preferable. As such a polymer compound, a resin having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, a known unit can be used.

It is particularly preferable that the resist composition includes the above-mentioned case (1), that is, contains the component (A) and the component (Z) and further contains the component (B).

<(A) component>
In the resist composition of the present embodiment, the component (A) is a base component whose solubility in a developing solution changes due to the action of 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, the film forming ability is improved and, in addition, a nano-level resist pattern is easily formed.
The organic compound used as the base material component is roughly classified into a non-polymer and a polymer.
As the non-polymer, one having a molecular weight of 500 or more and less than 4000 is usually used. Hereinafter, the term "low molecular weight compound" means a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, one having a molecular weight of 1,000 or more is usually used. Hereinafter, the term "resin", "polymer compound" or "polymer" refers to a polymer having a molecular weight of 1000 or more.
As the molecular weight of the polymer, a polystyrene-equivalent mass average molecular weight by GPC (gel permeation chromatography) is used.

When the resist composition of the present embodiment is a "negative resist composition for alkaline development process" that forms a negative resist pattern in an alkali development process, or a "solvent that forms a positive resist pattern in a solvent development process" In the case of the “positive resist composition for development process”, the component (A) is preferably a base component (A-2) soluble in an alkali developing solution (hereinafter referred to as “component (A-2)”). It is used, and a crosslinking agent component is further added. In such a resist composition, for example, when an acid is generated from the component (B) upon exposure, the acid acts to cause crosslinking between the component (A-2) and the crosslinking agent component, resulting in alkali development. Solubility in liquid decreases (solubility in organic developer increases). Therefore, in forming a resist pattern, when a resist film obtained by applying the resist composition onto a support is selectively exposed, the exposed portion of the resist film is hardly soluble in an alkali developing solution (in an organic developing solution). However, the unexposed area of the resist film remains soluble in the alkaline developer (hardly soluble in the organic developer) and does not change. Therefore, the negative resist is developed by developing with the alkaline developer. A pattern is formed. Further, at this time, a positive resist pattern is formed by developing with an organic developer.
As the preferable component (A-2), a resin soluble in an alkali developing solution (hereinafter referred to as "alkali-soluble resin") is used.
Examples of the alkali-soluble resin include α-(hydroxyalkyl)acrylic acid or an alkyl ester of α-(hydroxyalkyl)acrylic acid (preferably having 1 to 5 carbon atoms) disclosed in JP-A-2000-206994. A resin having a constitutional unit derived from at least one selected from the group consisting of alkyl esters); a hydrogen atom bonded to the α-position carbon atom having a sulfonamide group, which is disclosed in US Pat. No. 6,949,325, is substituted with a substituent. Acrylic resin or polycycloolefin resin which may be contained; U.S. Pat. No. 6,949,325, JP-A-2005-336452, JP-A-2006-317803. An acrylic resin in which a hydrogen atom bonded to a carbon atom may be substituted with a substituent; a polycycloolefin resin having a fluorinated alcohol, which is disclosed in JP-A-2006-259582, and the like are preferable with less swelling. It is preferable because a resist pattern can be formed.
It should be noted that the α-(hydroxyalkyl)acrylic acid is an acrylic acid in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, and hydrogen is present at the carbon atom at the α-position to which a carboxy group is bonded. One or both of acrylic acid having an atom bonded thereto and α-hydroxyalkylacrylic acid having a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 5 carbon atoms) bonded to the α-position carbon atom. .
As the cross-linking agent component, for example, an amino-based cross-linking agent such as glycoluril having a methylol group or an alkoxymethyl group, or a melamine-based cross-linking agent is preferably used because a good resist pattern with less swelling is easily formed. . The compounding amount of the crosslinking agent component is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.

When the resist composition of the present embodiment is a “positive resist composition for alkaline development process” which forms a positive resist pattern in an alkali development process, or a “solvent which forms a negative resist pattern in a solvent development process” In the case of a “negative resist composition for development process”, the component (A) is preferably a base component (A-1) whose polarity is increased by the action of an acid (hereinafter referred to as “component (A-1)”). ) Is used. By using the component (A-1), the polarity of the base material component changes before and after exposure, so that a good development contrast can be obtained not only in the alkali developing process but also in the solvent developing process.
When an alkali development process is applied, the component (A-1) is poorly soluble in an alkali developing solution before exposure, and, for example, when an acid is generated from the component (B) by exposure, the action of the acid causes The polarity is increased and the solubility in an alkaline developer is increased. Therefore, in forming a resist pattern, when a resist film obtained by coating the resist composition on a support is selectively exposed, the exposed portion of the resist film changes from poorly soluble to soluble in an alkali developing solution. On the other hand, since the unexposed portion of the resist film remains sparingly soluble in alkali, a positive resist pattern is formed by alkali development.
On the other hand, when a solvent development process is applied, the component (A-1) has a high solubility in an organic developing solution before exposure, and when an acid is generated from the component (B) by exposure, the action of the acid. This increases the polarity and reduces the solubility in organic developers. Therefore, in the formation of a resist pattern, when a resist film obtained by coating the resist composition on a support is selectively exposed, the exposed portion of the resist film is changed from soluble to slightly soluble in an organic developing solution. While the resist film unexposed area remains soluble, it does not change, so by developing with an organic developer, contrast can be provided between the exposed area and the unexposed area, and the negative resist pattern is formed. It is formed.

In the resist composition of this embodiment, as the component (A), one type may be used alone, or two or more types may be used in combination.
In the resist composition of this embodiment, the component (A) is preferably the component (A-1). That is, the resist composition of the present embodiment is a “positive resist composition for an alkali developing process” that forms a positive resist pattern in an alkali developing process, or a “solvent developing that forms a negative resist pattern in a solvent developing process. It is preferably a “negative resist composition for process”. As the component (A), at least one of a high molecular compound and a low molecular compound can be used.
When the component (A) is the component (A-1), the component (A-1) preferably contains the resin component (A1) (hereinafter also referred to as “component (A1)”).

Component (A1) The component (A1) is preferably a resin component containing a polymer compound having a structural unit (a1) containing an acid-decomposable group whose polarity increases due to the action of an acid.
As the component (A1), those having a structural unit (a10) containing a hydroxystyrene skeleton in addition to the structural unit (a1) are preferable.
Further, as the component (A1), those having a structural unit (st) derived from styrene or a derivative thereof in addition to the structural unit (a1) are also preferable.
Further, the component (A1) may have a structural unit other than the structural unit (a1), the structural unit (a10) and the structural unit (st).

<<Structural unit (a1)>>
The structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity increases due to the action of an acid.
The "acid-decomposable group" is an acid-decomposable group capable of cleaving at least a part of the bonds in the structure of the acid-decomposable group by the action of an acid.
Examples of the acid-decomposable group whose polarity increases by the action of an acid include groups that decompose to form a polar group by the action of an acid.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group _(-SO 3 H) and the like. Among these, a polar group containing —OH in the structure (hereinafter sometimes referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is more preferable, and a carboxy group is particularly preferable.
More specific examples of the acid-decomposable group include 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).

Here, the “acid-dissociable group” is a group having an acid-dissociable group capable of cleaving a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group by the action of (i) an acid, Alternatively, (ii) after a part of the bond is cleaved by the action of an acid, a decarboxylation reaction further occurs, whereby the bond between the acid dissociable group and an atom adjacent to the acid dissociable group is cleaved. Both groups are obtained groups.
The acid-dissociable group constituting the acid-decomposable group needs to be a group having a lower polarity than the polar group generated by the dissociation of the acid-dissociable group, which allows the acid-dissociable group to act under the action of an acid. When is dissociated, a polar group having a higher polarity than the acid dissociable group is generated and the polarity is increased. As a result, the polarity of the entire component (A1) increases. Due to the increase in polarity, the solubility in the developing solution relatively changes, the solubility increases when the developing solution is an alkaline developing solution, and the solubility changes when the developing solution is an organic developing solution. Decrease.

Examples of the acid dissociable group include those which have been proposed as the acid dissociable group of the base resin for the chemically amplified resist composition.
Specifically, “acetal-type acid dissociable group” and “tertiary alkyl ester-type acid dissociable group” described below are proposed as the acid dissociable group of the base resin for the chemically amplified resist composition. Group" and "tertiary alkyloxycarbonyl acid dissociable group".

Acetal-type acid-labile group:
Examples of the acid dissociable group that protects a carboxy group or a hydroxyl group among the polar groups include, for example, an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as “acetal-type acid dissociable group”). There are some cases).

［式中、Ｒａ’^１、Ｒａ’^２は水素原子またはアルキル基である。Ｒａ’^３は炭化水素基であって、Ｒａ’^３は、Ｒａ’^１、Ｒａ’^２のいずれかと結合して環を形成してもよい。］

[In the formula, Ra′ ¹ and Ra′ ² are a hydrogen atom or an alkyl group. Ra′ ³ is a hydrocarbon group, and Ra′ ³ may combine with either Ra′ ¹ or Ra′ ² to form a ring. ]

In the formula (a1-r-1), at least one of Ra′ ¹ and Ra′ ² is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
When Ra′ ¹ or Ra′ ² is an alkyl group, the alkyl group is the same as the alkyl group described as the substituent which may be bonded to the α-position carbon atom in the description of the α-substituted acrylate ester. The same thing is mentioned and a C1-C5 alkyl group is preferable. Specifically, a linear or branched alkyl group is preferably mentioned. More specific examples include 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, a neopentyl group, and the like. More preferably, a methyl group is particularly preferable.

In the formula (a1-r-1), examples of the hydrocarbon group represented by Ra′ ³ include a linear or branched alkyl group and a cyclic hydrocarbon group.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group and a 2,2-dimethylbutyl group, and an isopropyl group is preferable.

When Ra′ ³ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When the cyclic hydrocarbon group of Ra′ ³ is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle 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 for Ra′ ³ include a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle; two or more aromatic rings A group in which one hydrogen atom is removed from an aromatic compound (for example, biphenyl, fluorene, etc.); A group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (for example, a benzyl group , Phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, arylalkyl group such as 2-naphthylethyl group, etc.) and the like. The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom. preferable.

The cyclic hydrocarbon group for Ra′ ³ may have a substituent. As the substituent, for example, -R ^P1 , -R ^P2- O-R ^P1 , -R ^P2- CO-R ^P1 , -R ^P2- CO-OR ^P1 , -R ^P2- O-CO-R ^P1 , -R ^{P2 -OH,} (collectively hereinafter these substituents also referred to as ^{"Ra 05".) -R} P2 -CN or ^-R P2 -COOH and the like.
Here, R ^P1 is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic having 6 to 30 carbon atoms. It is a group hydrocarbon group. R ^P2 is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent group having 6 to 30 carbon atoms. Is an aromatic hydrocarbon group. However, some or all of the hydrogen atoms ^{contained in} the chain saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group and the aromatic hydrocarbon group of R ^P1 and R ^P2 may be substituted with a fluorine atom. The aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents singly, or may have one or more of each of the above-mentioned substituents.
Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and decyl group. ..
Examples of the monovalent aliphatic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group and the like. Monocyclic aliphatic saturated hydrocarbon group; bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.02,6]decanyl group, tricyclo[3.3.1.13,7]decanyl group , Polycycloaliphatic saturated hydrocarbon groups such as tetracyclo[6.2.1.1.13, 6.02, 7] dodecanyl group and adamantyl group.
Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene and phenanthrene.

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

Tertiary alkyl ester type acid dissociable group:
Among the polar groups, examples of the acid dissociable group that protects the carboxy group include acid dissociable groups represented by the following general formula (a1-r-2).
In addition, among the acid dissociable groups represented by the following formula (a1-r-2), a group composed of an alkyl group may be hereinafter referred to as a "tertiary alkyl ester-type acid dissociable group" for convenience. .

［式中、Ｒａ’^４〜Ｒａ’^６はそれぞれ炭化水素基であって、Ｒａ’^５、Ｒａ’^６は互いに結合して環を形成してもよい。］

[In the formula, Ra′ ^{4 to} Ra′ ⁶ are each a hydrocarbon group, and Ra′ ⁵ and Ra′ ⁶ may be bonded to each other to form a ring. ]

Examples of the hydrocarbon group of Ra′ ⁴ include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group.
A linear or branched alkyl group in Ra' ⁴ , a cyclic hydrocarbon group (an aliphatic hydrocarbon group which is a monocyclic group, an aliphatic hydrocarbon group which is a polycyclic group, an aromatic hydrocarbon group) Examples of () include the same as Ra' ³ described above.
The chain or cyclic alkenyl group for Ra′ ⁴ is preferably an alkenyl group having 2 to 10 carbon atoms.
Examples of the hydrocarbon group for Ra′ ⁵ and Ra′ ⁶ include the same as those for Ra′ ³ .

When Ra′ ⁵ and Ra′ ⁶ are bonded to each other to form a ring, a group represented by general formula (a1-r2-1) shown below and a group represented by general formula (a1-r2-2) shown below A group represented by general formula (a1-r2-3) shown below is preferable.
On the other hand, when Ra′ ^{4 to} Ra′ ⁶ are independent hydrocarbon groups that are not bonded to each other, groups represented by general formula (a1-r2-4) shown below are preferred.

［式（ａ１−ｒ２−１）中、Ｒａ’^１０は、炭素数１〜１０のアルキル基、又は下記一般式（ａ１−ｒ２−ｒ１）で表される基を示す。Ｒａ’^１１はＲａ’^１０が結合した炭素原子と共に脂肪族環式基を形成する基を示す。式（ａ１−ｒ２−２）中、Ｙａは炭素原子である。Ｘａは、Ｙａと共に環状の炭化水素基を形成する基である。この環状の炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ^０１〜Ｒａ^０３は、それぞれ独立して、水素原子、炭素数１〜１０の１価の鎖状飽和炭化水素基又は炭素数３〜２０の１価の脂肪族環状飽和炭化水素基である。この鎖状飽和炭化水素基及び脂肪族環状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ^０１〜Ｒａ^０３の２つ以上が互いに結合して環状構造を形成していてもよい。式（ａ１−ｒ２−３）中、Ｙａａは炭素原子である。Ｘａａは、Ｙａａと共に脂肪族環式基を形成する基である。Ｒａ^０４は、置換基を有していてもよい芳香族炭化水素基である。式（ａ１−ｒ２−４）中、Ｒａ’^１２及びＲａ’^１３は、それぞれ独立に、炭素数１〜１０の１価の鎖状飽和炭化水素基又は水素原子である。この鎖状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ’^１４は、置換基を有していてもよい炭化水素基である。＊は結合手を示す（以下同じ）。］

Wherein (a1-r2-1), Ra ' 10 represents a group represented by the alkyl group having 1 to 10 carbon atoms, or the following general formula (a1-r2-r1). Ra′ ¹¹ represents a group which forms an aliphatic cyclic group together with the carbon atom to which Ra′ ¹⁰ is bonded. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms contained in this cyclic hydrocarbon group may be substituted. Ra ^{01 to} Ra ⁰³ are each independently a hydrogen atom, a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms contained in the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra ^{01 to} Ra ⁰³ may combine with each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra ⁰⁴ is an aromatic hydrocarbon group which may have a substituent. In formula (a1-r2-4), Ra′ ¹² and Ra′ ¹³ are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Some or all of the hydrogen atoms contained in the chain saturated hydrocarbon group may be substituted. Ra′ ¹⁴ is a hydrocarbon group which may have a substituent. * Indicates a bond (hereinafter the same). ]

［式中、Ｙａ^０は、第４級炭素原子である。Ｒａ^０３１、Ｒａ^０３２及びＲａ^０３３は、それぞれ独立に、置換基を有していてもよい炭化水素基である。但し、Ｒａ^０３１、Ｒａ^０３２及びＲａ^０３３のうちの１つ以上は、少なくとも一つの極性基を有する炭化水素基である。］

[In the formula, Ya ⁰ is a quaternary carbon atom. Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ are each independently a hydrocarbon group which may have a substituent. However, one or more of Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ is a hydrocarbon group having at least one polar group. ]

In the above formula (a1-r2-1), the alkyl group having 1 to ¹⁰ carbon atoms of Ra′ ¹⁰ is the linear or branched alkyl group of Ra′ ³ in the formula (a1-r-1). The groups mentioned are preferred. Ra′ ¹⁰ is preferably an alkyl group having 1 to 5 carbon atoms.

In the formula (a1-r2-r1), Ya ⁰ is a quaternary carbon atom. That is, there are four adjacent carbon atoms bonded to Ya ⁰ (carbon atom).

In the formula (a1-r2-r1), Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ are each independently a hydrocarbon group which may have a substituent. The hydrocarbon group for Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ independently includes a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group.

The linear alkyl group in Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
The branched alkyl group in Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and an isopropyl group is preferable.
The chain-like or cyclic alkenyl group in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is preferably an alkenyl group having 2 to 10 carbon atoms.

