TW201331714A - Method for forming fine pattern, and coating forming agent for pattern miniaturizing - Google Patents

Abstract

The present invention provides a novel resist pattern forming method for further re-fining a resist pattern formed by a negative type developing process. The formation of the resist pattern includes the following steps: a resist film forming step of forming a resist film on a substrate by applying a resist composition containing (A) a base material having a solubility, in a developer liquid including an organic solvent, that decreases according to an action of an acid, (B) a compound which generates an acid when irradiated with actinic rays or radiation, and (C) a solvent; an exposure step; a first developing step of developing the exposed resist film; a coating film forming step of forming a first coating film by applying, on the resist pattern, a first coating forming agent including (A<1>) a resin having a solubility in an organic solvent that decreases according to an action of an acid, and (C<1>) a solvent; and a first thickening step of heating the resist pattern on which the first coating forming agent has been applied.

Description

Fine pattern forming method and coating forming agent for pattern miniaturization

The present invention relates to a method for forming a fine pattern and a coating forming agent for pattern miniaturization.

The method of forming a fine pattern by resist is used for the manufacture of various products. In particular, in the semiconductor element, as the performance of the semiconductor is improved, it is necessary to carry out various reviews in order to further refine the resist pattern.

As a method of forming the fine resist pattern, a positive-type chemically amplified resist composition has been proposed, and a chemically amplified resist composition which increases solubility in an alkaline developing solution by exposure has been proposed. A new negative development process in combination with a developing solution containing an organic solvent (see, for example, Patent Document 1). The positive chemically amplified resist composition can increase the solubility in the alkaline developing solution by exposure, but at this time, the solubility in the organic solvent is relatively lowered. Therefore, in the negative development process, the unexposed portion of the resist film is dissolved and removed by the organic-based developing solution to form a resist pattern, which is compared with the past positive-type developing process for the groove pattern or the hole pattern. The formation of the type is advantageous.

Further, as a method of further refining the resist pattern formed by the negative development process, the resist pattern formed by the negative development process is used to form a resist pattern in the presence of an acid. The cross-linking layer forming material forming the cross-linking layer on the interface of the pattern acts, and the pattern forming method of forming the cross-linking layer by forming the resist pattern-forming resin and the cross-linking layer forming material is also proposed. (Refer to Patent Document 2).

[prior technical literature] [Patent Document]

[Patent Document 1] JP-A-2008-292975

[Patent Document 2] JP-A-2008-310314

In view of the above-described requirements for miniaturization of the resist pattern and the negative development process, a method of further refining the resist pattern formed by the negative development process is expected.

The present invention has been made in view of the fact that the present invention has been made to provide a method for forming a novel resist pattern of a resist pattern formed by a negative development process.

The present inventors have found that the above problems can be solved by forming a resist pattern formed by the following method, and the present invention has been completed. The method comprises the steps of: (A) a substrate having a reduced solubility for an imaging solution containing an organic solvent by an action of an acid, (B) a compound which generates an acid by irradiation with actinic rays or radiation, and (C) a resist film forming step of applying a resist composition of a solvent onto a substrate, forming a resist film, an exposure step of exposing the resist film, and applying the exposed resist film to the developing liquid a first developing step of forming a resist pattern after development, and containing (A ¹ ) a resin having a reduced solubility in an organic solvent by an action of an acid, and a (C ¹ ) solvent on the resist pattern a first coating film forming step of forming a first coating film after coating with the first coating forming agent, and a resist pattern applied by heating the first coating forming agent, which is not formed on the resist pattern surface A first thickening step of thickening the pattern to form a first hardly soluble layer which is insoluble to the above-mentioned developing solution is formed by high molecular weight.

Specifically, the present invention provides the following.

A first aspect of the present invention is a method for forming a fine pattern comprising the following steps, which comprises the steps of: (A) reducing the solubility of an imaging solution containing an organic solvent by an action of an acid; (B) a resist film forming step of forming a resist film by applying an acid compound after irradiation with active light or radiation, and a resist composition of (C) solvent, to form a resist film, and the above-mentioned resist An exposure step of exposing the film, a first development step of forming a resist pattern by developing the exposed resist film by the developing solution, and coating the resist pattern on the resist pattern (A ¹ ) a first coating film forming step of forming a first coating film after a resin having a reduced solubility in an organic solvent by an action of an acid, and a first coating forming agent of the (C ¹ ) solvent, and heating the first coating forming agent The applied resist pattern forms a first thickening which thickens the pattern by forming a first hardly soluble layer which is insoluble to the developing liquid without causing high molecular weight on the surface of the resist pattern. Steps.

The second aspect of the present invention is formed like the first aspect of the fine pattern comprising the method used (A ¹⁾ by action of an acid to reduce the solubility of the organic solvent, a resin, and (C ¹⁾ of FIG solvent A coating forming agent for miniaturization.

The present invention is a method for forming a new resist pattern which further refines a resist pattern formed by a negative development process.

Type of implementation of the invention

The fine pattern forming method of the present invention includes each of the predetermined resist film forming step, the exposing step, the first developing step, the first coating film forming step, and the first thickening step, and may also contain the second portion if necessary Development steps. The following is a description of each step.

≪Resist film forming step≫

In the resist film forming step, (A) a substrate having reduced solubility in an organic solvent-containing developing solution by an action of an acid (hereinafter also referred to as "(A) component"), (B) by activity A resist composition which generates an acid after irradiation of light or radiation (hereinafter also referred to as "(B) component)" and (C) solvent (hereinafter also referred to as "(C) component") is formed on a substrate. Resist film.

The following is a resist composition and a resist for the resist film forming step. The film formation method will be described in order.

<resist composition>

Hereinafter, it is necessary to include the components (A), (B), and (C) and optional components in the order of the resist composition.

[(A) component]

The "base component" of the component (A) means an organic compound having a film forming ability. As the substrate component, an organic compound having a molecular weight of 500 or more is generally used. Since the molecular weight is 500 or more, it is possible to form a nano-level resist pattern while having sufficient film formation energy. "Organic compounds having a molecular weight of 500 or more" can be roughly classified into non-polymers and polymers. As the non-polymer, those having a molecular weight of 500 or more and less than 4,000 are generally used. Hereinafter, in the case of a "low molecular compound", a non-polymer having a molecular weight of 500 or more and less than 4,000 is shown. As the polymer, those having a molecular weight of 1,000 or more are generally used. For the purposes of this specification and the patent application, "polymer compound" means a polymer having a molecular weight of 1,000 or more. In the case of a polymer compound, the "molecular weight" is a mass average molecular weight in terms of polystyrene by GPC (gel permeation chromatography).

The component (A) is not particularly limited as long as it can be reduced in solubility in a developing solution containing an organic solvent by an acid action. As the component (A), a resin (A1) containing an "acid-decomposable group" protected by an acid dissociable protecting group as a hydrophilic group of a resin having a hydrophilic group (hydroxy group, carboxyl group, etc.) is used. material. As a resin having a hydrophilic group, for example A resin (PHS resin) having a constituent unit derived from hydroxystyrene such as a phenol resin, a polyhydroxystyrene (PHS) or a hydroxystyrene-styrene copolymer, having a constituent unit derived from an acrylate Acrylic resin etc. are mentioned.

In the present specification and the patent application, the "acid-decomposable group" is a group having the following acid-decomposability, which is caused by an acid (by exposure to an acid generated by the component (B)). It is known that at least a part of the bonds in the structure of the acid-decomposable group are cracked.

The "constituting unit derived from hydroxystyrene" means a constituent unit formed by cracking of an ethylenic double bond of hydroxystyrene.

The "hydroxystyrene" is a hydroxystyrene having a hydrogen atom bonded to a carbon atom at the α-position (a carbon atom to which a phenyl group is bonded), and has a substituent at a carbon atom at the α-position (atom or a group other than a hydrogen atom) The binder, as well as these derivatives. Specifically, at least the benzene ring and the hydroxyl group bonded to the benzene ring are maintained, for example, a hydrogen atom bonded to the α position of the hydroxystyrene is an alkyl group having 1 to 5 carbon atoms and a carbon number of 1 to 5. a substituent such as a halogenated alkyl group or a hydroxyalkyl group, and a benzene ring to which a hydroxyl group of a hydroxystyrene is bonded, further bonded to an alkyl group having 1 to 5 carbon atoms, or further bonded to a benzene ring to which the hydroxyl group is bonded When one or two hydroxyl groups are combined (in this case, the total number of hydroxyl groups is 2 to 3).

The "constituting unit derived from acrylate" means a constituent unit formed by cracking of an ethylenic double bond of an acrylate. The "acrylate" is substituted with a carbon atom at the α-position, in addition to an acrylate having a hydrogen atom bonded to a carbon atom at the α-position (a carbon atom bonded to a carbonyl group of acrylic acid). A group (atom or base other than a hydrogen atom). Examples of the substituent bonded to the carbon atom at the α-position include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a hydroxyalkyl group. Further, the carbon atom at the α-position of the acrylate is not particularly limited, and represents a carbon atom to which a carbonyl group of acrylic acid is bonded.

For hydroxystyrene or acrylate, the alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, specifically methyl, ethyl, propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and the like can be mentioned.

In addition, the halogenated alkyl group which is a substituent of the α-position is specifically a group in which the hydrogen atom of the above-mentioned "alkyl group as a substituent at the α-position" is partially or wholly substituted by a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom.

In addition, the hydroxyalkyl group which is a substituent at the α-position is specifically a group in which a part or all of a hydrogen atom of the above-mentioned "alkyl group as a substituent at the α-position" is substituted by a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably from 1 to 5, and 1 is most preferred.

The group to which the α-position of the hydroxystyrene or the acrylate is bonded is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom and a carbon number of 1 to 5. An alkyl group or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, and a hydrogen atom or a methyl group is particularly preferred.

Hereinafter, the acrylate-derived resin (resin (a)) will be described for the component (A1).

(Resin (a) (Acrylate Derivatized Resin))

The resin (a) is a constituent unit (a1) derived from an acrylate containing an acid-decomposable group. Further, the resin (a) contains, in addition to the constituent unit (a1), a -SO ₂ -containing cyclic group, and has a constituent unit (a0) derived from an acrylate, and an acrylate having a lactone-containing cyclic group. The constituent unit (a2) derived is preferred. The resin (a) is preferably a constituent unit (a3) derived from an acrylate having a polar group-containing aliphatic hydrocarbon group. Further, the resin (a) may contain a constituent unit (a4) derived from hydroxystyrene or a derivative thereof, and a constituent unit (a5) derived from styrene or a derivative thereof. Further, the resin (a) may contain various constituents of the acrylate-derived resin for the resist composition used in the past, in addition to the constituent units (a1) to (a5), insofar as the object of the present invention is not inhibited. unit.

[constitutive unit (a1)]

The constituent unit (a1) is a constituent unit derived from an acrylate containing an acid-decomposable group. The acid-decomposable group in the constituent unit (a1) is decomposed by the action of an acid generated by the component (B) by exposure, and becomes a hydrophilic group, and is reduced in solubility to a developing solution containing an organic solvent. The solubility of the resin (a).

The acid-dissociable group which forms the acid-decomposable group in the structural unit (a1) can be suitably selected from the base which has been proposed as an acid-dissociable group for the base resin for chemically amplified resist. It is generally known that the formation of a carboxyl group in (meth)acrylic acid or the like and a cyclic or chain-like third-order alkyl ester are generally known. An acetal type acid dissociable group such as an alkoxyalkyl group.

The "third-order alkyl ester" means that a hydrogen atom of a carboxyl group is substituted by a chain or a cyclic alkyl group to form an ester, and a terminal oxygen of a carbonyloxy group (-C(=O)-O-) is formed. A structure in which an atom, a third-order carbon atom of the aforementioned chain or cyclic alkyl group is bonded. For the third-order alkyl ester, if the acid acts, the bond is cleaved between the oxygen atom and the third-order carbon atom.

Further, the aforementioned chain or cyclic alkyl group may have a substituent.

The following is a third-order alkyl ester of a carboxylic acid, and the group having an acid dissociable property is simply referred to as a "third-order alkyl ester type acid dissociable group".

The acid-dissociable group having a branched aliphatic aliphatic group or an acid-dissociable group containing an aliphatic cyclic group may be mentioned as the third-stage alkyl ester type acid dissociable group.

The term "branched chain aliphatic" means a branched structure having no aromaticity. The structure of the "acid dissociable group having a branched aliphatic group" is not limited to a group (hydrocarbon group) composed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and is preferably saturated.

Examples of the aliphatic branched chain acid dissociable group include a group represented by -C(R ^a1 )(R ^a2 )(R ^a3 ). In the formula, R ^a1 to R ^{a3 are} each independently a linear alkyl group having 1 to 5 carbon atoms. The group represented by -C(R ^a1 )(R ^a2 )(R ^a3 ) preferably has 4 to 8 carbon atoms. Specific examples of the group represented by -C(R ^a1 )(R ^a2 )(R ^a3 ) include tert-butyl, 2-methylbutan-2-yl and 2-methylpentan-2- The base and the 3-methylpentan-3-yl group are particularly preferably tert-butyl.

The "aliphatic cyclic group" means a monocyclic group or a polycyclic group which does not have an aromatic group. The aliphatic cyclic group in the "acid-dissociable group containing an aliphatic cyclic group" may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, and an oxygen atom (=O). Etc.

The basic ring structure of the substituent which removes the aliphatic cyclic group is not limited to a group (hydrocarbon group) composed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the hydrocarbon group may be saturated or unsaturated, but is preferably saturated. The aliphatic cyclic group is preferably a polycyclic group.

Examples of the aliphatic cyclic group include a group in which one or more hydrogen atoms are removed from a monocycloalkane which is substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, and a bicycloalkane or A group in which one or more hydrogen atoms are removed from a polycycloalkane such as a tricycloalkane or a tetracycloalkane can be mentioned. More specifically, a group in which one or more hydrogen atoms are removed from a monocycloalkane such as cyclopentane or cyclohexane, or adamantane, norbornene, isobornene, tricyclodecane or tetracyclododecane A group in which one or more hydrogen atoms are removed from the polycycloalkane may be mentioned. Further, a group in which one or more hydrogen atoms are removed from the monocycloalkane or a part of a carbon atom constituting a ring in which one or more hydrogen atoms are removed from the polycycloalkane is composed of an etheric oxygen atom (-O-). Can also be replaced.

The acid dissociable group containing an aliphatic cyclic group is, for example, (i) on a ring skeleton of a monovalent aliphatic ring group, and an atom adjacent to an acid dissociable group (for example, -C(=O)- a group on the carbon atom to which O-) is bonded to a substituent (atom or a group other than a hydrogen atom) forms a group of a third-order carbon atom; (ii) A group having a monovalent aliphatic cyclic group and a branched alkyl group having a third-order carbon atom bonded thereto, and the like can be mentioned.

The substituent to be bonded to the carbon atom to which the atom adjacent to the acid dissociable group is bonded to the ring skeleton of the aliphatic ring group as the group of the above (i) is, for example, an alkyl group. The alkyl group is, for example, the same as the group of R ^a4 in the formulae (1-1) to (1-9) which will be described later.

Specific examples of the base of the above (i) include, for example, the groups represented by the following general formulae (1-1) to (1-9). In addition, as a specific example of the base of the above (ii), for example, the bases represented by the following general formulas (2-1) to (2-6) may be mentioned.

[In general formula (1-1) to (1-9), R ^a4 is an alkyl group, and g is an integer of 0 to 8]

[In general formula (2-1) to (2-6), R ^a5 and R ^{a6 are} each independently an alkyl group]

The alkyl group of the above R ^a4 is preferably a linear or branched alkyl group. The linear alkyl group preferably has 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2. Specific examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among them, methyl, ethyl or n-butyl is preferred, and methyl or ethyl is preferred.

The branched chain alkyl group preferably has 3 to 10 carbon atoms, and preferably 3 to 5 carbon atoms. Specific examples of the branched chain alkyl group include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, and neopentyl group, and isopropyl group is preferred.

g is preferably an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 1 or 2.

The alkyl group of R ^a5 to R ^a6 may be the same as the alkyl group of R ^a4 .