The cyclic hydrocarbon group in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group in Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The carbon number of 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, and phenanthrene; and aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle 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 (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle; aromatic containing two or more aromatic rings. A group in which one hydrogen atom is removed from a compound (for example, biphenyl, fluorene, etc.); A group in which one of the hydrogen atoms in the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (for example, benzyl group, phenethyl group) , An arylalkyl group such as a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group) and the like. The alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocycle has preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

When the hydrocarbon group represented by Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is substituted, examples of the substituent include a hydroxy group, a carboxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.). ), an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like), an alkyloxycarbonyl group and the like.

Among them, the hydrocarbon group ^optionally having a substituent in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is preferably a linear or branched alkyl group optionally having a substituent, A linear alkyl group is more preferable.

However, one or more of Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ is a hydrocarbon group having at least a polar group.
The “hydrocarbon group having a polar group” means that a methylene group (—CH ₂ —) forming a hydrocarbon group is substituted with a polar group, or at least one hydrogen atom forming a hydrocarbon group is Any of those substituted with a polar group is included.
As the "hydrocarbon group having a polar group", a functional group represented by the following general formula (a1-p1) is preferable.

［式中、Ｒａ^０７は、炭素数２〜１２の２価の炭化水素基を表す。Ｒａ^０８は、ヘテロ原子を含む２価の連結基を表す。Ｒａ^０６は、炭素数１〜１２の１価の炭化水素基を表す。ｎ_ｐ０は、１〜６の整数である。］

Wherein, ^{Ra 07} represents a divalent hydrocarbon group having 2 to 12 carbon atoms. Ra ⁰⁸ represents a divalent linking group containing a hetero atom. Ra ⁰⁶ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. n _p0 is an integer of 1 to 6. ]

In the formula (a1-p1), Ra ⁰⁷ represents a divalent hydrocarbon group having 2 to 12 carbon atoms.
The number of carbon atoms of ra ⁰⁷ is 2 to 12, 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, 2 carbon atoms being particularly preferred.
The hydrocarbon group for Ra ⁰⁷ is preferably a chain or cyclic aliphatic hydrocarbon group, and more preferably a chain hydrocarbon group.
Examples of Ra ⁰⁷ include ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1, 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, etc. A linear alkanediyl group of: propane-1,2-diyl group, 1-methylbutane-1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,4-diyl group, 2 -Branched alkanediyl group such as methylbutane-1,4-diyl group; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1 A cycloalkanediyl group such as a 5,5-diyl group; a multi-group such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group Examples thereof include cyclic divalent alicyclic hydrocarbon groups.
Among the above, an alkanediyl group is preferable, and a linear alkanediyl group is more preferable.

In the formula (a1-p1), Ra ⁰⁸ represents a divalent linking group containing a hetero atom.
Examples of Ra ⁰⁸ include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-, and -C(=O)-NH-. , -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group and an acyl group), -S-, -S(=O) _2- , -. S(=O) _2- O- and the like can be mentioned.
Among these, -O-, -C(=O)-O-, -C(=O)-, and -OC(=O)-O- are preferable from the viewpoint of solubility in a developing solution, and- O- and -C(=O)- are particularly preferable.

In the formula (a1-p1), Ra ⁰⁶ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms.
The carbon number of Ra ⁰⁶ is 1 to 12, and from the viewpoint of solubility in a developing solution, 1 to 8 carbon atoms are preferable, 1 to 5 carbon atoms are more preferable, 1 to 3 carbon atoms are further preferable, and carbon number is 1 or 2 is particularly preferable, and 1 is the most preferable.

Examples of the hydrocarbon group for Ra ⁰⁶ include a chain hydrocarbon group or a cyclic hydrocarbon group, or a hydrocarbon group combining a chain and a ring.
Examples of the chain hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n Examples include -heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.

The cyclic hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a methyl group. Examples thereof include cycloalkyl groups such as cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1-(adamantan-1-yl)alkane-1-yl group, and norbornyl. Group, methylnorbornyl group, isobornyl group and the like.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group and mesityl group. , Biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and the like.

From the viewpoint of solubility in a developing solution, Ra ⁰⁶ is preferably a chain hydrocarbon group, more preferably an alkyl group, and even more preferably a straight chain alkyl group.

In the formula (a1-p1), n _p0 is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

Specific examples of the hydrocarbon group having at least a polar group are shown below.
In the following formulas, * is a bond that bonds to the quaternary carbon atom (Ya ⁰ ).

In the above formula (a1-r2-r1), the number of hydrocarbon groups having at least a polar group among Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is 1 or more, but the number of hydrocarbon groups to be applied to the developing solution at the time of forming a resist pattern is not limited. It may be appropriately determined in consideration of the solubility of, for example, one or two of Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is preferable, and one is particularly preferable.

The hydrocarbon group having at least the polar group may have a substituent other than the polar group. Examples of this substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and a halogenated alkyl group having 1 to 5 carbon atoms.

In the formula (a1-r2-1), Ra′ ¹¹ (an aliphatic cyclic group formed together with the carbon atom to which Ra′ ¹⁰ is bonded) is a monocyclic group of Ra′ ³ in the formula (a1-r-1). Alternatively, the groups exemplified as the aliphatic hydrocarbon group which is a polycyclic group are preferable.

In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is a cyclic monovalent hydrocarbon group (aliphatic in Ra′ ³ in formula (a1-r-1) above. A group in which one or more hydrogen atoms are further removed from (hydrocarbon group) is included.
The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of the substituent include the same as the substituent that the cyclic hydrocarbon group for Ra′ ³ may have.
In formula (a1-r2-2), examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra ^{01 to} Ra ⁰³ include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group, decyl group and the like.
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in Ra ^{01 to} Ra ⁰³ include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group. Group, cyclododecyl group, and other monocyclic saturated aliphatic hydrocarbon groups; bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.02,6]decanyl group, tricyclo[3.3.1] .13,7] decanyl group, tetracyclo[6.2.1.13, 6.02,7] dodecanyl group, adamantyl group, and other polycyclic aliphatic saturated hydrocarbon groups.
Among them, Ra ^{01 to} Ra ⁰³ are preferably a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, from the viewpoint of easiness of synthesis of the monomer compound that induces the structural unit (a1). Among them, a hydrogen atom, a methyl group and an ethyl group are more preferable, and a hydrogen atom is particularly preferable.

Examples of the substituent contained in the chain saturated hydrocarbon group represented by Ra ^{01 to} Ra ⁰³ or the aliphatic cyclic saturated hydrocarbon group include the same groups as Ra ⁰⁵ described above.

Examples of the group containing a carbon-carbon double bond formed by combining two or more of Ra ^{01 to} Ra ⁰³ with each other to form a cyclic structure include, for example, a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, and methyl. Examples thereof include a cyclohexenyl group, a cyclopentylideneethenyl group, and a cyclohexylideneethenyl group. Among these, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylideneethenyl group are preferable from the viewpoint of easiness of synthesis of the monomer compound that induces the structural unit (a1).

In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is an aliphatic carbon group which is a monocyclic group or polycyclic group of Ra′ ³ in formula (a1-r-1). The groups mentioned as hydrogen groups are preferred.
In formula (a1-r2-3), examples of the aromatic hydrocarbon group for Ra ⁰⁴ include groups in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra ⁰⁴ is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene. , A group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene is more preferable, a group obtained by removing one or more hydrogen atoms from benzene or naphthalene is particularly preferable, and a group obtained by removing one or more hydrogen atoms from benzene is the most preferable. preferable.

Examples of the substituent that Ra ⁰⁴ in the formula (a1-r2-3) may have include a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, Bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group and the like.

In formula (a1-r2-4), Ra′ ¹² and Ra′ ¹³ are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra′ ¹² and Ra′ ¹³ include the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra ⁰¹ to Ra ⁰³ described above. The same as the group can be mentioned. Some or all of the hydrogen atoms contained in the chain saturated hydrocarbon group may be substituted.
Among them, Ra′ ¹² and Ra′ ¹³ are preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. preferable.
When the chain saturated hydrocarbon group represented by Ra′ ¹² and Ra′ ¹³ above is substituted, examples of the substituent include the same groups as Ra ⁰⁵ described above.

In the formula (a1-r2-4), Ra′ ¹⁴ is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group for Ra′ ¹⁴ include a linear or branched alkyl group or a cyclic hydrocarbon group.

The linear alkyl group in Ra′ ¹⁴ preferably has 1 to 5 carbon atoms, more preferably 1 to 4 and even more preferably 1 or 2. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

The branched chain alkyl group for Ra′ ¹⁴ preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and an isopropyl group is preferable.

When Ra′ ¹⁴ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

Examples of the aromatic hydrocarbon group for Ra′ ¹⁴ include the same as the aromatic hydrocarbon group for Ra ⁰⁴ . Among them, Ra′ ¹⁴ is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene. A group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene is more preferable, a group obtained by removing one or more hydrogen atoms from naphthalene or anthracene is particularly preferable, and a group obtained by removing one or more hydrogen atoms from naphthalene is preferable. Most preferred.
Examples of the substituent that Ra′ ¹⁴ may have include the same substituents that Ra ⁰⁴ may have.

When Ra′ ^{14 in the} formula (a1-r2-4) is a naphthyl group, the position bonded to the tertiary carbon atom in the formula (a1-r2-4) is the 1-position or 2-position of the naphthyl group. It may be either.
When Ra′ ^{14 in the} formula (a1-r2-4) is an anthryl group, the position bonded to the tertiary carbon atom in the formula (a1-r2-4) is 1-, 2- or It may be in 9th place.

Specific examples of the group represented by the formula (a1-r2-1) are shown below.

Specific examples of the group represented by the formula (a1-r2-2) are shown below.

Specific examples of the group represented by the formula (a1-r2-3) are shown below.

Specific examples of the group represented by the formula (a1-r2-4) are shown below.

Tertiary alkyloxycarbonyl acid dissociative group:
Examples of the acid dissociable group that protects a hydroxyl group among the polar groups include, for example, an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter referred to as “tertiary alkyloxycarbonyl acid dissociable group” for convenience. It may be said).

［式中、Ｒａ’^７〜Ｒａ’^９はそれぞれアルキル基である。］

[In the formula, Ra′ ^{7 to} Ra′ ⁹ are each an alkyl group. ]

In formula (a1-r-3), Ra′ ^{7 to} Ra′ ⁹ are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
The total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

As the structural unit (a1), a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, a structural unit derived from acrylamide, hydroxystyrene or hydroxy At least a part of hydrogen atoms in the hydroxyl group of the structural unit derived from a styrene derivative is protected by a substituent containing the acid-decomposable group, vinylbenzoic acid or a structural unit derived from a vinylbenzoic acid derivative- Examples include structural units in which at least a part of hydrogen atoms in C(=O)-OH are protected by a substituent containing the acid-decomposable group.

Among the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
Specific preferred examples of the structural unit (a1) include structural units represented by general formula (a1-1) or (a1-2) shown below.

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｖａ^１は、エーテル結合を有していてもよい２価の炭化水素基である。ｎ_ａ１は、０〜２の整数である。Ｒａ^１は、上記の一般式（ａ１−ｒ−１）又は（ａ１−ｒ−２）で表される酸解離性基である。Ｗａ^１はｎ_ａ２＋１価の炭化水素基であり、ｎ_ａ２は１〜３の整数であり、Ｒａ^２は上記の一般式（ａ１−ｒ−１）又は（ａ１−ｒ−３）で表される酸解離性基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ¹ is a divalent hydrocarbon group which may have an ether bond. n _a1 is an integer of 0 to 2. Ra ¹ is an acid dissociable group represented by the above general formula (a1-r-1) or (a1-r-2). Wa ¹ is a _n a2 +1 monovalent hydrocarbon _{group, n a2} is an integer from 1 to 3, Ra ² is represented by the above general formula (a1-r-1) or (a1-r-3) Acid dissociable group. ]

In the above formula (a1-1), the alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, a methyl group or an ethyl group. , Propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

In the above formula (a1-1), the divalent hydrocarbon group for Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

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

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. ..
As the linear aliphatic hydrocarbon group, preferably a linear alkylene group, and specific examples include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], trimethylene [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] , and the like.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, preferably a branched chain alkylene group, _{specifically, -CH (CH 3) -,} - CH (CH 2 CH 3) -, - C (CH 3) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 Alkylethylene group such as CH ₃ ) ₂ —CH ₂ —; alkyl trimethylene group such as —CH(CH ₃ )CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ —; —CH(CH ₃ ). Examples thereof include alkyl alkylene groups such as alkyl tetramethylene groups such as CH ₂ CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ CH ₂ — and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group having a linear or branched structure. Examples thereof include a group bonded to the end of a chain-like aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same groups as the straight-chain aliphatic hydrocarbon group or the branched-chain aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically, adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 12 carbon atoms. .. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring included in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; some of the carbon atoms constituting the aromatic hydrocarbon ring are hetero. Aromatic heterocycles substituted with atoms may be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group). Group in which one of the hydrogen atoms of (1) is substituted with an alkylene group (for example, arylalkyl such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group). Group in which one hydrogen atom is further removed from the aryl group in the group) and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the formula (a1-1), Ra ¹ is an acid dissociable group represented by the formula (a1-r-1) or (a1-r-2).

In the formula (a1-2), the na ₂ +1 valent hydrocarbon group for Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, may be saturated or unsaturated, and is usually preferably saturated. As the aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a linear or branched aliphatic hydrocarbon group Examples thereof include groups in which an aliphatic hydrocarbon group containing a ring in the structure is combined.
The _{na 2} +1 valence is preferably 2 to 4 valence, and more preferably 2 or 3 valence.

In the formula (a1-2), Ra ² is an acid dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).

Specific examples of the structural unit represented by the formula (a1-1) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

Specific examples of the structural unit represented by the formula (a1-2) are shown below.

The structural unit (a1) contained in the component (A1) may be one type or two or more types.
As the structural unit (a1), the structural unit represented by the above formula (a1-1) is more preferable because the characteristics (sensitivity, CDU, shape, etc.) in lithography by KrF can be more easily enhanced.
Among these, as the structural unit (a1), those containing a structural unit represented by the following general formula (a1-1-1) are particularly preferable.

［式中、Ｒａ^１”は、一般式（ａ１−ｒ２−１）、（ａ１−ｒ２−３）又は（ａ１−ｒ２−４）で表される酸解離性基である。］

[In the formula, Ra ¹ ″ is an acid-labile group represented by general formula (a1-r2-1), (a1-r2-3), or (a1-r2-4).]

In the formula (a1-1-1), R, Va ¹ and _{n a1} is, R in the formula (a1-1), the same as Va ¹ and _{n a1.}
The description of the acid dissociable group represented by formula (a1-r2-1), (a1-r2-3) or (a1-r2-4) is as described above.

The proportion of the structural unit (a1) in the component (A1) is preferably 1 to 80 mol%, and more preferably 5 to 70 mol%, based on the total (100 mol%) of all structural units constituting the component (A1). More preferably, 10-60 mol% is still more preferable.
By setting the proportion of the structural unit (a1) to be at least the lower limit value, lithography properties such as sensitivity, resolution, and roughness improvement are improved. When it is at most the upper limit value, it can be balanced with other structural units, and various lithographic properties will be good.

<<Structural Unit (a10) Containing Hydroxystyrene Skeleton>>
The component (A1) preferably has a structural unit (a10) containing a hydroxystyrene skeleton in addition to the structural unit (a1).
Suitable examples of the structural unit (a10) include structural units represented by general formula (a10-1) shown below.

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｙａ^ｘ１は、単結合又は２価の連結基である。Ｗａ^ｘ１は、（ｎ_ａｘ１＋１）価の芳香族炭化水素基である。ｎ_ａｘ１は、１〜３の整数である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is a (n _ax1 +1) _-valent aromatic hydrocarbon group. n _ax1 is an integer of 1 to 3. ]

In the above formula (a10-1), 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.
The alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n- Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms of R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

In the formula (a10-1), Ya ^x1 represents a single bond or a divalent linking group.
Preferred examples of the divalent linking group for Ya ^x1 include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom.

-A divalent hydrocarbon group which may have a substituent:
When Ya ^x1 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

.. Aliphatic hydrocarbon group in Ya ^x1 The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

... Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and carbon. Numbers 1 to 4 are more preferable, and numbers 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, preferably a linear alkylene group, and specific examples include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], trimethylene [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (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, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, preferably a branched chain alkylene group, _{specifically, -CH (CH 3) -,} - CH (CH 2 CH 3) -, - C (CH 3) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 Alkylethylene group such as CH ₃ ) ₂ —CH ₂ —; alkyl trimethylene group such as —CH(CH ₃ )CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ —; —CH(CH ₃ ). Examples thereof include alkyl alkylene groups such as alkyl tetramethylene groups such as CH ₂ CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ CH ₂ — and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

...Aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure. (A group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, the cyclic fat Examples thereof include a group in which a group hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same ones as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 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 two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, Examples include 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 halogenated alkyl 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 most 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 iso-propoxy group, an n-butoxy group, a tert-butoxy group, Most preferred are methoxy and ethoxy groups.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atom.
In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O) _2- , and -S(=O) _2- O- are preferable.

..Aromatic Hydrocarbon Group in Ya ^x1 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle 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 obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group in which two hydrogen atoms have been removed from (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms in a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) A group in which one is substituted with an alkylene group (for example, a hydrogen atom from an aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group). Group in which one atom is further removed) and the like. The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to the 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 halogenated alkyl group, a hydroxyl group and the like.
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 group, the halogen atom and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

-Divalent linking group containing a hetero atom:
When Ya ^x1 is a divalent linking group containing a hetero atom, preferable examples of the linking group include —O—, —C(═O)—O—, —C(═O)—, and —O—C. (=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H may be substituted with a substituent such as an alkyl group and an acyl group. _{.), - S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 - ^{C (= O) -O -,} - C (= O) -O-Y 21 -, - [Y 21 -C (= O) -O] m "-Y 22 -, - Y 21 -O-C ( = O) ^{-Y 22} - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - group represented by ^{wherein, Y 21} and ^{Y 22} have independently substituent Is a divalent hydrocarbon group, O is an oxygen atom, and m″ is an integer of 0 to 3. ] Etc. are mentioned.
The divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH. )-, the H may be substituted with a substituent such as an alkyl group or acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 - _{^{C (= O) -O] m}} "-Y 22 -, - Y 21 -O-C (= O) -Y 22 - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - in, Y ²¹ and Y ²² each independently represent a divalent hydrocarbon group which may have a substituent, and the divalent hydrocarbon group is mentioned in the description of the divalent linking group. And the same as the (divalent hydrocarbon group which may have a substituent).
As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkylmethylene group is more preferable. 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.
Formula _{^{- [Y 21 -C (= O}} ) -O] m "-Y 22 - In the group represented by, m" is an integer of 0 to 3, preferably an integer of 0 to 2, 0 Or, 1 is more preferable, and 1 is particularly preferable. In other words, the formula ^- Examples of the group represented by the formula ^{-Y 21 -C (= O) -O} -Y 22 - - [Y 21 -C (= O) -O] m "-Y 22 represented by group is particularly preferred among them, the formula _{-. (CH 2) a '} -C (= O) -O- (CH 2) b' -. in the group represented by the formula in the formula, a 'is from 1 to 10 Is an integer of 1-8, preferably an integer of 1-5, more preferably 1 or 2, and most preferably 1. b'is an integer of 1-10 and 1-8. An integer is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is further preferable, and 1 is most preferable.

As Ya ^x1 , a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), -C(=O)-NH-, a linear or branched alkylene group. , Or a combination thereof, and particularly preferably a single bond.

In the formula (a10-1), Wa ^x1 is a (n _ax1 +1) _-valent aromatic hydrocarbon group.
Examples of the aromatic hydrocarbon group for Wa ^x1 include a group obtained by removing (n _ax1 +1) hydrogen atoms from an aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle 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.

In the formula (a10-1), n _ax1 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

Below, the specific example of the structural unit represented by the said general formula (a10-1) is shown.
In the formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (a10) contained in the component (A1) may be one type or two or more types.
In the component (A1), the proportion of the structural unit (a10) is, for example, 1 to 90 mol%, or 10 to 85%, with respect to the total (100 mol%) of all the structural units constituting the component (A1). Mol% is preferable, 20-80 mol% is more preferable, 30-75 mol% is especially preferable.
By setting the proportion of the structural unit (a10) to be not less than the lower limit of the above-mentioned preferable range, lithography properties such as sensitivity, resolution, and roughness improvement are improved. When it is at most the upper limit value, it can be balanced with other structural units, and various lithographic properties will be good.

<<Structural unit (a2)>>
The component (A1) is a structural unit (a2) containing a lactone-containing cyclic group, a —SO ₂ —-containing cyclic group or a carbonate-containing cyclic group, in addition to the structural unit (a1) (provided that the structural unit (a a1) is excluded).
The lactone-containing cyclic group, -SO ₂ -containing cyclic group or carbonate-containing cyclic group of the structural unit (a2) adheres to the substrate of the resist film when the component (A1) is used for forming the resist film. It is effective in enhancing the sex. In addition, by having the structural unit (a2), for example, the acid diffusion length is appropriately adjusted, the adhesiveness of the resist film to the substrate is enhanced, and the solubility during development is appropriately adjusted. Etc. will be good.

The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C(═O)— in its ring skeleton. The lactone ring is counted as the first ring, and a lactone ring alone is referred to as a monocyclic group, and a lactone ring having another ring structure is referred to as a polycyclic group regardless of the structure. The lactone-containing cyclic group may be either a monocyclic group or a polycyclic group.
The lactone-containing cyclic group in the structural unit (a2) is not particularly limited and any one can be used. Specific examples thereof include groups represented by general formulas (a2-r-1) to (a2-r-7) shown below.

［式中、Ｒａ’^２１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子（−Ｏ−）もしくは硫黄原子（−Ｓ−）を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｎ’は０〜２の整数であり、ｍ’は０または１である。］

[Wherein Ra′ ²¹ is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR”, —OC(═O)R”, a hydroxyalkyl group or a cyano group. There; R "represents a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO 2 _- be-containing cyclic group; A" represents an oxygen atom (-O-) or a sulfur atom (- S-) is an alkylene group having 1 to 5 carbon atoms, which may contain S-), an oxygen atom or a sulfur atom, n'is an integer of 0 to 2, and m'is 0 or 1. ]

In the general formulas (a2-r-1) to (a2-r-7), the alkyl group for Ra′ ²¹ is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples thereof include 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, a neopentyl group and a hexyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
As the alkoxy group for Ra′ ^21, an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specific examples thereof include groups in which an alkyl group mentioned as the alkyl group in Ra′ ²¹ and an oxygen atom (—O—) are linked.
Examples of the halogen atom in Ra′ ²¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
'Examples of the halogenated alkyl group for ^21, the Ra' Ra part or all of the hydrogen atoms of the alkyl group in ²¹ can be mentioned it has been substituted with the aforementioned halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

In —COOR″ and —OC(═O)R″ of Ra′ ²¹ , R″ is any of a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO ₂ — containing cyclic group. Is.
The alkyl group for R″ may be linear, branched or cyclic, and preferably has 1 to 15 carbon atoms.
When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. preferable.
When R″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Or a group in which one or more hydrogen atoms have been removed from a monocycloalkane that may or may not be substituted with a fluorinated alkyl group; polycycloalkanes such as bicycloalkane, tricycloalkane, and tetracycloalkane From the monocycloalkane such as cyclopentane and cyclohexane; and adamantane, norbornane, isobornane, and trigroup. Examples thereof include groups in which one or more hydrogen atoms have been removed from polycycloalkane such as cyclodecane and tetracyclododecane.
Examples of the lactone-containing cyclic group for R″ include the same groups as those represented by the general formulas (a2-r-1) to (a2-r-7).
The carbonate-containing cyclic group for R″ is the same as the carbonate-containing cyclic group described below, and specifically, the groups represented by general formulas (ax3-r-1) to (ax3-r-3), respectively. Is mentioned.
The containing cyclic group, -SO ₂ below - - -SO ₂ in R "are the same as containing cyclic group, specifically the general formula (a5-r-1) ~ (a5-r-4) And the groups respectively represented by.
The hydroxyalkyl group for Ra′ ²¹ preferably has 1 to 6 carbon atoms, and specific examples thereof include a group in which at least one hydrogen atom of the alkyl group for Ra′ ²¹ is substituted with a hydroxyl group. ..

In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A″ is a straight chain or branched chain. An alkylene group is preferable, and examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, etc. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include the terminal or carbon atom of the alkylene group. between atoms -O- or -S- can be mentioned a group intervening, for example, _{-O-CH 2 -, - CH} 2 -O-CH 2 -, - S-CH 2 -, - CH 2 -S-CH _2- etc. are mentioned. As A", a C1-C5 alkylene group or -O- is preferable, a C1-C5 alkylene group is more preferable, and a methylene group is the most preferable.

Specific examples of the groups represented by general formulas (a2-r-1) to (a2-r-7) are shown below.

And _- "-SO 2 containing cyclic group", -SO 2 _- within the ring skeleton thereof shows a cyclic group containing a ring containing, in particular, -SO 2 _- sulfur atom (S) is in A cyclic group that forms part of the ring skeleton of the cyclic group. A ring containing —SO ₂ — in its ring skeleton is counted as the first ring, and if it is the only ring, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. Called. The —SO ₂ — containing cyclic group may be either a monocyclic group or a polycyclic group.
The —SO ₂ — containing cyclic group is particularly a cyclic group containing —O—SO ₂ — in its ring skeleton, that is, —O—S— in —O—SO ₂ — forms a part of the ring skeleton. It is preferably a cyclic group containing a sultone ring to be formed.
Specific examples of the —SO ₂ — containing cyclic group include groups represented by general formulas (a5-r-1) to (a5-r-4) shown below.

［式中、Ｒａ’^５１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｎ’は０〜２の整数である。］

[Wherein Ra′ ⁵¹ is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR”, —OC(═O)R”, a hydroxyalkyl group or a cyano group. R; is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO ₂ —-containing cyclic group; and A″ is a carbon that may contain an oxygen atom or a sulfur atom. It is an alkylene group of formulas 1 to 5, an oxygen atom or a sulfur atom, and n′ is an integer of 0 to 2. ]

In the general formulas (a5-r-1) to (a5-r-2), A″ represents the general formulas (a2-r-2), (a2-r-3), and (a2-r-5). It is similar to A" in the inside.
The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR″, —OC(═O)R″ and hydroxyalkyl group for Ra′ ⁵¹ are each represented by the general formula (a2-r-1) to (a2-r-1). The same as those mentioned in the description of Ra′ ^{21 in} a2-r-7) can be mentioned.
Specific examples of the groups represented by general formulas (a5-r-1) to (a5-r-4) are shown below. “Ac” in the formula represents an acetyl group.

The “carbonate-containing cyclic group” refers to a cyclic group containing a ring (carbonate ring) containing —O—C(═O)—O— in its ring skeleton. The carbonate ring is counted as the first ring, and when it has only a carbonate ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The carbonate-containing cyclic group may be either a monocyclic group or a polycyclic group.
The carbonate ring-containing cyclic group is not particularly limited, and any group can be used. Specific examples include groups represented by general formulas (ax3-r-1) to (ax3-r-3) shown below.

［式中、Ｒａ’^ｘ３１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｐ’は０〜３の整数であり、ｑ’は０または１である。］

[ ^Wherein Ra′ ^x31 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR”, —OC(═O)R”, a hydroxyalkyl group or a cyano group. R; is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO ₂ —-containing cyclic group; and A″ is a carbon that may contain an oxygen atom or a sulfur atom. It is an alkylene group of formulas 1 to 5, an oxygen atom or a sulfur atom, p'is an integer of 0 to 3, and q'is 0 or 1. ]

In the general formulas (ax3-r-2) to (ax3-r-3), A″ represents the general formulas (a2-r-2), (a2-r-3), and (a2-r-5). It is similar to A" in the inside.
The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR″, —OC(═O)R″ and hydroxyalkyl group for Ra′ ³¹ are each represented by the general formula (a2-r-1) to ( The same as those mentioned in the description of Ra′ ^{21 in} a2-r-7) can be mentioned.
Specific examples of the groups represented by general formulas (ax3-r-1) to (ax3-r-3) are shown below.

As the structural unit (a2), a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent is preferable.
The structural unit (a2) is preferably a structural unit represented by general formula (a2-1) shown below.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｙａ^２１は単結合または２価の連結基である。Ｌａ^２１は−Ｏ−、−ＣＯＯ−、−ＣＯＮ（Ｒ’）−、−ＯＣＯ−、−ＣＯＮＨＣＯ−又は−ＣＯＮＨＣＳ−であり、Ｒ’は水素原子またはメチル基を示す。ただしＬａ^２１が−Ｏ−の場合、Ｙａ^２１は−ＣＯ−にはならない。Ｒａ^２１はラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ²¹ is a single bond or a divalent linking group. La ²¹ is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, and R'represents a hydrogen atom or a methyl group. However, when La ²¹ is -O-, Ya ²¹ does not become -CO-. Ra ²¹ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO ₂ —-containing cyclic group. ]

In the formula (a2-1), R is the same as above. As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable from the viewpoint of industrial availability.

In the formula (a2-1), the divalent linking group for Ya ²¹ is not particularly limited, but may be a divalent hydrocarbon group which may have a substituent, or a divalent linking group containing a hetero atom. And the like are preferable. The description of the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom in Ya ²¹ is the same as the substitution in Ya ^x1 in the above general formula (a10-1). The same applies to the description of the divalent hydrocarbon group which may have a group and the divalent linking group containing a hetero atom.
Ya ²¹ is preferably a single bond, an ester bond [—C(═O)—O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof. .

In the formula (a2-1), Ra ²¹ represents a lactone-containing cyclic group, a —SO ₂ —-containing cyclic group or a carbonate-containing cyclic group.
The lactone-containing cyclic group, —SO ₂ — containing cyclic group, and carbonate-containing cyclic group for Ra ²¹ are each represented by the general formulas (a2-r-1) to (a2-r-7) described above. Groups represented by general formulas (a5-r-1) to (a5-r-4), groups represented by general formulas (ax3-r-1) to (ax3-r-3), respectively. Are preferred.
Among them, a lactone-containing cyclic group or a —SO ₂ — containing cyclic group is preferable, and the general formula (a2-r-1), (a2-r-2), (a2-r-6) or (a5-r) is used. The groups each represented by -1) are more preferable. Specifically, the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), (r- Any group represented by each of lc-6-1), (r-sl-1-1), and (r-sl-1-18) is more preferable.

The structural unit (a2) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a2), the proportion of the structural unit (a2) is 0 to 50 mol% with respect to the total (100 mol%) of all the structural units constituting the component (A1). Is more preferable, 5 to 45 mol% is more preferable, 10 to 40 mol% is still more preferable, and 10 to 30 mol% is particularly preferable.
By setting the proportion of the structural unit (a2) to the preferable lower limit value or more, the effect of containing the structural unit (a2) can be sufficiently obtained, and if it is the upper limit value or less, balance with other structural units is achieved. Therefore, various lithographic properties are improved.

<<Structural unit (a3)>>
The component (A1) is a structural unit (a3) containing a polar group-containing aliphatic hydrocarbon group in addition to the structural unit (a1) (provided that the structural unit (a1) and the structural unit (a2) are applicable. Other than) may be included. When the component (A1) has the structural unit (a3), for example, the acid diffusion length is appropriately adjusted, the adhesion of the resist film to the substrate is increased, the solubility during development is appropriately adjusted, and the etching resistance is improved. Due to the effects such as improvement, the lithography characteristics and the like are improved.

Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is replaced with a fluorine atom, and the like, and a hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group, and can be appropriately selected and used from, for example, a large number of proposals for resins for resist compositions for ArF excimer lasers. The cyclic group is preferably a polycyclic group, and more preferably has 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a fluorine atom. Is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, and the like. Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from norbornane, and a group obtained by removing two or more hydrogen atoms from tetracyclododecane are Industrially preferred.

The structural unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any unit can be used.
The structural unit (a3) is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and includes a polar group-containing aliphatic hydrocarbon group. Structural units are preferred.
When the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the structural unit (a3) is derived from hydroxyethyl ester of acrylic acid. The constituent units are preferred.
As the structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit (a3) -2) and the structural unit represented by formula (a3-3) are preferred.

［式中、Ｒは前記と同じであり、ｊは１〜３の整数であり、ｋは１〜３の整数であり、ｔ’は１〜３の整数であり、ｌは１〜５の整数であり、ｓは１〜３の整数である。］

[In the formula, R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t'is an integer of 1 to 3, and l is an integer of 1 to 5. And s is an integer of 1 to 3. ]

In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl groups are bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, it is preferable that the hydroxyl group be bonded to the 3-position of the adamantyl group.
j is preferably 1, and a hydroxyl group bonded to the 3rd position of the adamantyl group is particularly preferable.

In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornyl group.

In formula (a3-3), t′ is preferably 1. It is preferable that l is 1. It is preferable that s is 1. These preferably have a 2-norbornyl group or a 3-norbornyl group bonded to the terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.

The structural unit (a3) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a3), it is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, based on the total of all structural units constituting the component (A1). 5 to 25 mol% is more preferable, and 5 to 20 mol% is particularly preferable.
By setting the ratio of the structural unit (a3) to the preferred lower limit or more, the effect of including the structural unit (a3) can be sufficiently obtained, and if the ratio is the upper limit or less, balance with other structural units is achieved. Therefore, various lithographic properties are improved.