In the above general formulas (1-1) to (1-9) and (2-1) to (2-6), a part of the carbon atoms constituting the ring may be substituted by an etheric oxygen atom (-O-). Further, in the above general formulas (1-1) to (1-9) and (2-1) to (2-6), the hydrogen atom bonded to the carbon atom constituting the ring may be substituted with a substituent. As the substituent, there are an alkyl group having 1 to 5 carbon atoms, a fluorine atom, and a fluorinated alkane. The base can be cited.

The "acetal type acid dissociable group" is generally substituted with a hydrogen atom substituted with a hydrogen group having a hydroxyl group or a hydroxyl group, and is bonded to an oxygen atom. When an acid is generated by exposure, the acid acts, and the bond between the acetal type acid dissociable group and the oxygen atom to which the acetal type acid dissociable group is bonded is cleaved. The acetal type acid dissociable group is, for example, a group represented by the following general formula (p1).

[In the general formula (p1), R ^a7 and R ^a8 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 3, and Y represents an alkyl group having 1 to 5 carbon atoms or an aliphatic ring. Base

In the above formula (p1), n is preferably an integer of 0 to 2, preferably 0 or 1, and most preferably 0. ^Examples of the alkyl group of R ^a7 and R ^a8 include the same as the alkyl group exemplified as the substituent at the α position, and the methyl group or the ethyl group is preferably a methyl group. optimal.

It is preferred that at least one of R ^a7 and R ^a8 is a hydrogen atom. That is, the acid-dissociable group (p1) is preferably a group represented by the following general formula (p1-1).

[In the general formula (p1-1), R ^a7 , n, and Y are the same as the general formula (p1)]

The alkyl group of Y may be mentioned in the description of the above acrylate. The same as the alkyl group as the substituent at the α position.

The aliphatic cyclic group of Y may be suitably selected from the group consisting of a plurality of monocyclic or polycyclic aliphatic ring-based groups which have been proposed in the past ArF resist, and the like, for example, the above-mentioned "containing an aliphatic cyclic group" The aliphatic ring group represented by the acid dissociable group is the same.

Further, examples of the acetal-type acid dissociable group include the groups represented by the following general formula (p2).

[In the general formula (p2), R ^a8 and R ^{a9 are} each independently a linear or branched alkyl group or a hydrogen atom, and R ^a10 is a linear, branched or cyclic alkyl group, or R ^a8 and R Each of ^{a10 is} independently a linear or branched alkyl group, and the terminal of R ^a8 is bonded to the terminal of R ^a10 to form a ring. 〕

For R ^a8 and R ^a9 , the alkyl group preferably has 1 to 15 carbon atoms. When R ^a8 and R ^a9 are an alkyl group, the alkyl group may be linear or branched. As the alkyl group, an ethyl group or a methyl group is preferred, and a methyl group is preferred. Particularly, it is preferred that one of R ^a8 and R ^a9 is a hydrogen atom and the other is a methyl group.

R ^a10 is a linear, branched or cyclic alkyl group, and preferably has 1 to 15 carbon atoms. When R ^a10 is a linear or branched alkyl group, the carbon number is preferably from 1 to 5. As to R ^a10 ethyl, preferably methyl group, ethyl group is particularly preferred in order.

When R ^a10 is a ring ^shape , the carbon number is preferably 4 to 15, preferably 4 to 12, and particularly preferably 5 to 10. Specific examples of the case where R ^a10 is a cyclic alkyl group include a monocycloalkane which is substituted or unsubstituted with a fluorine atom or a fluorinated alkyl group; and is removed by a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. A group of one or more hydrogen atoms or the like. Specific examples thereof include a monocycloalkane such as cyclopentane or cyclohexane, or one or more hydrogen atoms removed from a polycycloalkane such as adamantane, norbornene, isobornene, tricyclodecane or tetracyclododecane. Bases and the like can be cited. Among them, a group in which one or more hydrogen atoms are removed from adamantane is preferred.

Further, in the above formula (p2), R ^a8 and R ^{a10 are} each independently a linear or branched alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), ^and the terminal of R ^a10 and R ^a8 are The ends can also be combined.

In this case, R ^a8, R ^a10, and R the oxygen atoms bonded ^a10, the carbon atom bonded with the oxygen atom and R ^A8 form a cyclic group. As a ring type, a 4 to 7 member ring is preferred, and a 4 to 6 member ring is preferred. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

Specific examples of the constituent unit (a1) include a constituent unit represented by the following general formula (a1 - 0), a constituent unit represented by the following general formula (a1-0-2), and the like.

[In the general formula (a1-0-1) to (a1-0-2), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and X ^a1 is an acid dissociation property. a group, Y ^a1 is a divalent linking group, and X ^a2 is an acid dissociable group]

For the general formula (a1-0-1), each of the alkyl group and the halogenated alkyl group of R The alkyl group or the halogenated alkyl group which is a substituent at the α-position which is mentioned in the description of the above acrylate is the same. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, and preferably a hydrogen atom or a methyl group.

X ^a1 is only an acid-dissociable group, and is not particularly limited, and examples thereof include a third-stage alkyl ester type acid dissociable group and an acetal acid dissociable group, and a third-order alkyl ester. The acid dissociable group is preferred.

For the general formula (a1-0-2), R is the same as described above. X ^a2 is the same as X ^a1 in the general formula (a1-0-1). The divalent linking group of Y ^a1 is not particularly limited, and examples thereof include an alkylene group, a divalent aliphatic cyclic group, a divalent aromatic ring group, and a divalent linking group containing a hetero atom.

When Y ^a1 is an alkylene group, the carbon number is preferably from 1 to 10, preferably from 1 to 6, particularly preferably from 1 to 4, and most preferably from 1 to 3.

When Y ^a1 is a divalent aliphatic cyclic group, the aliphatic cyclic group may be an acid-dissociating group containing an aliphatic cyclic group, in addition to a group having two or more hydrogen atoms removed. The aliphatic ring group represented by the group is the same. As the aliphatic cyclic group in Y ^a1 , two or more hydrogen atoms are removed from cyclopentane, cyclohexane, norbornene, isobornene, adamantane, tricyclodecane or tetracyclododecane. The base is especially good.

When Y ^a1 is a divalent aromatic ring group, the aromatic ring group may be a group in which two hydrogen atoms are removed from an aromatic hydrocarbon ring which may have a substituent. The carbon number of the aromatic hydrocarbon ring is preferably from 6 to 15. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. They are also particularly good at benzene or naphthalene rings.

Examples of the substituent which may have an aromatic hydrocarbon ring include a halogen atom, an alkyl group, an alkoxy group, a halogenated lower alkyl group, and an oxygen atom (=O). Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom.

When Y ^a1 is a divalent linking group containing a hetero atom, as a divalent linking group containing a hetero atom, there are -O-, -C(=O)-O-, -C(=O)-, -OC(= O)-O-, -C(=O)-NH-, -NH- (H may be substituted by a substituent such as an alkyl group or a fluorenyl group), -S-, -S(=O) ₂ -, -S ( =O) ₂ -O-, a group represented by the formula -AOB-, a formula -[AC(=O)-O] _m' -B-, a group represented by -AOC(=O)-B-, etc. may be mentioned. Wherein formula -AOB -, - [AC (= O) -O] m '-B-, or -AOC (= O) -B-, A is and B are each independently a substituent group may be a divalent hydrocarbon group of, -O- is an oxygen atom, and m' is an integer of 0-3.

When Y ^a1 is -NH-, H may be substituted by a substituent such as an alkyl group or a fluorenyl group. The number of carbon atoms of the substituent (alkyl group, mercapto group, etc.) is preferably from 1 to 10, more preferably from 1 to 8, and particularly preferably from 1 to 5.

When Y ^a1 is -AOB-, -[AC(=O)-O] _m' -B-, or -AOC(=O)-B-, A and B are each independently a divalent hydrocarbon group which may have a substituent. When the hydrocarbon group is "having a substituent", it means that a part or all of the hydrogen atom in the hydrocarbon group is substituted by a group or an atom other than the hydrogen atom.

The hydrocarbon group in A may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. The aliphatic hydrocarbon group in A may be saturated or unsaturated, and is generally preferably saturated.