≪Structural unit (st)≫
The component (A1) may further have a structural unit (st) derived from styrene or a derivative thereof, in addition to the structural unit (a1). The term “styrene” is a concept including styrene and styrene in which the hydrogen atom at the α-position is substituted with a substituent such as an alkyl group or a halogenated alkyl group. Examples of the alkyl group as the substituent here include alkyl groups having 1 to 5 carbon atoms, and examples of the halogenated alkyl group as the substituent include halogenated alkyl groups having 1 to 5 carbon atoms.
Examples of the “styrene derivative” include those in which a substituent is bonded to the benzene ring of styrene in which the hydrogen atom at the α-position may be substituted with the substituent.
The α-position (carbon atom at the α-position) means the carbon atom to which the benzene ring is bonded, unless otherwise specified.
The "structural unit derived from styrene" and "structural unit derived from styrene derivative" mean a structural unit formed by cleavage of the ethylenic double bond of styrene or a styrene derivative.
The structural unit (st) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a structural unit (st), the proportion of the structural unit (st) is 1 to 50 mol% based on the total (100 mol%) of all the structural units constituting the component (A1). Is preferable, and more preferably 3 to 40 mol %.

≪Other structural units≫
The component (A1) may have a structural unit (a1), a structural unit (a10), a structural unit (a2), a structural unit (a3), and a structural unit other than the structural unit (st) described above.
As the other structural unit, for example, a structural unit (a9) represented by the general formula (a9-1) described later, a structural unit derived from styrene, a structural unit derived from a styrene derivative (however, the structural unit (a10 A), a structural unit containing an acid non-dissociable aliphatic cyclic group, and the like.

Structural unit (a9):
The structural unit (a9) is a structural unit represented by general formula (a9-1) shown below.

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｙａ^９１は、単結合又は２価の連結基である。Ｙａ^９２は、２価の連結基である。Ｒ^９１は、置換基を有していてもよい炭化水素基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ⁹¹ is a single bond or a divalent linking group. Ya ⁹² is a divalent linking group. R ⁹¹ is a hydrocarbon group which may have a substituent. ]

In the formula (a9-1), R is the same as above.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable from the viewpoint of industrial availability.

In the formula (a9-1), examples of the divalent linking group for Ya ⁹¹ include the same divalent linking groups for Ya ^x1 in the general formula (a10-1). Among them, Ya ⁹¹ is preferably a single bond.

In the formula (a9-1), the divalent linking group for Ya ⁹² may be the same as the divalent linking group for Ya ^x1 in the general formula (a10-1).
In the divalent linking group for Ya ^92, the divalent hydrocarbon group which may have a substituent is preferably a linear or branched aliphatic hydrocarbon group.
Further, in the divalent linking group for Ya ^92, the divalent linking group containing a hetero atom includes —O—, —C(═O)—O—, —C(═O)—, and —O—C. (=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H may be substituted with a substituent such as an alkyl group and an acyl group. _{.), - S -, -} S (= O) 2 -, - S (= O) 2 -O -, - C (= S) -, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 ^{-O -, - Y 21 -C (} = O) -O -, - C (= O) -O - Y 21, [Y 21 -C (= O) -O] m '-Y 22 - or - A group represented by Y ²¹ —O—C(═O)—Y ²² — [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent. , O is an oxygen atom, and m′ is an integer of 0 to 3. ] Etc. are mentioned. Among them, -C(=O)- and -C(=S)- are preferable.

In the formula (a9-1), examples of the hydrocarbon group for R ⁹¹ include an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, an aralkyl group, and the like.
The alkyl group for R ⁹¹ preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and may be linear or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group.
The monovalent alicyclic hydrocarbon group for R ⁹¹ preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclobutane, cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
The aryl group for R ⁹¹ preferably has 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably a phenyl group.
The aralkyl group for R ^91, an alkylene group and the aralkyl group is preferably a bound "aryl group for R ⁹¹ ', an alkylene group and aryl group in the" R ⁹¹ having 1 to 6 carbon atoms having 1 to 8 carbon atoms Is more preferable, and an aralkyl group in which an alkylene group having 1 to 4 carbon atoms and the above "aryl group for R ⁹¹ " are bonded is particularly preferable.
The hydrocarbon group for R ⁹¹ is preferably such that a part or all of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, and 30 to 100% of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. Is more preferable. Among them, it is particularly preferable that the above-mentioned alkyl group is a perfluoroalkyl group in which all the hydrogen atoms are substituted with fluorine atoms.

The hydrocarbon group for R ⁹¹ may have a substituent. Examples of the substituent include a halogen atom, an oxo group (= O), a hydroxyl group (-OH), a amino group _{(-NH 2), - SO 2} -NH 2 , and the like. Further, a part of carbon atoms constituting the hydrocarbon group may be replaced with a substituent containing a hetero atom. Examples of the substituent containing the hetero atom include -O-, -NH-, -N=, -C(=O)-O-, -S-, -S(=O) _2- , -S(=O. ) _2- O- is mentioned.
Examples of the hydrocarbon group having a substituent in R ⁹¹ include the lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7).

Further, in R ⁹¹ , the hydrocarbon group having a substituent is a —SO ₂ — containing cyclic group represented by any of the above general formulas (a5-r-1) to (a5-r-4); A substituted aryl group represented by a chemical formula, a monovalent heterocyclic group, and the like are also included.

Among the structural units (a9), structural units represented by general formula (a9-1-1) shown below are preferable.

［式中、Ｒは前記と同様であり、Ｙａ^９１は単結合または２価の連結基であり、Ｒ^９１は置換基を有していてもよい炭化水素基であり、Ｒ^９２は酸素原子又は硫黄原子である。］

[In the formula, R is as defined above, Ya ⁹¹ is a single bond or a divalent linking group, R ⁹¹ is a hydrocarbon group which may have a substituent, and R ⁹² is an oxygen atom or It is a sulfur atom. ]

In general formula (a9-1-1), the description of Ya ⁹¹ , R ⁹¹ , and R is the same as above. R ⁹² is an oxygen atom or a sulfur atom.

Specific examples of the structural unit represented by the formula (a9-1) or the general formula (a9-1-1) are shown below. In the formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (a9) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a9), the proportion of the structural unit (a9) is from 1 to 40 mol% based on the total (100 mol%) of all the structural units constituting the component (A1). Is more preferable, 3 to 30 mol% is more preferable, 5 to 25 mol% is further preferable, and 10 to 20 mol% is particularly preferable.
By adjusting the ratio of the structural unit (a9) to the lower limit or more, for example, the acid diffusion length is appropriately adjusted, the adhesion of the resist film to the substrate is increased, the solubility during development is appropriately adjusted, and the etching resistance And other effects can be achieved, and various lithographic properties are improved.

Structural unit (a4):
The structural unit (a4) is a structural unit containing an acid non-dissociable aliphatic cyclic group. The component (A1) may further have a structural unit (a4) in addition to the structural unit (a1).
When the component (A1) has the structural unit (a4), the dry etching resistance of the resist pattern formed is improved. Further, the hydrophobicity of the component (A) is increased. It is considered that the improvement of the hydrophobicity contributes to the improvement of the resolution, the resist pattern shape, etc., especially in the case of the solvent development process.
The “acid non-dissociable cyclic group” in the structural unit (a4) is an acid when an acid is generated in the resist composition by exposure (for example, when an acid is generated from the component (B) described below). Is a cyclic group which remains in the structural unit as it is without being dissociated by the action of.
As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing an acid non-dissociable aliphatic cyclic group is preferable. As the cyclic group, many ones conventionally known as those used as a resin component of a resist composition for ArF excimer laser, KrF excimer laser (preferably ArF excimer laser) and the like can be used. ..
Particularly, at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
Specific examples of the structural unit (a4) include structural units represented by general formulas (a4-1) to (a4-7) shown below.

［式中、Ｒ^αは前記と同じである。］

[In the formula, R ^α is the same as above. ]

The structural unit (a4) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a4), the proportion of the structural unit (a4) is preferably 1 to 30 mol% with respect to the total of all the structural units constituting the component (A1), 3-20 mol% is more preferable.
By setting the proportion of the structural unit (a4) to the preferred lower limit or more, the effect of containing the structural unit (a4) can be sufficiently obtained, while by setting it to the preferred upper limit or less, other structural units can be obtained. It will be easier to balance.

As the component (A1) contained in the resist composition, one type may be used alone, or two or more types may be used in combination.
The component (A1) preferably contains the polymer compound (A1-1) having the structural unit (a1) (hereinafter also referred to as “component (A1-1)”).
The preferred component (A1-1) is, for example, a polymer compound having a repeating structure of the structural unit (a1) and the structural unit (a10), or a repeating structure of the structural unit (a1) and the structural unit (st). Examples thereof include polymer compounds.
In addition to the combination of the above-mentioned two constituent units, the constituent units described above may be combined appropriately as a third or three or more constituent units in accordance with a desired effect. Examples of the combination of three or more constituent units include a combination of the constituent unit (a1), the constituent unit (a10), and the constituent unit (st).

The component (A1) dissolves a monomer that induces each structural unit in a polymerization solvent, and initiates radical polymerization of, for example, azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (for example, V-601). It can be produced by adding an agent and polymerizing. Alternatively, the component (A1) includes a monomer that induces the structural unit (a1) and, if necessary, a precursor of a monomer that induces a structural unit other than the structural unit (a1) (the functional group of the monomer is protected. Monomer) and a monomer are dissolved in a polymerization solvent, the radical polymerization initiator as described above is added thereto to polymerize, and then a deprotection reaction is carried out to produce the compound. At the time of polymerization, for _example, by using a combination of chain transfer agent such as _{HS-CH 2 -CH 2 -CH 2} -C (CF 3) 2 -OH, -C terminated _(CF 3) _{A 2-} OH group may be introduced. As described above, the copolymer having a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is substituted with a fluorine atom is introduced, the development defects are reduced and LER (line edge roughness: uneven unevenness of the line side wall) is obtained. Is effective in reducing

The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography (GPC)) of the component (A1) is not particularly limited and is preferably 1000 to 50000, more preferably 2000 to 30000, and 3000 to 3000. 20000 is more preferable.
When the Mw of the component (A1) is less than or equal to the preferred upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and when it is more than the preferred lower limit of this range, dry etching resistance and The resist pattern cross-sectional shape is good.
The dispersity (Mw/Mn) of the component (A1) is not particularly limited and is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0. . In addition, Mn shows a number average molecular weight.

-Regarding Component (A2) In the resist composition of the present embodiment, as the component (A), a base component which does not correspond to the component (A1) and whose solubility in a developing solution is changed by the action of an acid (hereinafter referred to as “(A2) ) Component”)) may be used in combination.
The component (A2) is not particularly limited and may be arbitrarily selected from a large number of conventionally known base components for chemically amplified resist compositions.
As the component (A2), one type of polymer compound or low molecular weight compound may be used alone, or two or more types 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 100% by mass with respect to the total mass of the component (A). May be When the proportion is 25% by mass or more, a resist pattern excellent in various lithographic properties such as high sensitivity, resolution, and roughness improvement can be easily formed.

<(Z) component>
In the resist composition of this embodiment, the component (Z) is a dissolution inhibitor that suppresses solubility in a developing solution.
The component (Z) has a mass average molecular weight of 3000 or less, and a compound (Z1) having a phenolic hydroxyl group or a carboxyl group in the molecule (hereinafter also referred to as “(Z1) component”) and a mass average molecular weight of 3000 or less. And a compound (Z2) represented by the general formula (z2) described later (hereinafter, also referred to as “component (Z2)”).

Component (Z1) The component (Z1) is not particularly limited as long as it has a mass average molecular weight of 3000 or less and has a phenolic hydroxyl group or a carboxyl group in the molecule.
The mass average molecular weight of the component (Z1) is preferably 150 to 3000, more preferably 200 to 2500, and further preferably 250 to 2000.
When the mass average molecular weight of the component (Z1) is at least the lower limit value of the above preferred range, the substrate adhesion performance will be improved.

As the component (Z1), compounds represented by general formula (z1-1) or (z1-2) shown below are preferable.

［式（ｚ１−１）中、Ｖ_ｚ ^１は２価の連結基である。式（ｚ１−２）中、Ｒ_ｚ ^１０は置換基を有してもよい多環式の脂環式炭化水素基又は置換基を有してもよい芳香族炭化水素基である。ｎ１１及びｎ１２は、それぞれ独立に、１〜３の整数である。式（ｚ２−１）中、Ｒｚ^２は、炭化水素基である。ｎ２１は１又は２である。ｎ２２は２〜５の整数である。ただし、ｎ２１＋ｎ２２≦６である。］

[In formula (z1-1), V _z ¹ is a divalent linking group. In formula (z1-2), R _z ¹⁰ is a polycyclic alicyclic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. n11 and n12 are each independently an integer of 1 to 3. In formula (z2-1), Rz ² is a hydrocarbon group. n21 is 1 or 2. n22 is an integer of 2-5. However, n21+n22≦6. ]

In the formula _(Z1-1), as the divalent linking group for _V ^{z 1,} it is the same as those of the divalent linking group for ^{Ya x1} in general formula (A10-1). Further, the divalent linking group of V _z ¹ is a linear or branched aliphatic hydrocarbon group as the divalent linking group of Ya ^x1 in the general formula (a10-1) described above. Also included are groups in which some of the hydrogen atoms are substituted with aromatic hydrocarbon groups.

The linear or branched aliphatic 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” is , a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], - CH (CH 3) -, - CH (CH 2 CH 3) -, - C (CH 3) 2 -, - Examples thereof include alkylmethylene groups such as C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, and -C(CH ₂ CH ₃ ) _2- .
The aromatic hydrocarbon group in the "group in which a part of hydrogen atoms constituting a linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group" includes benzene, fluorene, naphthalene and anthracene. , A group obtained by removing one hydrogen atom from an aromatic ring such as phenanthrene and biphenyl.
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 Good. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl 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.
As the alkoxy group, the halogen atom and the halogenated alkyl group as the substituent, the hydrogen atom contained in the cyclic aliphatic hydrocarbon group in the divalent linking group for Ya ^x1 in the general formula (a10-1) described above. What was illustrated as a substituent which substitutes is mentioned.
Examples of the arylalkyl group as the substituent include a benzyl group, a phenethyl group, a phenyl-t-butyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group and a 2-naphthylethyl group. Be done. The arylalkyl group may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group and an arylalkyl group.

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

［式中、Ｒ_ｚ ^１１及びＲ_ｚ ^１２は、それぞれ独立して、水素原子又は置換基を有してもよい炭化水素基である。Ｒ_ｚ ^１１及びＲ_ｚ ^１２は、相互に結合して環を形成してもよい。ｎ１１及びｎ１２は、それぞれ独立に、１〜３の整数である。］

[In the formula, R _z ¹¹ and R _z ¹² are each independently a hydrogen atom or a hydrocarbon group which may have a substituent. R _z ¹¹ and R _z ¹² may combine with each other to form a ring. n11 and n12 are each independently an integer of 1 to 3. ]

In the formula (z1-1-1), the hydrocarbon group represented by R _z ¹¹ and R _z ¹² is a linear or branched alkyl group, an aromatic hydrocarbon group which may have a substituent, or the like. Is mentioned.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and an isopropyl group is preferable.

_Examples of the aromatic hydrocarbon group for R _z ¹¹ and R _z ¹² include groups obtained by removing one hydrogen atom from an aromatic ring such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl.
The aromatic hydrocarbon group for R _z ¹¹ and R _z ¹² may have a substituent. The substituent has an aromatic hydrocarbon group in the above-mentioned "group in which a part of hydrogen atoms constituting a linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group". It is the same as the optionally substituted substituent.

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

In the formula (z1-1-1), R _z ¹¹ and R _z ¹² are each a linear alkyl group having 1 to 5 carbon atoms or an aromatic hydrocarbon group which may have a substituent, Alternatively, R _z ¹¹ and R _z ¹² are preferably bonded to each other to form an aliphatic ring, and are a methyl group, a phenyl group, or a 4-(4-hydroxyphenyl-t-butyl)phenyl group, or Alternatively, it is more preferable that R _z ¹¹ and R _z ¹² are bonded to each other to form a cyclopentane ring.

Examples of the hydrocarbon group of Rz ^{2 in} the formula (z1-2) include those exemplified as the hydrocarbon groups of R _z ¹¹ and R _z ^{12 in} the formula (z1-1-1). Among them, Rz ² is preferably an aromatic hydrocarbon group, more preferably a phenyl group or a benzyl group, and even more preferably a phenyl group.
In the formula (z1-2), n21 is 1 or 2, and 1 is preferable. n22 is an integer of 2 to 5, preferably 2 or 3, and more preferably 2.

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

［式中、Ｒｚ^２１及びＲｚ^２２は、それぞれ独立に、芳香族炭化水素基である。］

[In the formula, Rz ²¹ and Rz ²² are each independently an aromatic hydrocarbon group. ]

In the formula (z1-2-1), examples of the hydrocarbon group of Rz ² include those exemplified as the hydrocarbon groups of R _z ¹¹ and R _z ^{12 in} the formula (z1-1-1). Among them, Rz ² is preferably a phenyl group or a benzyl group, more preferably a phenyl group.