Specific examples of the aliphatic hydrocarbon group in A include a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group having a ring in the structure. Straight The carbon number of the branched or branched aliphatic hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 8, more preferably from 2 to 5, and most preferably 2.

As the linear aliphatic hydrocarbon group, a linear alkyl group is preferred, and specifically, a methyl group, an ethyl group [-(CH ₂ ) ₂ -], a tris-methyl [-(CH ₂ ) ₃ -] Further, tetramethyl-[-(CH ₂ ) ₄ -], pentamethyl-[-(CH ₂ ) ₅ -], and the like can be mentioned.

As the branched chain aliphatic hydrocarbon group, a branched alkyl group is preferred. Specifically, there are -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 - or the like alkyl-extension methyl group; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, - An alkyl vinyl group of C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, etc.; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -alkyl-alkyl-methyl, etc.; alkyl-alkylene such as -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, etc. Bases and the like can be cited. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

These linear or branched aliphatic hydrocarbon groups may or may not have a substituent. Examples of the substituent include a fluorinated alkyl group having 1 to 5 carbon atoms and an oxygen atom (=O) substituted by a fluorine atom or a fluorine atom.

The cyclic aliphatic hydrocarbon group has a cyclic aliphatic hydrocarbon group (a group from which two hydrogen atoms are removed from the aliphatic hydrocarbon ring), a cyclic aliphatic hydrocarbon group bonded to the terminal of the aforementioned chain aliphatic hydrocarbon group, or a chain-like The base etc. in the middle of an aliphatic hydrocarbon group are mentioned. The carbon number of the cyclic aliphatic hydrocarbon group is preferably from 3 to 20, more preferably from 3 to 12.

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic group, two hydrogens are removed from a monocycloalkane having 3 to 6 carbon atoms. The base of the atom is preferred, and examples of the monocycloalkane include cyclopentane, cyclohexane and the like. As the polycyclic group, a group in which two hydrogen atoms are removed by a polycycloalkane having 7 to 12 carbon atoms is preferable, and as the polycycloalkane, specifically, adamantane, norbornene, isobornene, tricyclodecane, Tetracyclododecane and the like can be mentioned.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, and an oxygen atom (=O).

As A, a linear aliphatic hydrocarbon group is preferred, and a linear alkyl group is preferred, and a linear alkyl group having 1 to 5 carbon atoms is more preferred, and a methyl group or an ethyl group is preferred. Very good.

As B, a linear or branched aliphatic hydrocarbon group is preferred, and a methyl group, an ethyl group or an alkyl group is preferred. The alkyl group in the alkyl 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.

Further, for the group of the formula -[AC(=O)-O] _m' -B-, m' is an integer of 0 to 3, preferably an integer of 0 to 2, preferably 0 or 1, 1 is the best.

Specific examples of the constituent unit (a1) include the following structural formulas (a1-1) to (a1-4).

[In the general formulae (a1-1) to (a1-4), R, R ^a7 , R ^a8 , n, Y and Y ^{a1 are} each the same as defined above, and X ^a3 represents a third-order alkyl ester type acid dissociation. Sex base

In the general formulae (a1-1) and (a1-3), X ^a3 may be the same as the above-mentioned third-stage alkyl ester type acid dissociable group.

As ^{R a7, R a8, n,} Y, may be mentioned in each of "acetal-type acid solution dissociable group" as mentioned above illustrated by the general formula ^{(p1) R a7, R a8} , n, Y The same.

As Y ^a1, include those the same as in the above general formula (a1-0-2) Y ^a1 is.

Specific examples of the constituent units shown in the above general formulas (a1-1) to (a1-4) will be given below. In the following formulae, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

As the constituent unit (a1), one type or two types may be used alone. Used on. The constituent unit (a1) is preferably a constituent unit represented by the general formula (a1-1) or (a1-3), and specifically, is selected from the above formula (a1-1-1) to (a1-1). -4), (a1-1-20)~(a1-1-23), formula (a1-1-26), formula (a1-1-32)~(a1-1-33) and formula (a1- It is preferable that at least one of the constituent units represented by 3-25) to (a1-3-32) is preferable.

Further, as a constituent unit (a1), the following general formula (a1-1-01) including the constituent units represented by the formulas (a1-1-1) to (a1-1-3) and the formula (a1-1-26) ), including (a1-1-16)~(a1-1-17), (a1-1-20)~(a1-1-23), and (a1-1-32)~(a1) -1-33) The following general formula (a1-1-02) of the structural unit shown, and the following general structural units including the formula (a1-3-25) to (a1-3-26) In the formula (a1-3-01), the following general formula (a1-3-02) including the constituent units represented by the formulas (a1-3-27) to (a1-3-28), including The constituent units of the formulae (a1-3-29) to (a1-3-32) are preferably the following general formula (a1-3-03).

[In the general formula (a1-1-01) to (a1-1-02), 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, and R ^a11 represents a carbon number of 1; ~5 alkyl, R ^a12 represents an alkyl group having 1 to 5 carbon atoms, and h represents an integer of 1 to 6]

The general formula (a1-1-01) is the same as the above for R. The alkyl group of R ^a11 may be the same as the alkyl group of R, and a methyl group, an ethyl group or an isopropyl group is preferred.

For the general formula (a1-1-02), it is the same as the above for R. The alkyl group of R ^a12 may be the same as the alkyl group in R, and a methyl group, an ethyl group or an isopropyl group is preferred. H is preferably 1 or 2, and 2 is optimal.

[In general formula (a1-3-01) to (a1-3-02), 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, and R ^a4 is an alkyl group; R ^a13 is a hydrogen atom or a methyl group, y is an integer of 1 to 10, and n' is an integer of 1 to 6]

In the general formula (a1-3-01) or (a1-3-02), it is the same as the above for R. R ^a13 is preferably a hydrogen atom. R ^a4 is the same as the alkyl group ~ (1-9) of R in the formula (1-1) ^a4, methyl, ethyl or isopropyl group is preferred. Y is preferably an integer from 1 to 8, and an integer from 2 to 5 is particularly preferred, with 2 being the best. n' is preferably 1 or 2.

[In general formula (a1-3-03), R is the same as above, and Y ^a2 and Y ^{a3 are} each independently a divalent linking group, X ^a4 is an acid dissociable group, and w is an integer of 0 to 3]

In the general formula (a1-3-03), the divalent linking group in Y ^a2 and Y ^a3 may be the same as Y ^a1 in the above general formula (a1-3). As Y ^a2 , a divalent hydrocarbon group which may have a substituent is preferred, a linear aliphatic hydrocarbon group is preferred, and a linear alkyl group is more preferred. Among them, a linear alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group and an ethyl group are preferred. As Y ^a3 , a divalent hydrocarbon group which may have a substituent is preferred, a linear aliphatic hydrocarbon group is preferred, and a linear alkyl group is more preferred. Among them, a linear alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group and an ethyl group are preferred. The acid dissociable group in X ^a4 may be the same as the above, and the third-stage alkyl ester type acid dissociable group is preferably the above-mentioned ring skeleton of the (i) monovalent aliphatic ring group. The group of the third-order carbon atom is preferred, and the group represented by the above general formula (1-1) is also preferred. w is an integer of 0 to 3, w is preferably an integer of 0 to 2, preferably 0 or 1, and 1 is optimal.

Further, as the constituent unit (a1), the unit represented by the following general formula (1-5) is also preferable.

[In the general formula (a1-5), R is a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Y ^a4 is an aliphatic hydrocarbon group having a substituent, and Z is An acid-decomposable group containing a third-stage ester type acid dissociable group or an acetal type acid dissociable group is a terminal monovalent organic group, a is an integer of 1 to 3, and b is an integer of 0 to 2, and a+b=1~3, c, d, and e are each an integer of 0~3]

In the general formula (a1-5), specific examples of R are the same as described above. Among them, R is preferably a hydrogen atom or a methyl group.

In the general formula (a1-5), Y ^a4 is an aliphatic hydrocarbon group which may have a substituent. The aliphatic hydrocarbon group in Y ^a4 may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group. Specific examples of the substituent which substitutes a part or all of the hydrogen atom constituting the aliphatic hydrocarbon group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (=O), a cyano group, an alkyl group and the like.