Specific examples of the component (Z1) will be given below.

Other specific examples of the component (Z1) are described in JP-A 2008-122932, paragraph [0158], and JP-A 10-097075, paragraphs [0036]-[0055]. And the like.

As the component (Z1) contained in the resist composition, one type may be used alone, or two or more types may be used in combination.

-About the (Z2) component The (Z2) component is a compound having a mass average molecular weight of 3000 or less and represented by the following general formula (z2).

［式中、Ｒ_ｚ ^２０は酸解離性基である。Ｒ_ｚ ^３０は水素原子又は有機基である。ｎ１は１〜６の整数であり、ｎ２は０〜５の整数である。ただし、ｎ１＋ｎ２＝６である。］

[In the formula, R _z ²⁰ is an acid dissociable group. R _z ³⁰ is a hydrogen atom or an organic group. n1 is an integer of 1 to 6, and n2 is an integer of 0 to 5. However, n1+n2=6. ]

The mass average molecular weight of the component (Z2) is preferably 150 to 3000, more preferably 200 to 2500, and further preferably 250 to 2000.
When the mass average molecular weight of the component (Z2) is within the above-mentioned preferable range, the amount of slippage of the resist film made of the radiation-sensitive resin composition can be reduced.

In the formula (z2), examples of the acid dissociable group represented by R _z ²⁰ include groups represented by general formulas (z2-r-1) to (z2-r-4) shown below.

［式中、Ｒ_ｚ ^２０１〜Ｒ_ｚ ^２０６は、それぞれ独立に、直鎖状又は分枝状のアルキル基、直鎖状又は分枝状のアルコキシ基、直鎖状又は分枝状のアルコキシアルキル基、直鎖状又は分枝状のアルケニル基、又はアリール基であり、これら基は鎖中にカルボニル基を含んでいてもよい。あるいは、Ｒ_ｚ ^２０１とＲ_ｚ ^２０２、Ｒ_ｚ ^２０４とＲ_ｚ ^２０５は互いに結合して環を形成していてもよい。Ｒ_ｚ ^２０７及びＲ_ｚ ^２０８は、それぞれ独立に、水素原子、直鎖状又は分枝状のアルキル基、直鎖状又は分枝状のアルコキシ基、直鎖状又は分枝状のアルコキシアルキル基、直鎖状又は分枝状のアルケニル基、又はアリール基である。Ｒ_ｚ ^２０９は、直鎖状又は分枝状のアルキル基、直鎖状又は分枝状のアルコキシアルキル基、直鎖状又は分枝状のアルケニル基、又はアリール基であり、これら基は鎖中にカルボニル基を含んでいてもよい。あるいは、Ｒ_ｚ ^２０９はＲ_ｚ ^２０８と結合して環を形成していてもよい。Ｒ_ｚ ^２１０は２価の脂肪族、脂環式又は芳香族基であり、Ｒ_ｚ ^２１１は酸解離性基である。ｑは０又は１である。］

[Wherein, R _z ^{201 to} R _z ²⁰⁶ are each independently a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group. , A linear or branched alkenyl group, or an aryl group, which may contain a carbonyl group in the chain. Alternatively, R _z ²⁰¹ and R _z ²⁰² , and R _z ²⁰⁴ and R _z ²⁰⁵ may be bonded to each other to form a ring. R _z ²⁰⁷ and R _z ²⁰⁸ are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, It is a linear or branched alkenyl group or aryl group. R _z ²⁰⁹ is a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl group, or an aryl group, and these groups are in the chain. May contain a carbonyl group. Alternatively, R _z ²⁰⁹ may combine with R _z ²⁰⁸ to form a ring. R _z ²¹⁰ is a divalent aliphatic, alicyclic or aromatic group, and R _z ²¹¹ is an acid dissociable group. q is 0 or 1. ]

In the formulas (z2-r-1) to (z2-r-2), R _z ^{201 to} R _z ²⁰⁶ each independently represents a linear or branched alkyl group, a linear or branched alkyl group. Is an alkoxy group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl group, or an aryl group, which may contain a carbonyl group in the chain.
_Examples of the alkyl group in R _z ^{201 to} R _z ²⁰⁶ 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, a hexyl group, a cyclohexyl group, and an adamantyl group. And the like, having 1 to 10 carbon atoms are preferable, and among them, a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group are more preferably used.
_Examples of the alkoxy group in R _z ^{201 to} R _z ²⁰⁶ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a hexyloxy group and a cyclohexyloxy group. Those having 1 to 8 carbon atoms are preferable, and among them, a methoxy group, an ethoxy group, an isopropoxy group, and a tert-butoxy group are more preferably used.
As the alkoxyalkyl group for R _z ^{201 to} R _z ²⁰⁶ , those having 2 to 10 carbon atoms such as methoxymethyl group, ethoxypropyl group, propoxyethyl group, tert-butoxyethyl group and the like are preferable, and among them, methoxymethyl group , Methoxyethyl group, ethoxypropyl group, propoxyethyl group and the like are preferable.
As the alkenyl group in R _z ^{201 to} R _z ²⁰⁶ , those having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group and a butenyl group are preferable.
The aryl group in R _z ^{201 to} R _z ²⁰⁶ is preferably an aryl group having a carbon number of 6 to 14, such as a phenyl group, a xylyl group, a toluyl group, and a cumenyl group.

In the formulas (z2-r-1) to (z2-r-2), R _z ²⁰¹ and R _z ²⁰² , and R _z ²⁰⁴ and R _z ²⁰⁵ may be bonded to each other to form a ring.
The ring formed by combining R _z ²⁰¹ and R _z ²⁰² with each other includes, for example, carbon numbers such as cyclohexylidene group, cyclopentylidene group, 3-oxocyclohexylidene group, and 4-methylcyclohexylidene group. The thing of 4-10 is mentioned.
Examples of the ring formed by combining R _z ²⁰⁴ and R _z ²⁰⁵ with each other include 1-silacyclohexylidene group, 1-silacyclopentylidene group, 3-oxo-1-silacyclopentylidene group, 4- Examples thereof include those having 3 to 9 carbon atoms such as methyl-1-silacyclopentylidene group.

In the formula (z2-r-3), R _z ²⁰⁷ and R _z ²⁰⁸ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, or a straight chain. It is a linear or branched alkoxyalkyl group, a linear or branched alkenyl group, or an aryl group. R _z ²⁰⁹ is a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl group, or an aryl group, and these groups are in the chain. May contain a carbonyl group.
The alkyl group in R _z ²⁰⁷ ~R _z ^209, alkoxy group, alkoxyalkyl group, alkenyl group and aryl group, the formula (z2-r-1) ~ (z2-r-2) in the _R ^z 201 to R _z The same as the alkyl group, the alkoxy group, the alkoxyalkyl group, the alkenyl group and the aryl group in ²⁰⁶ .

In the formula (z2-r-3), R _z ²⁰⁹ may combine with R _z ²⁰⁸ to form a ring.
The ring formed by R _z ²⁰⁹ binding to R _z ²⁰⁸ is, for example, a carbon number such as a 2-oxacyclohexylidene group, a 2-oxacyclopentylidene group, a 2-oxa-4-methylcyclohexylidene group. The thing of 4-10 is mentioned.

In the formula (z2-r-4), R _z ²¹⁰ is a divalent aliphatic, alicyclic or aromatic group.
As the divalent aliphatic group for R _z ²¹⁰ , those having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a 2-methylpropylene group, and a 2-methyl-3-ethoxybutylene group. Of these, a methylene group, an ethylene group and a propylene group are more preferably used.
_Examples of the divalent alicyclic group for R _z ²¹⁰ include those having 5 to 10 carbon atoms such as a cyclohexylene group.
_Examples of the divalent aromatic group for R _z ²¹⁰ include those having 6 to 14 carbon atoms such as a phenylene group, a xylylene group, a toluylene group, and a cumenylene group.

In the formula (z2-r-4), examples of the acid dissociable group for R _z ²¹¹ include groups represented by the formulas (z2-r-1) to (z2-r-3).

In the formula (z2), R _z ³⁰ is a hydrogen atom or an organic group.
_Examples of the organic group of R _z ³⁰ include a hydrocarbon group which may have a substituent.
_Examples of the hydrocarbon group for R _z ³⁰ include a linear or branched alkyl group or a cyclic hydrocarbon group.
The linear alkyl group for R _z ³⁰ preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like.
The branched chain alkyl group for R _z ³⁰ preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group and a 2,2-dimethylbutyl group.

The cyclic hydrocarbon group for R _z ³⁰ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Examples thereof include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group for R _z ³⁰ is a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, or phenanthrene; a hydrogen atom derived from an aromatic heterocycle such as a pyridine ring or a thiophene ring. A group excluding one; a group excluding one hydrogen atom from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle. A group in which one is substituted with an alkyl group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group). . The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

The substituent which the hydrocarbon group in R _z ³⁰ may have is a linear, branched or cyclic alkyl group, an aromatic hydrocarbon group, a linear or branched alkoxy group, a hydroxy group, Examples thereof include a carboxy group, a halogen atom, and groups represented by the formulas (z2-r-1) to (z2-r-4). The aromatic hydrocarbon group as a substituent which the hydrocarbon group in R _z ³⁰ may have is further a linear, branched or cyclic alkyl group as the substituent or the above formula (z2-r-1). It may have a group represented by ~(z2-r-4).

As the component (Z2), at least one selected from the group consisting of groups represented by general formulas (z2-1) to (z2-2) shown below is preferable.

［式中、Ｖ_ｚ ^２は、２価の連結基である。Ｒ_ｚ ^２０、Ｒ_ｚ ^３３は、それぞれ独立に、酸解離性基である。Ｒ_ｚ ^３１、Ｒ_ｚ ^３２は、それぞれ独立に、水素原子又は有機基である。Ｒ_ｚ ^２５、Ｒ_ｚ ^２６は、それぞれ独立に、水素原子又は置換基を有してもよい炭化水素基である。ｎ１１は、１〜５の整数である。ｎ１２は、０〜４の整数である。ただし、ｎ１１＋ｎ１２＝５である。ｎ１３は、１〜５の整数である。ｎ１４は、０〜４の整数である。ただし、ｎ１１＋ｎ１２＝５である。］

[In the formula, V _z ² is a divalent linking group. R _z ²⁰ and R _z ³³ are each independently an acid dissociable group. R _z ³¹ and R _z ³² are each independently a hydrogen atom or an organic group. R _z ²⁵ and R _z ²⁶ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent. n11 is an integer of 1 to 5. n12 is an integer of 0-4. However, n11+n12=5. n13 is an integer of 1 to 5. n14 is an integer of 0-4. However, n11+n12=5. ]

In the formula (z2-1), the divalent linking group for V _z ² is the same as the divalent linking group for Ya ^x1 in the formula (a10-1). Among them, the divalent linking group for V _z ² is preferably a linear alkylene group having 1 to 10 carbon atoms, and is a methylene group [—CH ₂ —] or an ethylene group [—(CH ₂ ) ₂ —. ], a trimethylene group _{[- (CH 2) 3 -} ], a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] are more preferable, and a methylene group is more preferable.

In formulas (z2-1) to (z2-2), the acid dissociable group for R _z ²⁰ and R _z ³³ is the same as the acid dissociable group for R _z ²⁰ in formula (z2). Among them, the acid dissociable group for R _z ²⁰ and R _z ³³ is preferably a group represented by the formula (z2-r-4), and R _z ²¹¹ in the formula (z2-r-4) is preferable. The acid dissociable group is more preferably a group represented by the formula (z2-r-1).

In formulas (z2-1) to (z2-2), the organic group for R _z ³¹ and R _z ³² is the same as the organic group for R _z ³⁰ in formula (z2). Among them, as the organic group for R _z ³¹ and R _z ³² , an aromatic hydrocarbon group which may have a substituent is preferable, and a group represented by the following general formula (z2-r-5) is more preferable. .

［式中、Ｒ_ｚ ^２０１は酸解離性基である。Ｒ_ｚ ^３０１は水素原子又はアルキル基である。ｎ１５は１〜６の整数であり、ｎ１６は０〜５の整数である。ただし、ｎ１５＋ｎ１６＝６である。ｎ１７は、０又は１である。＊は結合手を示す。］

[In the formula, R _z ²⁰¹ is an acid dissociable group. R _z ³⁰¹ is a hydrogen atom or an alkyl group. n15 is an integer of 1 to 6, and n16 is an integer of 0 to 5. However, n15+n16=6. n17 is 0 or 1. * Indicates a bond. ]

In the formula (z2-r-5), the acid dissociable group for R _z ²⁰¹ is the same as the acid dissociable group for R _z ²⁰ in the formula (z2). Among them, the acid dissociable group for R _z ²⁰¹ is preferably a group represented by the formula (z2-r-4), and an acid dissociable group for R _z ²¹¹ in the formula (z2-r-4). Is more preferably a group represented by the above formula (z2-r-1).
In formula (z2-r-5), R _z ³⁰¹ is preferably an alkyl group, which is preferably a methyl group, an ethyl group or a cyclohexyl group, more preferably a methyl group or a cyclohexyl group.
In the formula (z2-r-5), n15 is preferably 1 or 2, and more preferably 1.
In the formula (z2-r-5), n16 is preferably 4 or 5, and more preferably 5.

In the formula (z2-2), the hydrocarbon group for R _z ²⁵ and R _z ²⁶ is the same as the hydrocarbon group as the organic group for R _z ³⁰ in the formula (z2). Among them, as R _z ²⁵ and R _z ²⁶ , a hydrogen atom or an aromatic hydrocarbon group which may have a substituent is preferable, and a hydrogen atom or a group represented by the above formula (z2-r-5). Is more preferable.

In the formulas (z2-1) to (z2-2), n11 and n13 are preferably 1 or 2, and more preferably 1.
In the formulas (z2-1) to (z2-2), n16 is preferably 4 or 5, and more preferably 5.

Hereinafter, as specific examples of the component (Z2), compounds represented by the following chemical formulas (Z2-1) and (Z2-2) are described in paragraphs [0046] to [0050] of JP-A-2005-122097. The compound etc. are mentioned.

Other specific examples of the component (Z2) include the compounds described in paragraphs [0034], [0036] and [0037] of JP-A-9-278699, and paragraph [0119] of JP-A-10-097075. ]-[0122] and the like.

As the component (Z2) contained in the resist composition, one type may be used alone, or two or more types may be used in combination.

In the resist composition of the present embodiment, the content of the component (Z) is preferably 30 parts by mass or less, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the component (A).
When the ratio of the component (Z) is within the above-mentioned preferable range, the etching resistance is good and a pattern having a good shape is easily formed.
In the resist composition of the present embodiment, the compounding ratio (mass ratio) of the (Z1) component and the (Z2) component in the (Z) component is Z1:Z2=75:25 to 25:75. Is preferred, Z1:Z2=70:30 to 40:60 is more preferred, and Z1:Z2=67:33 to 45:55 is even more preferred.
When the compounding ratio (mass ratio) of the (Z1) component and the (Z2) component in the (Z) component is within the above-mentioned preferable range, the etching resistance is good and a pattern having a good shape is formed. It's easy to do.

<Arbitrary ingredients>
<<(B) component: Acid generator component>>
The resist composition of the present embodiment preferably contains an acid generator component (component (B)) that generates an acid upon exposure, in addition to the components (A) and (Z).
The component (B) is not particularly limited, and those which have been proposed as acid generators for chemically amplified resist compositions can be used.
Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes. Acid generators: various types such as nitrobenzyl sulfonate-based acid generators, imino sulfonate-based acid generators, disulfone-based acid generators and the like can be mentioned.

Examples of the onium salt-based acid generator include a compound represented by the following general formula (b-1) (hereinafter also referred to as “component (b-1)”) and a general formula (b-2). The compound (henceforth "(b-2) component") or the compound represented by the general formula (b-3) (henceforth "(b-3) component") is mentioned.

［式中、Ｒ^１０１、Ｒ^１０４〜Ｒ^１０８はそれぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。Ｒ^１０４、Ｒ^１０５は、相互に結合して環を形成していてもよい。Ｒ^１０２はフッ素原子又は炭素数１〜５のフッ素化アルキル基である。Ｙ^１０１は単結合、又は酸素原子を含む２価の連結基である。Ｖ^１０１〜Ｖ^１０３はそれぞれ独立に単結合、アルキレン基又はフッ素化アルキレン基である。Ｌ^１０１〜Ｌ^１０２はそれぞれ独立に単結合又は酸素原子である。Ｌ^１０３〜Ｌ^１０５はそれぞれ独立に単結合、−ＣＯ−又は−ＳＯ_２−である。ｍは１以上の整数であって、Ｍ’^ｍ＋はｍ価のオニウムカチオンである。］

[In formula, R< ¹⁰¹ >, R< ¹⁰⁴ >-R< ¹⁰⁸ > has a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a substituent each independently. Is also a chain alkenyl group. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ^{101 to} V ¹⁰³ are each independently a single bond, an alkylene group or a fluorinated alkylene group. L ^{101 to} L ¹⁰² each independently represent a single bond or an oxygen atom. L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —. m is an integer of 1 or more, and M′ ^m+ is an m-valent onium cation. ]

{Anion part}
-Anion part of component (b-1) In formula (b-1), R ¹⁰¹ is a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a substituent. It is a chain alkenyl group which may have a group.