When the substituent is an alkoxy group, it is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert- group. The butoxy group is more preferred, and the methoxy group and the ethoxy group are most preferred. When the substituent is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine. Atom, an iodine atom, etc., preferably a fluorine atom. When the substituent is a halogenated alkyl group, it is an alkyl group having 1 to 5 carbon atoms, for example, a part or all of a hydrogen atom of an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. The group substituted by the above halogen atom is exemplified. When the substituent is an alkyl group, it is an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

When Y ^a4 is a linear or branched aliphatic hydrocarbon group, the carbon number is preferably from 1 to 10, more preferably from 1 to 5, and most preferably from 1 to 3. Specifically, a chain alkyl group is preferred.

When Y ^a4 is a cyclic aliphatic hydrocarbon group (aliphatic cyclic group), the structure of the basic ring (aliphatic ring) other than the substituent of the aliphatic cyclic group is not limited to the ring formed of carbon and hydrogen ( The hydrocarbon ring may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom in the structure of the ring (aliphatic ring). Further, the "hydrocarbon ring" may be either saturated or unsaturated, and is preferably saturated.

The aliphatic cyclic group may be any of a polycyclic group or a monocyclic group. The aliphatic cyclic group may be substituted by a lower alkyl group, a fluorine atom or a fluorinated alkyl group. Examples of the aliphatic cyclic group include a group in which two or more hydrogen atoms are removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane. More specifically, monocycloalkane such as cyclopentane or cyclohexane, or two polycycloalkanes such as adamantane, norbornene, isobornene, tricyclodecane, and tetracyclododecane are removed. The base of the above hydrogen atom and the like can be mentioned.

Further, examples of the aliphatic cyclic group include a group in which two or more hydrogen atoms are removed from tetrahydrofuran or tetrahydropyran.

In the case of the general formula (a1-5), when Y ^a4 is an aliphatic cyclic group, a polycyclic group is preferred, and a group in which two or more hydrogen atoms are removed from adamantane is particularly preferred.

In the general formula (a1-5), Z is an acid-decomposable group containing a third-stage ester type acid dissociable group or an acetal type acid dissociable group. In the present specification and the scope of the patent application, "organic group" means a group containing a carbon atom and may have an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom). Atom, etc.), etc.).

Preferable examples of the case where Z is an acid-decomposable group containing a third-stage ester type acid dissociable group include a third-order alkoxycarbonyl group and a third-order alkoxycarbonyl group. The alkylene group contained in the alkoxycarbonyl group of the 3rd stage is preferably an alkylene group having a carbon number of 1 to 5 such as a methyl group or an ethyl group.

The preferred third-order alkyl group contained in the acid-decomposable group containing the third-stage ester type acid dissociable group may be a group having a branched chain or a cyclic aliphatic group. A preferred example of the case where the third-order alkyl group is a branched chain is the group represented by the above -C(R ^a1 )(R ^a2 )(R ^a3 ). Specific examples of the group represented by -C(R ^a1 )(R ^a2 )(R ^a3 ) include tert-butyl, 2-methylbutan-2-yl and 2-methylpentan-2- The base and the 3-methylpentan-3-yl group are particularly preferably tert-butyl. Preferred examples of the case where the third-order alkyl group is a group of a cyclic aliphatic group are the above general formulas (1-1) to (1-9) and general formulas (2-1) to (2-6). The base shown can be cited.

Among Z, an acid-decomposable group which already contains a third-stage ester type acid dissociable group is preferred, and a third-order alkoxycarbonyl group is preferred. Preferred examples of the third alkoxycarbonyl group include tert-butoxycarbonyl (t-boc), Tert-pentyloxycarbonyl or the like is preferably tert-butoxycarbonyl.

In the general formula (a1-5), a is an integer of 1 to 3, b is an integer of 0 to 2, and a + b = 1 to 3. a is preferably 1, b is preferably 0, and a+b is preferably 1.

Further, c is an integer of 0 to 3, preferably 0 or 1, and 0 is preferred. d is an integer of 0 to 3, preferably 0 or 1, and 0 is preferred. e is an integer of 0 to 3, preferably 0 or 1, and 0 is preferred.

The constituent unit (a1-5) is preferably a constituent unit represented by the following general formula (a1-5-1) or (a1-5-2).

[In general formula (a1-5-1), R, Z, b, c, d, and e are the same as described above]

[In the general formula (a1-5-2), R, Z, a, b, c, d, and e are each the same as described above. c" is an integer from 1 to 3]

In the general formula (a1-5-2), c" is an integer of 1 to 3, preferably 1 or 2, and preferably 1 is preferred.

When c in the general formula (a1-5-2) is 0, the oxygen atom at the terminal of the carbonyloxy group (-C(=O)-O-) of the acrylate is not bonded to the oxygen atom in the ring group. It is preferred that the combined carbon atoms are combined. That is, when c is 0, it is preferable that two or more carbon atoms are present between the terminal oxygen atom and the oxygen atom in the cyclic group (except that the number of the carbon atoms is 1 (that is, an acetal bond)) .

In the resin (a), the ratio of the constituent unit (a1) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and preferably 25 to 90% of the total constituent unit constituting the resin (a). 50% of the mole is better. By setting the ratio of the constituent unit (a1) to this range, it is possible to easily prepare an easy-to-form resist composition in which the pattern is formed.

[constitutive unit (a0)]

The constituent unit (a0) is a constituent unit derived from an acrylate containing a ring group containing -SO ₂ -. Wherein called containing -SO ₂ - group is a cyclic, skeleton containing ring containing -SO ₂ - group of the cyclic ring, specifically, -SO ₂ - in the sulfur atom (S) to form a cyclic group A part of the ring base of the ring skeleton. For containing -SO ₂ - cyclic group, which will be contained in the ring skeleton -SO ₂ - as a ring start number of the first ring, called a monocyclic group if only one ring, further having When other loops are constructed, they are called polycyclic bases regardless of their structure.

The ring group containing -SO ₂ - may be a monocyclic ring or a polycyclic ring. Further, the -SO ₂ -containing ring group has a ring group of -O-SO ₂ - in its ring skeleton, that is, -OS- in -O-SO ₂ - forms a sulphur of a part of the ring skeleton A sultone ring is preferred.

The carbon number of the ring group containing -SO ₂ - is preferably from 3 to 30, preferably from 4 to 20, particularly preferably from 4 to 15, and most preferably from 4 to 12. However, the carbon number is the number of carbon atoms constituting the ring skeleton, which is the number of carbons which are not contained in the substituent.

Containing -SO ₂ - may be a cyclic group containing -SO ₂ - aliphatic cyclic group, also containing -SO ₂ - aromatic cyclic group, containing -SO ₂ - aliphatic cyclic group It is better. As the aliphatic ring group containing -SO ₂ -, at least one of the carbon atoms constituting the ring skeleton thereof is removed by at least one of -SO ₂ - or -O-SO ₂ -. A base of a hydrogen atom. More specifically, by constituting the ring skeleton thereof -CH ₂ - group removing at least one hydrogen atom of the substituted aliphatic hydrocarbon ring, the ring is composed of -CH ₂ -CH ₂ - - In order -SO ₂ -O A group in which -SO ₂ - is substituted with at least one hydrogen atom in the aliphatic hydrocarbon ring to be substituted may be mentioned. The carbon number of the aliphatic hydrocarbon ring is preferably from 3 to 20, more preferably from 3 to 12.

The alicyclic hydrocarbon group which removes at least one hydrogen atom from the aliphatic hydrocarbon ring may be a polycyclic ring or a monocyclic ring. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms are removed from a monocycloalkane having 3 to 6 carbon atoms, and examples of the monocycloalkane include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms. Specific examples of the polycycloalkane include adamantane, norbornene, and isobornene. , tricyclodecane, and tetracyclododecane.

The cyclic group containing -SO ₂ - may have a substituent. The substituent is, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (=O), -COOR", -OC(=O)R"(R" is a hydrogen atom or an alkyl group. And a hydroxyalkyl group, a cyano group, etc. are mentioned.

The alkyl group as a substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably a linear or branched chain. 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, a hexyl group and the like. Among them, methyl or ethyl is preferred, and methyl is preferred.

The alkoxy group as a substituent is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably a linear or branched chain. Specific examples of the alkyl group-bonded oxygen atom (-O-) group exemplified as the alkyl group as the above substituent are exemplified.

The halogen atom as a substituent may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferred.

The halogenated alkyl group as a substituent may be a group in which a part or all of a hydrogen atom of the above-mentioned alkyl group is substituted by the above halogen atom. The halogenated alkyl group as the substituent may be a group in which a part or all of the hydrogen atom of the alkyl group exemplified as the alkyl group as the substituent is substituted by the halogen atom. As the halogenated alkyl group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is particularly preferred.

R- in the above -COOR" and -OC(=O)R" are preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R" is a linear chain. The number of carbon atoms in the case of a branched or branched alkyl group is preferably from 1 to 10, more preferably from 1 to 5. As the linear or branched chain alkyl group, a methyl group or an ethyl group is particularly preferred. When R" is a cyclic alkyl group, the carbon number is preferably from 3 to 15, and from 4 to 12 is compared. Good, with 5~10 as the best. Specific examples of the cyclic alkyl group include a group in which one or more hydrogen atoms are removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane. More specifically, a monocycloalkane such as cyclopentane or cyclohexane or one or more polycycloalkanes such as adamantane, norbornene, isobornene, tricyclodecane or tetracyclododecane may be removed. The base of a hydrogen atom, etc.

The hydroxyalkyl group as the substituent is preferably a group having 1 to 6 carbon atoms, and specific examples of the hydrogen atom of the alkyl group exemplified as the alkyl group as the substituent are substituted with a hydroxyl group.

Specific examples of the ring group containing -SO ₂ - include the groups represented by the following general formulas (0-1) to (0-4).

[In the general formula (0-1) to (0-4), A' is an alkylene group, an oxygen atom or a sulfur atom which may have an oxygen atom or a sulfur atom and has a carbon number of 1 to 5, and z is an integer of 0 to 2. , R ^a14 is alkyl, alkoxy, alkyl halide, hydroxy, -COOR", -OC(=O)R", hydroxyalkyl or cyano, and R" is a hydrogen atom or an alkyl group]

In the general formula (0-1) to (0-4), A' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), or an oxygen atom, or Sulfur atom.

As the alkyl group having 1 to 5 carbon atoms in A', a linear or branched chain alkyl group is preferred, and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, etc. may be mentioned. Out. When the alkylene group contains an oxygen atom or a sulfur atom, as a specific example thereof, a terminal of the alkylene group or a group of -O- or -S-, such as -O-CH ₂ may be mentioned. -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ -, etc. may be mentioned. As A', an alkylene group or a -O- having a carbon number of 1 to 5 is preferred, and an alkylene group having a carbon number of 1 to 5 is preferred, and a methyl group is preferred.

z can be any of 0~2, with 0 being the best. When z is 2, the plural R ^a14 may be the same or different.

Examples of the alkyl group, the alkoxy group, the alkyl halide group, the -COOR", the -OC(=O)R", and the hydroxyalkyl group in R ^a14 may be the ring group having the -SO ₂ - group as described above. The alkyl group, the alkoxy group, the halogenated alkyl group, the -COOR", the -OC(=O)R" group, and the hydroxyalkyl group are the same as the substituent.

Specific ring groups represented by the above general formulas (0-1) to (0-4) are exemplified below. Further, "Ac" in the formula represents an ethyl group.

As the cyclic group containing -SO ₂ -, the above is preferably a group represented by the general formula (0-1), and is selected from the group consisting of formulas (0-1-1), (0-1-18), (0). At least one of the groups shown in any of -3-1) and (0-4-1) is preferred, and the group represented by the above chemical formula (0-1-1) is preferred.

More specifically, examples of the constituent unit (a0) include constituent units represented by the following general formula (a0-1).

[In the general formula (a0-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R ^a15 is a cyclic group having -SO ₂ -, and R ^a16 is Single bond or divalent linkage]

In the formula (a0-1), R is the same as described above. R ^a15 is the same as the above-mentioned ring-form group containing -SO ₂ -. R ^a16 may be any of a single bond or a divalent linking group. From the viewpoint of exhibiting an excellent effect of the present invention, a divalent linking group is preferred.

The divalent linking group in R ^a16 is not particularly limited, and examples thereof include a divalent linking group in Y ^a1 in the general formula (a1-0-2) exemplified in the structural unit (a1). The same as those cited. Among them, those having an alkyl group or an ester bond (-C(=O)-O-) are preferred. The alkyl group is preferably a linear or branched alkyl group. Specifically, the same as the linear alkylene group or the branched alkyl group which is an aliphatic hydrocarbon group in the above Y ^a1 can be mentioned. The divalent linking group having an ester bond is preferably a group represented by the general formula: -R ^a17 -C(=O)-O- (wherein, R ^a17 is a divalent linking group). That is, the constituent unit (a0) is preferably a constituent unit represented by the following general formula (a0-11).

[In the general formula (a0-11), R and R ^{a15 are} each the same as (a0-1), and R ^a17 is a divalent linking group]

R ^a17 is not particularly limited, and examples thereof include a divalent linking group in Y ^a1 in the general formula (a1-0-2) described in the description of the constituent unit (a1). The same.

The divalent linking group of R ^a17 is preferably a linear or branched alkyl group, a divalent alicyclic hydrocarbon group or a divalent linking group containing a hetero atom. Examples of the linear or branched chain alkyl group, the divalent alicyclic hydrocarbon group, and the hetero atom-containing divalent linking group include a linear or branched chain which is a preferred example of the above Y2. The same ones of the alkyl group, the divalent alicyclic hydrocarbon group, and the divalent linking group containing a hetero atom. In the above, a linear or branched chain alkyl group or a divalent linking group containing an oxygen atom as a hetero atom is preferred.

As the linear alkyl group, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred. As a branched chain alkyl group, preferably an alkyl methyl group or an alkyl vinyl group, and -CH(CH ₃ )-, -C(CH ₃ ) ₂ - or -C(CH ₃ ) ₂ CH ₂ - Very good.

As the divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferred, and the above-mentioned general formula -AOB-, or -[AC(=O)-O]m'-B- Or a group represented by -AOC(=O)-B- is preferred. Among them, the group represented by the formula -AOC(=O)-B- is preferred, and the group represented by -(CH ₂ ) _c0 -C(=O)-O-(CH ₂ ) _d0 - is particularly preferred. C0 is an integer from 1 to 5, preferably 1 or 2. D0 is an integer from 1 to 5, preferably 1 or 2.

The constituent unit (a0) is preferably a constituent unit represented by the following general formula (a0-21) or (a0-22), and a constituent unit represented by the formula (a0-22) is preferable.

[In the general formula (a0-21) to (a0-22), R, A', R ^a14 , z and R ^{a17 are} each the same as described above. 〕

In the general formula (a0-21), A' is preferably a methyl group, an oxygen atom (-O-) or a sulfur atom (-S-).

R ^{a17 is} preferably a linear or branched alkyl group or a divalent linking group containing an oxygen atom. ^Examples of the linear or branched chain alkyl group in R ^a17 and the divalent linking group containing an oxygen atom include a linear or branched alkyl group and an oxygen atom-containing compound. The same price chain.

The constituent unit represented by the general formula (a0-22) is preferably a constituent unit represented by the following general formula (a0-22a) or (a0-22b).

[In the general formula (a0-22a) to (a0-22b), R and A' are each the same as described above, and f0, g0, and h0 are each independently an integer of 1 to 3]

The constituent unit (a0) containing the resin (a) may be one type or two or more types. The ratio of the constituent unit (a0) in the resin (a) is preferably 5 to 60 mol%, and preferably 10 to 50 mol%, based on the total of the constituent units constituting the resin (a). It is better to use 15 to 40% of the moles. When it is more than the lower limit value, sensitivity, resolution, and etching characteristics can be improved. When it is less than the upper limit, the balance with other constituent units can be obtained, and the solubility in an organic solvent is also good.