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 aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group for R ¹⁰¹ is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and 6 to 6 carbon atoms. 10 is most preferred. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring ^contained in the aromatic hydrocarbon group for R ¹⁰¹ are benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings is substituted with a hetero atom. An aromatic heterocycle etc. are mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group for R ¹⁰¹ include a group in which one hydrogen atom is removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and one of the hydrogen atoms in the aromatic ring is an alkylene group. Groups substituted with (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group and 2-naphthylethyl group). The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

Examples of the cyclic aliphatic hydrocarbon group for R ¹⁰¹ include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group in which one hydrogen atom is removed from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group is linear or branched. Examples thereof include a group bonded to the terminal of a chain-like aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group.
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 one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane includes a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; a condensed ring system such as a cyclic group having a steroid skeleton. A polycycloalkane having a polycyclic skeleton of is more preferable.

Among them, the cyclic aliphatic hydrocarbon group for R ¹⁰¹ is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, and more preferably a group obtained by removing one hydrogen atom from a polycycloalkane. Of these, an adamantyl group, a norbornyl group, and a cyclic group having a steroid skeleton are particularly preferable, and an adamantyl group and a cyclic group having a steroid skeleton are most preferable.

The linear or branched aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and carbon. Numbers 1 to 4 are more preferable, and numbers 1 to 3 are particularly preferable.
As the linear aliphatic hydrocarbon group, preferably a linear alkylene group, and specific examples include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], trimethylene [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] , and the like.
As the branched aliphatic hydrocarbon group, preferably a branched chain alkylene group, _{specifically, -CH (CH 3) -,} - CH (CH 2 CH 3) -, - C (CH 3) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 Alkylethylene group such as CH ₃ ) ₂ —CH ₂ —; alkyl trimethylene group such as —CH(CH ₃ )CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ —; —CH(CH ₃ ). Examples thereof include alkyl alkylene groups such as alkyl tetramethylene groups such as CH ₂ CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ CH ₂ — and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Further, the cyclic hydrocarbon group for R ¹⁰¹ may contain a hetero atom such as a heterocycle. Specifically, the lactone-containing cyclic groups respectively represented by the general formulas (a2-r-1) to (a2-r-7) and the general formulas (a5-r-1) to (a5-r-). -SO ₂ respectively represented by 4) - containing cyclic group, other following chemical formula (r-hr-1) include heterocyclic groups respectively represented by ~ (r-hr-16) .

Examples of the substituent in the cyclic group of R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group and the like.
As the alkyl group as a substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are the most preferable.
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 iso-propoxy group, an n-butoxy group, a tert-butoxy group, and a methoxy group. Most preferred is the group ethoxy.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group are the above. A group substituted with a halogen atom can be mentioned.
The carbonyl group as a substituent is a group that substitutes a methylene group (—CH ₂ —) forming a cyclic hydrocarbon group.

Chain-like alkyl group which may have a substituent:
The chain alkyl group for R ¹⁰¹ may be linear or branched.
The linear 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, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group. Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group and the like.
The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples thereof include a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group and a 4-methylpentyl group.

Chain-like alkenyl group which may have a substituent:
The chain alkenyl group for R ¹⁰¹ may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably has 2 to 5 carbon atoms, and has 2 to 4 carbon atoms. More preferably, carbon number 3 is particularly preferable. 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 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like.
Among the above, the chain alkenyl group is preferably a straight chain alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.

Examples of the substituent in the chain alkyl group or alkenyl group for R ¹⁰¹ include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group for R ¹⁰¹ above. Can be mentioned.

Among them, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; the general formulas (a2-r-1), (a2-r-3) to (a2-r). Preferred are lactone-containing cyclic groups each represented by -7); -SO ₂ -containing cyclic groups each represented by the above general formulas (a5-r-1) to (a5-r-4).

In the formula (b-1), Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom.
When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, Y ¹⁰¹ may contain an atom other than an oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms and the like.
Examples of the divalent linking group containing an oxygen atom include the linking groups represented by the general formulas (y-al-1) to (y-al-8).
Y ¹⁰¹ is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, and each is represented by the above general formulas (y-al-1) to (y-al-5). A linking group is more preferred.

In the formula (b-1), V ¹⁰¹ is a single bond, an alkylene group or a fluorinated alkylene group. The alkylene group and fluorinated alkylene group for V ¹⁰¹ preferably have 1 to 4 carbon atoms. ^Examples of the fluorinated alkylene group for V ¹⁰¹ include groups in which some or all of the hydrogen atoms of the alkylene group for V ¹⁰¹ have been substituted with fluorine atoms. Among them, V ¹⁰¹ is preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.

In the formula (b-1), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R ¹⁰² is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

(B-1) Specific examples of the anion moiety of the component, for example, if the Y ¹⁰¹ is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion can be exemplified; Y ¹⁰¹ is In the case of a divalent linking group containing an oxygen atom, an anion represented by any of the following formulas (an-1) to (an-3) can be mentioned.

［式中、Ｒ”^１０１は、置換基を有してもよい脂肪族環式基、上記の化学式（ｒ−ｈｒ−１）〜（ｒ−ｈｒ−６）でそれぞれ表される１価の複素環式基、又は置換基を有してもよい鎖状のアルキル基である。Ｒ”^１０２は、置換基を有してもよい脂肪族環式基、前記一般式（ａ２−ｒ−１）、（ａ２−ｒ−３）〜（ａ２−ｒ−７）でそれぞれ表されるラクトン含有環式基、又は前記一般式（ａ５−ｒ−１）〜（ａ５−ｒ−４）でそれぞれ表される−ＳＯ_２−含有環式基である。Ｒ”^１０３は、置換基を有してもよい芳香族環式基、置換基を有してもよい脂肪族環式基、又は置換基を有してもよい鎖状のアルケニル基である。Ｖ”^１０１は、単結合、炭素数１〜４のアルキレン基、又は炭素数１〜４のフッ素化アルキレン基である。Ｒ^１０２は、フッ素原子又は炭素数１〜５のフッ素化アルキル基である。ｖ”はそれぞれ独立に０〜３の整数であり、ｑ”はそれぞれ独立に１〜２０の整数であり、ｎ”は０または１である。］

[In the formula, R" ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by each of the above chemical formulas (r-hr-1) to (r-hr-6). R″ ¹⁰² is a cyclic group or a chain-like alkyl group which may have a substituent, R″ ¹⁰² is an aliphatic cyclic group which may have a substituent, and the general formula (a2-r-1) above. , A lactone-containing cyclic group represented by each of (a2-r-3) to (a2-r-7), or each of the above general formulas (a5-r-1) to (a5-r-4). Is a —SO ₂ —-containing cyclic group. R″ ¹⁰³ 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″ ¹⁰¹ is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v" is independently an integer of 0 to 3, q" is independently an integer of 1 to 20, and n" is 0 or 1."

The aliphatic cyclic group which may have a substituent of R″ ¹⁰¹ , R″ ¹⁰² and R″ ¹⁰³ is preferably the group exemplified as the cyclic aliphatic hydrocarbon group for R ¹⁰¹ . As the group, the same groups as the substituents which may substitute the cyclic aliphatic hydrocarbon group for R ¹⁰¹ can be mentioned.

The aromatic cyclic group which may have a substituent in R″ ¹⁰³ is preferably the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R ^101. The substituent is The same as the substituent which may substitute the aromatic hydrocarbon group for R ¹⁰¹ can be mentioned.

The chain alkyl group which may have a substituent in R″ ¹⁰¹ is preferably the group exemplified as the chain alkyl group in the above R ^101. The chain alkyl group which may have a substituent in R″ ¹⁰⁴ The good chain alkenyl group is preferably the group exemplified as the chain alkenyl group for R ¹⁰¹ .

V″ ¹⁰¹ is preferably a single bond or a fluorinated alkylene group, more preferably a single bond or a fluorinated alkylene group having 1 to 3 carbon atoms. When V″ ¹⁰¹ is a fluorinated alkylene group, —V″ V″ ¹⁰¹ in ¹⁰¹ —C(F)(R″ ¹⁰² )—SO ₃ ^— is —CF ₂ —, —CHF—, —CF ₂ CF ₂ —, —CHFCF ₂ —, —CF(CF ₃ )CF _{2 -, - CH (CF 3)} CF 2 - is _preferably, -CF 2 _-, - CHF- are more preferred.

R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R ¹⁰² is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and 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, and more preferably an integer of 1 to 5. And more preferably 1, 2 or 3, and particularly preferably 1 or 2. n″ is 0 or 1.

Anion Part of Component (b-2) In Formula (b-2), R ¹⁰⁴ and R ¹⁰⁵ are each independently a cyclic group which may have a substituent, or a chain which may have a substituent. A linear alkyl group or a chain alkenyl group which may have a substituent, and examples thereof include the same ones as R ¹⁰¹ in the above formula (b-1). However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.
R ¹⁰⁴ and R ¹⁰⁵ are preferably chain alkyl groups which may have a substituent, and are linear or branched alkyl groups or linear or branched fluorinated alkyl groups. Is more preferable.
The chain-like alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and further preferably 1 to 3 carbon atoms. The carbon number of the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably as small as possible within the range of the above carbon number, for reasons such as good solubility in a resist solvent. Further, in the chain alkyl group of R ¹⁰⁴ and R ^105, the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The ratio of fluorine atoms in the chain alkyl group, that is, the fluorination ratio is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are replaced with fluorine atoms. It is a perfluoroalkyl group.
In formula (b-2), V ¹⁰² and V ¹⁰³ each independently represent a single bond, an alkylene group, or a fluorinated alkylene group, and each of them has the same meaning as V ¹⁰¹ in formula (b-1). Can be mentioned.
In formula (b-2), L ¹⁰¹ and L ¹⁰² each independently represent a single bond or an oxygen atom.

Anion Part of Component (b-3) In Formula (b-3), R ^{106 to} R ¹⁰⁸ are each independently a cyclic group that may have a substituent, or a chain that may have a substituent. Alkyl group or a chain alkenyl group which may have a substituent, and examples thereof include the same ones as R ¹⁰¹ in the formula (b-1).
L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —.

{Cation part}
In formulas (b-1), (b-2) and (b-3), m is an integer of 1 or more, M'm ⁺ is an m-valent onium cation, and a sulfonium cation and an iodonium cation are preferable. Examples thereof include organic cations represented by the above general formulas (ca-1) to (ca-4).

［式中、Ｒ^２０１〜Ｒ^２０７及びＲ^２１１〜Ｒ^２１２はそれぞれ独立に、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、又は置換基を有してもよいアルケニル基を表す。Ｒ^２０１〜Ｒ^２０３、Ｒ^２０６〜Ｒ^２０７、Ｒ^２１１〜Ｒ^２１２はそれぞれ、相互に結合して式中のイオウ原子と共に環を形成していてもよい。Ｒ^２０８〜Ｒ^２０９は、それぞれ独立に、水素原子もしくは炭素数１〜５のアルキル基を表すか、又は相互に結合して式中のイオウ原子と共に環を形成していてもよい。Ｒ^２１０は、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、又は置換基を有してもよい−ＳＯ_２−含有環式基である。Ｌ^２０１は、−Ｃ（＝Ｏ）−又は−Ｃ（＝Ｏ）−Ｏ−を表す。複数のＹ^２０１はそれぞれ独立に、アリーレン基、アルキレン基又はアルケニレン基を表す。ｘは、１又は２である。Ｗ^２０１は、（ｘ＋１）価の連結基を表す。］

[In the formula, R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² each independently have an aryl group which may have a substituent, an alkyl group which may have a substituent, or a substituent which may have a substituent. Represents a good alkenyl group. R ^{201 to} R ²⁰³ , R ^{206 to} R ²⁰⁷ , and R ^{211 to} R ²¹² may be bonded to each other to form a ring together with the sulfur atom in the formula. R ^{208 to} R ²⁰⁹ each independently represent 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. R ²¹⁰ is 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 —SO ₂ — which may have a substituent. It is a cyclic group containing. ^L201 represents -C(=O)- or -C(=O)-O-. A plurality of Y ^201's each independently represent an arylene group, an alkylene group or an alkenylene group. x is 1 or 2. W ²⁰¹ represents a (x+1)-valent linking group. ]

Examples of the aryl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² include an aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
The alkyl group for R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² preferably has 2 to 10 carbon atoms.
Examples of the substituent that R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and the following general groups. Examples thereof include groups represented by formulas (ca-r-1) to (ca-r-7).

［式中、Ｒ’^２０１は、それぞれ独立に、水素原子、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、又は置換基を有していてもよい鎖状のアルケニル基である。］

[In the formula, each R′ ²⁰¹ independently has a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group which may be present. ]

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 of R′ ²⁰¹ will be described later. In addition to the same as those of R ^{101 in} the formula (b-1), a cyclic group which may have a substituent or a chain alkyl group which may have a substituent is mentioned above. The same as the acid dissociable group represented by the formula (a1-r-2) of

When R ^{201 to} R ²⁰³ , R ^{206 to} R ²⁰⁷ , and R ^{211 to} R ²¹² are bonded to each other to form a ring with the sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or carbonyl _{group, -SO -, - SO 2 -} , - SO 3 -, - COO -, - CONH- , or -N _(R N) - (. the _{R N} is an alkyl group having 1 to 5 carbon atoms), etc. You may couple|bond through the functional group of. As the ring to be formed, one ring containing a sulfur atom in the formula in its ring skeleton is preferably a 3 to 10-membered ring including a sulfur atom, and particularly preferably a 5 to 7-membered ring. preferable. Specific examples of the ring formed include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxathiin ring, tetrahydro. Examples thereof include a thiophenium ring and a tetrahydrothiopyranium ring.

R ^{208 to} R ²⁰⁹ each independently represent 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, and when they are alkyl groups, they are bonded to each other. You may form a ring.

R ²¹⁰ may have 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 an substituent. -SO ₂ - containing cyclic group.
^Examples of the aryl group for R ²¹⁰ include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
The alkyl group for R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R ²¹⁰ preferably has 2 to 10 carbon atoms. Table is preferably the general formula (a5-r-1) The content cyclic group, - at R ^210, which may have -SO ₂ substituents "- containing polycyclic group - SO _2" More preferred are groups represented by

Y ^201's each independently represent an arylene group, an alkylene group or an alkenylene group.
Examples of the arylene group for Y ²⁰¹ include groups in which one hydrogen atom has been removed from the aryl group exemplified as the aromatic hydrocarbon group for R ¹⁰¹ in formula (b-1) described below.
Examples of the alkylene group and alkenylene group for Y ²⁰¹ include groups obtained by removing one hydrogen atom from the groups exemplified as the chain alkyl group and the chain alkenyl group for R ¹⁰¹ in formula (b-1) described later. ..

In the formula (ca-4), x is 1 or 2.
W ²⁰¹ is a (x+1)-valent, that is, a divalent or trivalent linking group.
As the divalent linking group for W ^{201, a} divalent hydrocarbon group which may have a substituent is preferable, and a divalent hydrocarbon group similar to Ya ²¹ in the above general formula (a2-1) has a substituent. Examples thereof include a divalent hydrocarbon group which may be added. The divalent linking group for W ²⁰¹ may be linear, branched, or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
^Examples of the trivalent linking group for W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group for W ²⁰¹ , a group in which the divalent linking group is further bonded to the divalent linking group, and the like. Can be mentioned. As the trivalent linking group for W ²⁰¹ , a group in which two carbonyl groups are bonded to an arylene group is preferable.

Specific examples of the suitable cation represented by the formula (ca-1) include the following chemical formulas (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-. And cations represented by 1-149).
In the chemical formula below, g1 represents the number of repetitions, and g1 is an integer of 1 to 5. g2 shows the number of repetitions, and g2 is an integer of 0-20. g3 shows the repeating number, and g3 is an integer of 0-20.

［式中、Ｒ”^２０１は水素原子又は置換基である。該置換基としては、上記Ｒ^２０１〜Ｒ^２０７およびＲ^２１１〜Ｒ^２１２が有してもよい置換基として挙げた、アルキル基、ハロゲン原子、ハロゲン化アルキル基、カルボニル基、シアノ基、アミノ基、アリール基、一般式（ｃａ−ｒ−１）〜（ｃａ−ｒ−７）でそれぞれ表される基が挙げられる。］

[In the formula, R″ ²⁰¹ is a hydrogen atom or a substituent. Examples of the substituent include the alkyl group and the halogen which are mentioned as the substituents which the above R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² may have. Examples include an atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by general formulas (ca-r-1) to (ca-r-7).]

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

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

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

Among the above, the cation moiety ((M ^m+ ) _1/m ) is preferably a cation represented by the general formula (ca-1) or (ca-2), and the chemical formulas (ca-1-1) to (ca-). 1-78), (ca-1-101) to (ca-1-149), and cations represented by chemical formulas (ca-2-1) to (ca-2-3) are more preferable.

Examples of the iminosulfonate-based acid generator include compounds represented by the following general formula (b-4) (hereinafter also referred to as “(b-4) component”).

［式中、Ｒ^２１３は、置換を有してもよいアルキル基、又は置換基を有してもよいアリール基である。Ａは、置換を有してもよいアルキレン基、置換を有してもよいアルケニレン基、又は置換を有してもよいアリーレン基である。］

[In the formula, R ²¹³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. A is an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted arylene group. ]

Specific examples of the component (b-4) include compounds represented by the following chemical formula (B1-1) and compounds described in paragraphs [0089] to [0091] of JP-A-10-097075. Be done.

In the resist composition of this embodiment, as the component (B), one type may be used alone, or two or more types may be used in combination.
When the resist composition contains the component (B), the content of the component (B) in the resist composition is preferably 50 parts by mass or less, and 0.1 to 40 parts by mass with respect to 100 parts by mass of the component (A). A mass part is more preferable, 0.1-30 mass parts is still more preferable, 0.1-20 mass parts is especially preferable.
By setting the content of the component (B) within the above range, pattern formation is sufficiently performed.

≪(D) ingredient≫
The resist composition in the present embodiment may further contain an acid diffusion controlling agent component (hereinafter referred to as “(D) component”) in addition to the (A) component and the (Z) component. The component (D) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition.
Examples of the component (D) include, for example, a nitrogen-containing organic compound (D1) (hereinafter referred to as “(D1) component”, a photodegradable base (D2) that does not correspond to the (D1) component and is decomposed by exposure to lose acid diffusion controllability ) (Hereinafter referred to as “(D2) component”) and the like.
By using the resist composition containing the component (D), it is possible to further improve the contrast between the exposed portion and the unexposed portion of the resist film when forming a resist pattern.

Component (D1) The component (D1) is a base component and is a nitrogen-containing organic compound component that acts as an acid diffusion controller in the resist composition.

The component (D1) is not particularly limited as long as it acts as an acid diffusion controller, and examples thereof include an aliphatic amine and an aromatic amine.

Among the aliphatic amines, secondary aliphatic amines and tertiary aliphatic amines are preferable.
The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.
Examples of the aliphatic amine include amines (alkylamines or alkylalcohol amines) or cyclic amines in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms.
Specific examples of alkylamines and alkylalcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; diethylamine, di-n-propylamine, di-amine. Dialkylamines such as -n-heptylamine, di-n-octylamine and dicyclohexylamine; 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, tri-n-dodecylamine and like trialkylamines; diethanolamine, triethanolamine, diisopropanolamine, tri Examples thereof include alkyl alcohol amines such as isopropanol amine, di-n-octanol amine and tri-n-octanol amine. Among these, a trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

Examples of the cyclic amine include a heterocyclic compound 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 aliphatic monocyclic amine include piperidine and piperazine.
The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, specifically, 1,5-diazabicyclo[4.3.0]-5-nonene and 1,8-diazabicyclo[5. 4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane and the like can be mentioned.

Other aliphatic amines 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, triethanolamine triacetate, and the like, with triethanolamine triacetate being preferred.

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

As the component (D1), one type may be used alone, or two or more types may be used in combination.
Among the above, the component (D1) is preferably an aromatic amine, more preferably an aniline compound. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline and the like.

Component (D2) The component (D2) is not particularly limited as long as it is decomposed by exposure and loses acid diffusion controllability, and is a compound represented by the following general formula (d2-1) (hereinafter referred to as “( "d2-1) component"), a compound represented by the following general formula (d2-2) (hereinafter referred to as "(d2-2) component") and a compound represented by the following general formula (d2-3). (Hereinafter, referred to as “(d2-3) component”.) One or more compounds selected from the group consisting of are preferable.
The components (d2-1) to (d2-3) are decomposed in the exposed portion of the resist film and lose the acid diffusion controllability (basicity) and therefore do not act as a quencher, and the quencher in the unexposed portion of the resist film. Acts as.

［式中、Ｒｄ^１〜Ｒｄ^４は置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。但し、一般式（ｄ２−２）中のＲｄ^２における、Ｓ原子に隣接する炭素原子にはフッ素原子が結合していないものとする。Ｙｄ^１は単結合又は２価の連結基である。ｍは１以上の整数であって、Ｍ’^ｍ＋はそれぞれ独立にｍ価のオニウムカチオンである。］

[In the formula, Rd ^{1 to} Rd ⁴ are cyclic groups which may have a substituent, chain alkyl groups which may have a substituent, or chain alkenyl groups which may have a substituent. Is. However, a fluorine atom is not bonded to the carbon atom adjacent to the S atom in Rd ² in the general formula (d2-2). Yd ¹ is a single bond or a divalent linking group. m is an integer of 1 or more, and M′ ^m+ are each independently an m-valent onium cation. ]

{(D2-1) component}
Anion part In formula (d2-1), Rd ¹ may have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group, and examples thereof include the same ones as R ¹⁰¹ and the like in the above formula (b-1).
Among these, Rd ¹ is an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like group which may have a substituent. Alkyl groups are preferred. 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 fluorinated alkyl group, and the above general formulas (a2-r-1) to (a2-r-7). ), a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When it contains an ether bond or an ester bond as a substituent, it may be via an alkylene group, and the substituent in this case is represented by each of the above formulas (y-al-1) to (y-al-5). A linking group is preferred.
Preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (for example, a polycyclic structure including a ring structure of the bicyclooctane skeleton and other ring structures). Be done.
The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The chain alkyl group preferably has 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Linear alkyl groups such as nonyl group and decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl Examples thereof include branched chain alkyl groups such as a group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group and a 4-methylpentyl group.

When the chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the carbon number of the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8 and 1 To 4 are more preferable. The fluorinated alkyl 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.
Rd ¹ is preferably a fluorinated alkyl group in which some or all of the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms, and the hydrogen atom of the linear alkyl group It is particularly preferable that all are fluorinated alkyl groups (linear perfluoroalkyl groups) substituted with fluorine atoms.

Specific preferred examples of the anion moiety of the component (d2-1) are shown below.

-Cation part In formula (d2-1), M'm ⁺ is a m-valent onium cation.
Preferable examples of the M'm ⁺ onium cation include the same cations represented by the general formulas (ca-1) to (ca-4), and are represented by the general formula (ca-1). Cations represented by formulas (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149) are more preferable.
As the component (d2-1), one type may be used alone, or two or more types may be used in combination.

{(D2-2) component}
Anion formula (d2-2), Rd ^2, the substituents cyclic group which may have a may have a substituent which may chain having alkyl group, or a substituent It is a chain alkenyl group, and examples thereof include the same ones as R ¹⁰¹ and the like in the above formula (b-1).
However, a fluorine atom is not bonded to the carbon atom adjacent to the S atom in Rd ² (not fluorine-substituted). Thereby, the anion of the component (d2-2) becomes an appropriate weak acid anion, and the quenching ability as the component (D2) is improved.
Rd ² is preferably a chain-like alkyl group which may have a substituent, or an aliphatic cyclic group which may have a substituent. The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. As the aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane or the like (which may have a substituent); one or more from camphor or the like More preferably, it is a group excluding the hydrogen atom of.
The hydrocarbon group of Rd ² may have a substituent, and examples of the substituent include the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain in Rd ¹ of the formula (d2-1). The same as the substituent which the alkyl group) may have.

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

-Cation part In formula (d2-2), M'm ⁺ is an m-valent onium cation and is the same as M'm ⁺ in the formula (d2-1).
As the component (d2-2), one type may be used alone, or two or more types may be used in combination.

{(D2-3) component}
During Anion formula (d2-3), Rd ³ is an optionally substituted cyclic group, an alkyl group which may chain have a substituent or may chains may have a substituent A cyclic alkenyl group, examples of which include the same as R ¹⁰¹ and the like in formula (b-1) above, and a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. Is preferred. Among them, a fluorinated alkyl group is preferable, and a group similar to the fluorinated alkyl group for Rd ¹ is more preferable.

In the formula (d2-3), Rd ⁴ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain group which may have a substituent. It is an alkenyl group, and examples thereof include the same ones as R ¹⁰¹ and the like in the above formula (b-1).
Of these, an alkyl group, an alkoxy group, an alkenyl group and a cyclic group which may have a substituent are preferable.
The alkyl group for Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group. , Tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A part of hydrogen atoms of the alkyl group of Rd ⁴ may be substituted with a hydroxyl group, a cyano group or the like.
The alkoxy group for Rd ⁴ 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 methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n- Examples thereof include butoxy group and tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferable.

Examples of the alkenyl group for Rd ⁴ include those similar to R ¹⁰¹ and the like in the above formula (b-1), and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group are preferable. .. These groups may further have, as a substituent, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

Examples of the cyclic group for Rd ⁴ include those similar to R ¹⁰¹ and the like in the above formula (b-1), and cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Is preferably an alicyclic group from which one or more hydrogen atoms have been removed, or an aromatic group such as a phenyl group or a naphthyl group. When Rd ⁴ is an alicyclic group, the resist composition is well dissolved in the organic solvent, and thus the lithographic properties are good.

In formula (d2-3), Yd ¹ is a single bond or a divalent linking group.
The divalent linking group for Yd ¹ is not particularly limited, but may be a divalent hydrocarbon group which may have a substituent (aliphatic hydrocarbon group, aromatic hydrocarbon group), divalent hetero atom-containing divalent group. And a linking group thereof. These are each a divalent hydrocarbon group which may have a substituent and a hetero atom-containing 2 which are mentioned in the description of the divalent linking group for Ya ^x1 in the above formula (a10-1). The same as the valent linking group can be mentioned.
Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, further preferably a methylene group or an ethylene group.

Specific preferred examples of the anion moiety of the component (d2-3) are shown below.

-Cation part In formula (d2-3), M'm ⁺ is a m-valent onium cation, and is the same as M'm ⁺ in the said formula (d2-1).
As the component (d2-3), one type may be used alone, or two or more types may be used in combination.

As the component (D2), only one type of the above-mentioned components (d2-1) to (d2-3) may be used, or two or more types 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, and 1 to 100 parts by mass of the component (A). 25 parts by mass is more preferable, 2 to 20 parts by mass is further preferable, and 3 to 15 parts by mass is particularly preferable.
When the content of the component (D2) is at least the preferred lower limit value, particularly good lithographic properties and resist pattern shapes are likely to be obtained. On the other hand, when it is at most the upper limit value, it is possible to balance with other components, and various lithographic properties are improved.

Method for producing component (D2):
The method for producing the above-mentioned component (d2-1) and component (d2-2) is not particularly limited and can be produced by a known method.
The method for producing the component (d2-3) is not particularly limited, and for example, it is produced in the same manner as the method described in US2012-0149916.

<<Component (E): at least one compound selected from the group consisting of organic carboxylic acids and phosphorus oxo acids and their derivatives>>
The resist composition of the present embodiment comprises an organic carboxylic acid and an oxo acid of phosphorus and its derivative as an optional component for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, leaving stability over time, and the like. At least one compound (E) selected from the group (hereinafter referred to as “(E) component”) can be contained.
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 suitable.
Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid, and phosphinic acid. Of these, phosphonic acid is particularly preferable.
Examples of the phosphorus oxo acid derivative include esters in which the hydrogen atom of the above oxo acid is substituted with a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. The aryl group of 15 and the like can be mentioned.
Examples of phosphoric acid derivatives include phosphoric acid esters such as phosphoric acid di-n-butyl ester and phosphoric acid diphenyl ester.
Examples of phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.
Examples of the phosphinic acid derivative include phosphinic acid ester and phenylphosphinic acid.
In the resist composition of this embodiment, as the component (E), one type may be used alone, or two or more types 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 with respect to 100 parts by mass of the component (A).

≪(F) component: Fluorine additive component≫
The resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as “(F) component”) in order to impart water repellency to the resist film or improve the lithographic properties.
Examples of the component (F) are described in JP2010-002870A, JP2010-032994A, JP2010-277043A, JP2011-13569A, and JP2011-128226A. The fluorine-containing polymer compound can be used.
More specifically, the component (F) includes a polymer having a structural unit (f1) represented by the following formula (f1-1). As this polymer, a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1) It is preferably a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1). Here, as the structural unit (a1) copolymerized with the structural unit (f1), a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, 1-methyl-1-adamantyl ( Structural units derived from (meth)acrylate are preferred.

［式中、Ｒは前記と同様であり、Ｒｆ^１０２およびＲｆ^１０３はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基を表し、Ｒｆ^１０２およびＲｆ^１０３は同じであっても異なっていてもよい。ｎｆ^１は１〜５の整数であり、Ｒｆ^１０１はフッ素原子を含む有機基である。］

[In the formula, R is the same as defined above, and Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, Rf ¹⁰² and Rf ¹⁰³ may be the same or different. nf ¹ is an integer of ¹ to 5, and Rf ¹⁰¹ is a fluorine atom-containing organic group. ]

In formula (f1-1), R bonded to the carbon atom at the α-position is the same as above. R is preferably a hydrogen atom or a methyl group.
In formula (f1-1), examples of the halogen atom of Rf ¹⁰² and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable. Examples of the alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ are the same as those of the alkyl group having 1 to 5 carbon atoms of R above, and a methyl group or an ethyl group is preferable. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Be done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. Among them, Rf ¹⁰² and Rf ¹⁰³ are preferably a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom, a fluorine atom, a methyl group or an ethyl group is preferable.
In the formula (f1-1), nf ¹ is an integer of ¹ to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

In formula (f1-1), Rf ¹⁰¹ is an organic group containing a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom.
The hydrocarbon group containing a fluorine atom may be linear, branched or cyclic and has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms. Particularly preferably, the carbon number is 1 to 10.
Further, in the hydrocarbon group containing a fluorine atom, 25% or more of the hydrogen atoms in the hydrocarbon group are preferably fluorinated, more preferably 50% or more, and more preferably 60% or more. Fluorination is particularly preferable because the hydrophobicity of the resist film during immersion exposure increases.
Among them, as Rf ¹⁰¹ , a fluorinated hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a trifluoromethyl group, —CH ₂ —CF ₃ , —CH ₂ —CF ₂ —CF ₃ , or —CH(CF _{3). ) 2, -CH 2 -CH 2 -CF} 3, it is _{-CH 2 -CH 2 -CF 2 -CF 2} -CF 2 -CF 3 particularly preferred.

The mass average molecular weight (Mw) of the component (F) (polystyrene conversion standard by gel permeation chromatography) is preferably from 1000 to 50,000, more preferably from 5,000 to 40,000, and most preferably from 10,000 to 30,000. When it is at most the upper limit of this range, it has sufficient solubility in a resist solvent for use as a resist, and when it is at least the lower limit of this range, the water repellency of the resist film is good.
The dispersity (Mw/Mn) of the component (F) 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 this embodiment, as the component (F), one type may be used alone, or two or more types may be used in combination.
When the resist composition contains the component (F), the content of the component (F) is usually 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A).

<<(S) component: organic solvent component>>
The resist composition of this embodiment can be manufactured by dissolving a resist material in an organic solvent component (hereinafter referred to as “(S) component”).
As the component (S), any component capable of dissolving each component used to form a uniform solution may be used, and any one of the conventionally known solvents for chemically amplified resist compositions may be appropriately used. It can be selected and used.
Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol. , Polyhydric alcohols such as dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, having the polyhydric alcohols or having the ester bond Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate. , Esters such as methyl methoxypropionate and ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, Examples thereof include aromatic organic solvents such as xylene, cymene and mesitylene, and dimethyl sulfoxide (DMSO).
In the resist composition of this embodiment, the component (S) may be used alone or as a mixed solvent of two or more kinds.
Of these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferable.
A mixed solvent obtained by mixing PGMEA and a polar solvent is also preferable. The compounding ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. It is preferably within the range.
More specifically, when EL or cyclohexanone is blended as the polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. .. When PGME is blended as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and further preferably 3:7 to 7:. It is 3. Further, a mixed solvent of PGMEA, PGME and cyclohexanone is also preferable.
In addition, as the component (S), a mixed solvent of γ-butyrolactone with at least one selected from PGMEA and EL is also preferable. In this case, as the mixing ratio, the mass ratio of the former and the latter is preferably 70:30 to 95:5.
The amount of the component (S) used is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. Generally, the component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 50% by mass, preferably 10 to 50% by mass.