[constitutive unit (a2)]

The constituent unit (a2) is an acrylate containing a cyclic group containing a lactone. The constituent units derived. Here, the lactone-containing cyclic group represents a cyclic group containing one ring (lactone ring) having a -O-C(=O)- structure. When the lactone ring is calculated as the first ring, if it is only a lactone ring, it is called a monocyclic group. If there are other ring structures, it is called a polycyclic group regardless of its structure.

The lactone ring group of the structural unit (a2) is effective from the viewpoint of improving the adhesion to the substrate of the resist film when the resin (a) is used for the formation of the resist film.

The lactone ring group in the structural unit (a2) is not particularly limited, and any of them may be used. Specifically, examples of the lactone-containing monocyclic group include a group in which one hydrogen atom is removed from 4 to 6 membered ring lactones, for example, a group in which one hydrogen atom is removed from β-propiolactone, A group in which one hydrogen atom is removed from γ-butyrolactone, a group in which one hydrogen atom is removed from δ-valerolactone, or the like. Further, examples of the polycyclic group having a lactone include a group in which one hydrogen atom is removed from a bicycloalkane, a tricycloalkane or a tetracycloalkane having a lactone ring.

Specific examples of the constituent unit (a2) are as follows. In the following formulae, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The resin (a) may be used singly or in combination of two or more kinds as the constituent unit (a2). In the resin (a), the ratio of the constituent unit (a2) is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, based on the total of the constituent units constituting the resin (a). ~50% of the mole is better.

[constitutive unit (a3)]

The constituent unit (a3) is a constituent unit (a3) derived from an acrylate containing a polar group-containing aliphatic hydrocarbon group. Resin (a) has a composition The unit (a3) can improve the hydrophilicity of the resin (a), and can improve sensitivity, resolution, etching characteristics, and the like. The constituent unit (a3) is a constituent unit that is not equivalent to the constituent units (a1), (a0), and (a2). In other words, even if it is a "constituting unit derived from an acrylate containing a polar group-containing aliphatic hydrocarbon group", the constituent units corresponding to the constituent units (a1), (a0), and (a2) are not equivalent to constituent units ( A3).

Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group (a hydroxyalkyl group in which a part of a hydrogen atom of an alkyl group is substituted by a fluorine atom). Among them, hydroxyl groups and carboxyl groups are preferred, and hydroxyl groups are particularly preferred.

The number of polar groups bonded to the aliphatic hydrocarbon group in the constituent unit (a3) is not particularly limited, and is preferably 1 to 3, and more preferably one. The aliphatic hydrocarbon group to which the polar group is bonded may be saturated or unsaturated, and is preferably saturated.

More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group having a ring in the structure.

The "linear or branched aliphatic hydrocarbon group" preferably has a carbon number of 1 to 12, preferably 1 to 10, more preferably 1 to 8, and more preferably 1 to 6. The linear or branched aliphatic hydrocarbon group may be partially or wholly substituted by a substituent other than a polar group. Examples of the substituent other than the polar group include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (=O). Further, the linear or branched aliphatic hydrocarbon group may have a divalent group containing a hetero atom between the carbon atoms. The "divalent group containing a hetero atom" is exemplified as "a heterovalent group which is a divalent linking group of Y ^a1 in the general formula (a1-0-2) in the description of the above-mentioned constituent unit (a1). The same as the two-valent linking group of the atom.

When the aliphatic hydrocarbon group is linear or branched, the constituent unit (a3) is preferably a constituent unit represented by the following general formula (a3-1) or (a3-2).

[In the general formulas (a3-1) and (a3-2), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and R ⁸¹ is a linear or branched chain. An alkyl group, R ⁸² is an alkyl group which may contain a divalent group containing a hetero atom.

In the general formula (a3-1), the carbon number of the alkyl group in R ⁸¹ is preferably from 1 to 12, more preferably from 1 to 10. In the general formula (a3-2), the carbon number of the alkylene group in R ⁸² is preferably from 1 to 12, more preferably from 1 to 10, particularly preferably from 1 to 6.

When the alkylene group is an alkylene group having 2 or more carbon atoms, a divalent group containing a hetero atom may be interposed between the carbon atoms of the alkylene group. The "divalent group containing a hetero atom" is a "containing a hetero atom" as a divalent linking group of Y ^a1 in the general formula (a1-0-2) in the description of the constituent unit (a1). The same as the two-valent link.

R ^{82 is} particularly preferably an alkylene group which does not contain a divalent group containing a hetero atom or an alkylene group which contains a divalent group which is an oxygen atom of a hetero atom. As the alkylene group having a divalent group containing an oxygen atom, a group represented by -AOB- or -AOC(=O)-B- is preferred. In the formula, each of A and B is independently a divalent hydrocarbon group which may have a substituent, and may be exemplified by -AOB- or -AOC(=O)-B- and A in the description of the constituent unit (a1) And B are the same. Among them, the group represented by -AOC(=O)-B- is preferably -(CH ₂ ) _f -OC(=O)-(CH ₂ ) _g' - [wherein f and g' are each Independently an integer from 1 to 3 is preferred.

The "aliphatic hydrocarbon group containing a ring in the structure" may be a group in which a cyclic aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group is bonded to the terminal of the chain aliphatic hydrocarbon group or to the chain aliphatic hydrocarbon group. The cyclic aliphatic hydrocarbon group preferably has a carbon number of from 3 to 30. Further, the cyclic aliphatic hydrocarbon group may be a polycyclic ring or a monocyclic ring, and a polycyclic ring is preferred.

Specific examples of the cyclic aliphatic hydrocarbon group include a resin for a resist composition for an ArF excimer laser, which is selected by a majority of the applicants. For example, a monocyclic aliphatic hydrocarbon group is preferably a group in which two or more hydrogen atoms are removed from a monocycloalkane having 3 to 20 carbon atoms, and examples of the monocycloalkane include cyclopentane and cyclohexane. The polycyclic aliphatic hydrocarbon group is preferably a group in which two or more hydrogen atoms are removed from a polycycloalkane having 7 to 30 carbon atoms. Specific examples of the polycycloalkane include adamantane, norbornene, and isobornyl. Alkene, tricyclodecane, tetracyclododecane, and the like.

The cyclic aliphatic hydrocarbon group is such that a part or the whole of the hydrogen atom may be substituted by a substituent other than the aforementioned polar group. Examples of the substituent other than the polar group include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, and an oxygen atom (=O).

When the aliphatic hydrocarbon group contains a ring in the structure, the constituent unit (a3) is represented by the following general formula (a3-3), (a3-4) or (a3-5). The constituent units are better.

[In general formulas (a3-3) to (a3-5), R is the same as above, j is an integer from 1 to 3, k' is an integer from 1 to 3, t' is an integer from 1 to 3, and 1' is An integer from 1 to 5, s' is an integer from 1 to 3]

In the general formula (a3-3), j is preferably 1 or 2, and more preferably 1 is used. When j is 2, it is preferred to combine the hydroxyl group with the third and fifth positions of the adamantyl group. When j is 1, the third position of the hydroxy group and the adamantyl group is preferred.

In the general formula (a3-4), k' is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornene group.

In the general formula (a3-5), t' is preferably 1, 1' is preferably 1 and s' is preferably 1. In the formula (a3-5), the oxygen atom (-O-) of the carbonyloxy group is preferably bonded to the second or third position of the norbornene ring. The fluorinated alkyl alcohol group is preferably bonded to the 5th or 6th position of the norbornene group.

The constituent unit (a3) containing the resin (a) may be one type or two or more types. The constituent unit (a3) is preferably a constituent unit having any one of the above general formulas (a3-1) to (a3-5), and is a constituent unit having a general formula (a3-3). good.

The resin (a) is a ratio of the constituent unit (a3) in the resin (a) when the constituent unit (a3) is present, and is 1 to 50 mol% for the total of the constituent units constituting the resin (a). Preferably, 5 to 40 mol% is preferred, and 5 to 25 mol% is preferred.

[constitutive unit (a4)]

The constituent unit (a4) is a constituent unit derived from hydroxystyrene. Specific examples of the structural unit (a4) include the following structural formulae (a4-1) to (a4-2).