The resist composition of the present embodiment further includes, if desired, an additive that is miscible, for example, an additional resin for improving the performance of the resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent. , Dyes, and the like can be appropriately added and contained.

The resist composition of the present embodiment may be obtained by dissolving the above resist material in the component (S), and then removing impurities and the like using a polyimide porous film, a polyamideimide porous film or the like. For example, the resist composition may be filtered using a filter composed of a polyimide porous film, a filter composed of a polyamideimide porous film, a filter composed of a polyimide porous film and a polyamideimide porous film, or the like. Examples of the polyimide porous film and the polyamideimide porous film include those described in JP-A-2016-155121.

The resist composition of the present embodiment contains a base material component (A) and a dissolution inhibitor (Z). The dissolution inhibitor (Z) contains the compound (Z1) and the compound (Z2).
Generally, in a resist film formed by using a resist composition, a space is generated between molecules constituting a base material component. When the molecular weight of the base material component becomes large, the molecules themselves constituting the base material component also become large, so that the space generated between the molecules also becomes large. Such a space formed in the resist film may reduce the adhesion of the resist film to the substrate.
In the resist composition of the present embodiment, the compound (Z1) and the compound (Z2) both have a mass average molecular weight of 3000 or less, and therefore have a relatively small molecular size. Therefore, in the resist film formed by using the resist composition of the present embodiment, the compound (Z1) and the compound (Z2) are easily dispersed appropriately in the space generated between the molecules constituting the base component (A). ..
Since the compound (Z1) has a phenolic hydroxyl group or a carboxyl group in the molecule, it tends to segregate to the lower layer in the resist film. Therefore, it is presumed that the compound (Z1) contributes to the improvement of the adhesion between the resist film and the substrate interface, and the etching resistance (particularly the wet etching resistance) is improved.
On the other hand, since the compound (Z1) has a phenolic hydroxyl group or a carboxyl group in the molecule, it may cause a reduction in the resist film especially in the alkali developing process. However, the compound (Z2) is more hydrophobic than the compound (Z1). Therefore, it is presumed that the compound (Z2) contributes to the reduction of the film thickness of the resist film that may be caused by the compound (Z1).
It is presumed that a resist pattern having good etching resistance and a good shape can be obtained by the synergistic effect of the compound (Z1) and the compound (Z2) as described above.

(Method of forming resist pattern)
A second aspect of the present invention is a step (i) of forming a resist film on the support using the resist composition according to the first aspect, a step (ii) of exposing the resist film, and The resist pattern forming method includes a step (iii) of forming a resist pattern by developing the exposed resist film.
An example of such a resist pattern forming method is a resist pattern forming method performed as follows.

Process (i):
First, the resist composition of the above-described embodiment is applied on a support by a spinner or the like, and baking (post-apply bake (PAB)) treatment is performed, for example, at a temperature condition of 80 to 160° C. for 40 to 200 seconds, It is preferably applied for 60 to 150 seconds to form a resist film.

Step (ii):
Next, the resist film is subjected to selective exposure such as exposure through a mask (mask pattern) on which a predetermined pattern is formed using an exposure device such as a KrF exposure device, and then baked (post). The exposure bake (PEB) treatment is performed, for example, at a temperature condition of 80 to 150° C. for 40 to 150 seconds, preferably 60 to 120 seconds.

Step (iii):
Next, the resist film is developed. The development treatment is performed using an alkali developing solution in the case of an alkali developing process, and using a developing solution containing an organic solvent (organic developing solution) in the case of a solvent developing process.
After the development processing, rinsing processing is preferably performed. The rinse treatment is preferably a water rinse using pure water in the case of an alkali developing process, and preferably a rinse liquid containing an organic solvent in the case of a solvent developing process.
In the case of the solvent developing process, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be performed.

After development or rinsing, drying is performed. In addition, depending on the case, a bake treatment (post bake) may be performed after the above development treatment. The baking treatment (post-baking) here is performed, for example, at a temperature of 80° C. or higher, preferably 90 to 120° C. for 10 to 120 seconds, preferably 300 to 90 seconds.
In this way, the resist pattern can be formed.

The support is not particularly limited, and a conventionally known support can be used, and examples thereof include a substrate for electronic parts and a substrate having a predetermined wiring pattern formed thereon. More specifically, a silicon wafer, a substrate made of metal such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
Further, the support may be the above-mentioned substrate on which an inorganic and/or organic film is provided. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). Examples of the organic film include an organic antireflection film (organic BARC) and an organic film such as a lower organic film in a multilayer resist method.
Here, the multi-layer resist method means that at least one organic film (lower organic film) and at least one resist film (upper resist film) are provided on a substrate, and the resist pattern formed on the upper resist film is used as a mask. It is a method of patterning the lower organic film and is said to be capable of forming a pattern with a high aspect ratio. That is, according to the multi-layer resist method, since the required thickness can be secured by the lower organic film, the resist film can be thinned and a fine pattern with a high aspect ratio can be formed.
The multi-layer resist method basically includes a method of forming a two-layer structure of an upper resist film and a lower organic film (two-layer resist method), and one or more intermediate layers between the upper resist film and the lower organic film. A method of forming a multi-layered structure having three or more layers (three-layer resist method) provided with (metal thin film etc.).

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

The wavelength used for the exposure is not particularly limited, and ultraviolet rays such as g-line and i-line, ArF excimer laser light, KrF excimer laser light, F ₂ excimer laser light, EUV (extreme ultraviolet ray), VUV (vacuum ultraviolet ray), EB ( Electron beam), X-rays, soft X-rays and the like can be used.
The resist composition according to the first aspect described above is highly useful for ultraviolet rays such as g-rays and i-rays, KrF excimer laser light, ArF excimer laser light, EB or EUV, and is useful for g-ray, i-ray and the like. It is more useful for ultraviolet rays, KrF excimer laser light, ArF excimer laser light, and particularly useful for ultraviolet rays such as g-line and i-line and KrF excimer laser light. The resist pattern forming method according to the second aspect is a particularly suitable method when the resist film is irradiated with ultraviolet rays such as g-line or i-line or KrF excimer laser light in the step (ii).

The exposure method of the resist film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or a liquid immersion exposure (Liquid Immersion Lithography).
In the immersion exposure, the space between the resist film and the lens at the lowest position of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index higher than that of air, and exposure (immersion exposure) is performed in that state. It is an exposure method.
As the immersion medium, a solvent having a refractive index higher than that of air and lower than that of the resist film to be exposed is preferable. The refractive index of the solvent is not particularly limited as long as it falls 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 examples of the fluorine-based inert _liquid, mainly composed of _{C 3 HCl 2 F 5, C} 4 F 9 OCH 3, C 4 F 9 OC 2 H 5, C 5 H 3 F 7 , etc. A fluorine- Examples thereof include liquids, those having a boiling point of 70 to 180° C. are preferable, and those having a boiling point of 80 to 160° C. are more preferable. It is preferable that the fluorine-based inert liquid has a boiling point within the above range because the medium used for immersion can be removed by a simple method after the exposure is completed.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are replaced with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
More specifically, examples of the perfluoroalkyl ether compound include perfluoro(2-butyl-tetrahydrofuran) (boiling point 102° C.), and examples of the perfluoroalkylamine compound include perfluorotributylamine( The boiling point is 174° C.).
As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility and the like.

Examples of the alkaline developer used for the developing treatment in the alkaline developing process include an aqueous solution of tetramethylammonium hydroxide (TMAH) of 0.1 to 10% by mass.
The organic solvent contained in the organic developing solution used for the developing treatment in the solvent developing process may be any one capable of dissolving the component (A) (component (A) before exposure), and among known organic solvents It can be selected appropriately. Specific examples 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 an alcoholic hydroxyl group in its structure. "Alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. A nitrile solvent is an organic solvent containing a nitrile group in its structure. The amide solvent is an organic solvent containing an amide group in its structure. The ether solvent is an organic solvent containing C—O—C in the structure.
Among the organic solvents, there are also organic solvents containing a plurality of functional groups that characterize each of the above-mentioned solvents in the structure, but in that case, it corresponds to any solvent species containing a functional group that the organic solvent has. I shall. For example, diethylene glycol monomethyl ether corresponds to both the alcohol solvent and the ether solvent in the above classification.
The hydrocarbon solvent is a hydrocarbon solvent that may be halogenated and does not have a substituent other than a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
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, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone. , Methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, methylamylketone (2-heptanone) and the like. Among these, methyl amyl ketone (2-heptanone) is preferable 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 monoester. Propyl 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3. -Methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, formic acid Propyl, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, propionic acid Ethyl, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate , Propyl-3-methoxypropionate and the like. Of these, butyl acetate is preferable as the ester solvent.

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

If desired, known additives can be added to the organic developer. Examples of the additive include a surfactant. The surfactant is not particularly limited, but, 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 0.01 to 0. 5 mass% is more preferable.

The development treatment can be carried out by a known development method, for example, a method of dipping the support in a developing solution for a certain period of time (dip method), raising the developing solution to the surface of the support by surface tension, and then standing still for a certain period of time. Method (paddle method), spraying the developer on the surface of the support (spray method), and applying the developer while scanning the developer application nozzle at a constant speed on the support rotating at a constant speed. A method of continuing (dynamic dispensing method) and the like can be mentioned.

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, among the organic solvents used as the organic solvent used in the organic developer, those which hardly dissolve the resist pattern are appropriately selected. Can be used. Usually, at least one solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent is used. Among these, at least one selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent and an amide solvent is preferable, and at least one selected from an alcohol solvent and an ester solvent is more preferable. Alcohol solvents are particularly preferred.
The alcohol solvent used for the rinse liquid is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specific examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Be done. Among these, 1-hexanol, 2-heptanol and 2-hexanol are preferable, and 1-hexanol and 2-hexanol are more preferable.
These organic solvents may be used alone or in combination of two or more. Further, it may be used by mixing with an organic solvent or water other than the above. However, considering development characteristics, the content of water in the rinse liquid is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and more preferably 3% by mass with respect to the total amount of the rinse liquid. The following are particularly preferred.
Known additives may be added to the rinse liquid, if necessary. Examples of the additive include a surfactant. As the surfactant, the same ones as mentioned above can be mentioned, and a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
When compounding a surfactant, the compounding quantity is usually 0.001 to 5 mass%, preferably 0.005 to 2 mass%, and 0.01 to 0.5 mass% with respect to the total amount of the rinse liquid. % Is more preferable.

The rinse treatment (washing treatment) using the rinse liquid can be carried out by a known rinse method. Examples of the rinsing method include a method of continuously applying a rinsing solution onto a support rotating at a constant speed (rotational coating method), a method of immersing the support in the rinsing solution for a certain time (dip method), Examples thereof include a method of spraying a rinse liquid on the surface of the support (spray method).

In the resist pattern forming method of the present embodiment described above, since the resist composition according to the first aspect described above is used, it is possible to obtain a resist pattern having good etching resistance and a good shape. Guessed.

Such a resist composition and a resist pattern forming method are useful for applications in which a thick resist film is required, for example. Further, such a resist composition and a resist pattern forming method are useful for processing a stepped structure having a plurality of steps, and by applying the present invention, stacking of memory films (three-dimensionalization, production of large-capacity memory). ) Can be realized with high accuracy.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Preparation of resist composition>
(Examples 1-10, Comparative Examples 1-3)
The components shown in Table 1 were mixed and dissolved to prepare the resist composition of each example (solid content concentration 30% by mass).

In Table 1, each abbreviation has the following meanings. The numerical value in [] is a compounding amount (part by mass).
(A)-1: A polymer compound represented by the following chemical formula (A1-1). The mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 10,000, and the molecular weight dispersity (Mw/Mn) is 2.14. ^The copolymerization composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by ¹³ C-NMR was 1/m/n=61/14/25.

(B1)-1: a compound represented by the following chemical formula (B1-1).

(Z1)-1: a compound represented by the following chemical formula (Z1-1). Mass average molecular weight (Mw) is 268.35.
(Z1)-2: a compound represented by the following chemical formula (Z1-2). Mass average molecular weight (Mw) is 424.53.
(Z1)-3: a compound represented by the following chemical formula (Z1-3). Mass average molecular weight (Mw) is 352.43.
(Z1)-4: a compound represented by the following chemical formula (Z1-4). Mass average molecular weight (Mw) is 246.31.
(Z1)-5: a compound represented by the following chemical formula (Z1-5). Mass average molecular weight (Mw) is 292.29.

(Z2)-1: a compound represented by the following chemical formula (Z1-1). Mass average molecular weight (Mw) is 953.21.
(Z2)-2: a compound represented by the following chemical formula (Z1-2). Mass average molecular weight (Mw) is 827.1.

(S)-1: Mixed solvent of propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether (mass ratio 50/50).

<Method of forming resist pattern>
Process (i):
The resist composition of each example was applied onto a silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner, and prebaked (PAB) was performed on a hot plate at 90° C. for 120 seconds. Then, by drying, a resist film having a film thickness of 5.0 μm was formed.
Step (ii):
Then, a high-pressure mercury lamp (365 nm) was applied to the resist film by an i-line stepper (reduction projection exposure apparatus: NSR-2205i14E (manufactured by Nikon Corporation; NA (numerical aperture)=0.57, σ=0.67)). , And selectively irradiated through a mask pattern (6% halftone).
Then, post-exposure bake (PEB) treatment was performed at 110° C. for 60 seconds.
Step (iii):
Then, using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a developer, alkali development is performed under the conditions of 23° C. for 60 seconds. It was
After that, a baking treatment (post-baking) was performed at 100° C. for 60 seconds.
As a result, an isolated line pattern (hereinafter referred to as “IS pattern”) having a space width of 3 μm and a pitch of 15 μm was formed.

<Dry etching resistance evaluation>
The IS pattern formed by the resist pattern forming method described above was dry-etched under the following conditions using an etching apparatus manufactured by Tokyo Ohka Kogyo.
conditions:
Type and flow rate of etching gas: tetrafluoromethane 30 cc/min. And trifluoromethane 30 cc/min. And helium 100 cc/min. Mixed gas pressure: 300 mmTorr
Output: 600w
Time: 120 seconds The cross-sectional shape of the IS pattern after dry etching was observed with a scanning electron microscope (product name: S4500; manufactured by Hitachi, Ltd.) to evaluate the presence or absence of undercut (etching at the bottom of the pattern). The results are shown in Table 2.

<Wet etching resistance evaluation>
A part of the substrate on which the IS pattern was formed by the above-described resist pattern forming method was cut off and immersed in 23% buffered hydrofluoric acid for 12 minutes.
The cross-sectional shape of the IS pattern after immersion was observed with a scanning electron microscope (product name: S4500; manufactured by Hitachi, Ltd.) to evaluate the side etching amount (μm). The results are shown in Table 2.

(Evaluation of pattern film loss)
The resist composition of each example was applied onto an 8-inch silicon wafer by using a spinner, prebaked (PAB) at 120° C. for 90 seconds on a hot plate, and dried to obtain a film thickness. A 5.0 μm resist film was formed.
Then, the resist film is treated with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a developing solution at 23° C. for 60 seconds. Alkali development was carried out.
After that, spin-drying was performed by spin coating, and the film thickness (nm) of the resist film was measured by using Nanospec 6100A (manufactured by Nanometrics). The results are shown in Table 2.

From the results shown in Table 2, when a resist pattern is formed using the resist compositions of Examples 1 to 10 to which the present invention is applied, film reduction of the pattern is suppressed, and both dry etching resistance and wet etching resistance are exhibited. Was also confirmed to be good.

Claims (4)

A resist composition which generates an acid upon exposure and whose solubility in a developing solution is changed by the action of the acid,
A base material component (A) whose solubility in a developer is changed by the action of an acid,
A dissolution inhibitor (Z) which suppresses solubility in a developing solution,
Containing
The dissolution inhibitor (Z) is
A compound (Z1) having a mass average molecular weight of 3000 or less and having a phenolic hydroxyl group or a carboxyl group in the molecule,
A compound (Z2) having a mass average molecular weight of 3000 or less and represented by the following general formula (z2):
A resist composition comprising:

[In the formula, R _z ²⁰ is an acid dissociable group. R _z ³⁰ is a hydrogen atom or an organic group. n1 is an integer of 1 to 6, and n2 is an integer of 0 to 5. However, n1+n2=6. ] The resist composition according to claim 1, wherein the content of the dissolution inhibitor (Z) is 30 parts by mass or less based on 100 parts by mass of the base component (A). The compounding ratio (mass ratio) of the compound (Z1) and the compound (Z2) is
The resist composition according to claim 1 or 2, wherein Z1:Z2=75:25 to 25:75. A step (i) of forming a resist film using the resist composition according to any one of claims 1 to 3 on a support, a step (ii) of exposing the resist film, and a step after the exposure. A method for forming a resist pattern, comprising a step (iii) of developing a resist film to form a resist pattern.