[In the general formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and R ^a18 is a halogen atom, a lower alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group, p It is an integer from 1 to 3, and q is an integer from 0 to 4. However, p+q is 1 or more and 5 or less. In the general formula (a5-2), X ^a5 represents an acid dissociable dissolution inhibiting group]

In the general formulae (a4-1) to (a4-2), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. The preferred ones of R are the same as those described above.

In the general formulae (a4-1) to (a4-2), R ^a18 is a halogen atom, a lower alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group. The halogen atom of R ^a18 may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is particularly preferably a fluorine atom. The lower alkyl group of R ^{a18 is} a lower alkyl group having 1 to 5 carbon atoms, and 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, and a pentyl group. A lower linear or branched chain alkyl group such as isopentyl or neopentyl. A partially or totally substituted with halogen atoms of the halogenated alkyl group R may include R ^{a18 a18} of the lower alkyl hydrogen atoms, lower alkyl groups preferably fluoride.

In the general formulae (a4-1) to (a4-2), p is an integer of 1 to 3, preferably 1.

The binding position of the hydroxyl group may be the o-position, the m-position, and the p-position of the phenyl group. When p is 1, the p-position is preferred from the standpoint of easy start and low price. When p is 2 or 3, any substitution position can be combined.

In the general formulae (a4-1) to (a4-2), q is an integer of 0 to 4, preferably an integer of 0 to 2, preferably 0 or 1, and particularly preferably 0.

The substitution position of R ^a18 is such that when q is 1, it may be any of the o-position, the m-position, and the p-position. When q is 2, any substitution position can be combined. The plural R ^a18 can each be the same or different. However, p+q is 1 or more and 5 or less.

In the above formula (a4-2), X ^a5 is not particularly limited as long as it is an acid-dissociable group. Preferable examples of the acid-dissociable group include the third-stage alkyl ester type acid dissociable group and the acetal type acid dissociable group, and the acetal acid dissociable group is preferred. Specific examples of the preferred acid-dissociable group include the groups represented by the above general formulas (p1) and (p2).

The component (a4) may be used alone or in combination of two or more.

Ratio of constituent units (a4) in the resin (a) to the general formula The constituent unit shown in (a4-1) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and 40 to 40% of the total constituent units constituting the resin (a). 80% of the moles is better. The total number of constituent units constituting the resin (a) is preferably from 5 to 90 mol%, and preferably from 10 to 60 mol%, based on the constituent unit represented by the general formula (a4-2).

[constitutive unit (a5)]

The constituent unit (a5) is a constituent unit derived from styrene. In the present invention, the constituent unit (a5) is not essential, and when it is contained, the solubility of the resin (a) for the developing solution containing the organic solvent can be easily adjusted.

The "styrene" in the present specification contains a concept in which a hydrogen atom at the alpha position of styrene and styrene is replaced by another substituent such as an alkyl group.

The "constituting unit derived from styrene" means a constituent unit composed of hydroxy cracking of ethylene double bond of styrene. The hydrogen atom in which styrene is a phenyl group may be substituted with a substituent such as an alkyl group having 1 to 5 carbon atoms.

Specific examples of the structural unit (a5) include the following structural formula (a5-1).

[In the general formula (a5-1), R is the same as defined above, and R ^a19 is a halogen atom, a lower alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group, and r is an integer of 0 to 3)

In the general formula (a5-1), R is the same as R in the above formula (a4-1). R ^a19 is the same as R ^a18 in the above formula (a4-1). r is an integer of 0 to 3, preferably 0 or 1, and 0 is preferred.

When r is 1, the substitution position of R ^a18 may be any of the o-position, the m-position, and the p-position of the phenyl group. When r is 2 or 3, any substitution position can be combined. The plural R ^a18 can each be the same or different.

The constituent unit (a5) may be used singly or in combination of two or more.

When the resin (a) has a constituent unit (a5), the ratio of the constituent unit (a5) in the resin (a) is preferably 1 to 20 mol%, based on the total of the constituent units constituting the resin (a). It is preferably 3 to 15 mol%, and more preferably 5 to 15 mol%.

The component (A) described above may be used singly or in combination of two or more. In the resist composition, the content of the component (A) is not particularly limited, and can be appropriately adjusted in accordance with the thickness of the resist film to be formed.

[(B) component]

The component (B) is a compound which generates an acid by irradiation with active light or radiation, and can be suitably selected from compounds which are used as an acid generator for a material for forming a resist film. The compound used as the component (B) may be used alone or in combination of two or more.

As an example of the acid generator, an sulfonium acid generator such as an iodonium salt or a phosphonium salt, an oxime sulfonate acid generator, a dialkyl or bisarylsulfonyldiazonane, or a poly( Production of diazane-based acids such as disulfonyl)diazones A nitrobenzylsulfonate-based acid generator, an imiline sulfonate-based acid generator, a biguanide acid generator, and the like.

As the onium salt acid generator, for example, a compound represented by the following general formula (b1) or (b2) can be used.

[For the general formulae (b1) and (b2), R ^b1 to R ^b3 and R ^b5 to R ^b6 each independently represent an aryl group or an alkyl group which may have a substituent. In the general formula (b1), any of R ^b1 to R ^b3 may be bonded to a sulfur atom in the formula to form a ring. R ^b4 represents an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent. At least one of R ^b1 to R ^b3 represents an aryl group, and at least one of R ^b5 to R ^b6 represents an aryl group. 〕

In the general formula (b1), R ^b1 to R ^b3 each independently represent an aryl group or an alkyl group which may have a substituent. Further, in R ^b1 to R ^b3 of the general formula (b1), any two of them may be bonded to each other and a sulfur atom in the formula may form a ring. Further, at least one of R ^b1 to R ^b3 represents an aryl group. ^Among R ^b1 to R ^b3 , those having 2 or more aryl groups are preferred, and all of R ^b1 to R ^b3 are aryl groups.

The aryl group of R ^b1 to R ^b3 is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms. As the aryl group, from the viewpoint of being inexpensively synthesized, an aryl group having 6 to 10 carbon atoms is preferred. Specifically, a phenyl group and a naphthyl group are mentioned, for example.

The aryl group may have a substituent. The "having a substituent" means that a part or all of a hydrogen atom of an aryl group may be substituted by a substituent. As the substituent having an aryl group, there are an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, an alkoxyalkoxy group, -OR ^b7 -C(=O)-(O) _n" -R ^b8 [wherein R ^b7 is an alkylene group or a single bond, and R ^b8 is an acid dissociable group or an acid non-dissociable group, and n" is 0 or 1] and the like.

The alkyl group which may be substituted with a hydrogen atom of an aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group which may be substituted by a hydrogen atom of an aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, and an n- Butoxy and tert-butoxy are preferred, and methoxy and ethoxy are preferred.

As the halogen atom to which the hydrogen atom of the aryl group can be substituted, a fluorine atom is preferred.

The alkoxyalkoxy group to which the hydrogen atom of the aryl group may be substituted may, for example, be a group represented by the following general formula.

-OC(R ^b9 )(R ^b10 )-OR ^b11 [In the general formula, R ^b9 and R ^{b10 are} each independently a hydrogen atom or a linear or branched alkyl group, and R ^b11 is an alkyl group, R ^b10 and R ^b11 Combining with each other can form one ring structure. However, at least one of R ^b9 and R ^b10 is a hydrogen atom]

For R ^b9 and R ^b10 , the alkyl group preferably has 1 to 5 carbon atoms, preferably ethyl or methyl groups, and the methyl group is most preferred. On the other hand, one of R ^b9 and R ^b10 is a hydrogen atom, and the other is preferably a hydrogen atom or a methyl group. When both R ^b9 and R ^b10 are a hydrogen atom, it is particularly preferable.

The alkyl group of R ^b11 is preferably a carbon number of 1 to 15, and may be any of a linear chain, a branched chain, and a cyclic group. The linear or branched chain alkane in R ^b11 is preferably a carbon number of 1 to 5, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

The cyclic alkyl group in R ^b11 is preferably a carbon number of 4 to 15, preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, it may be a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane which may be substituted by an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, or may be unsubstituted. A group in which one or more hydrogen atoms are removed may be mentioned. Examples of the monocycloalkane include cyclopentane, cyclohexane, and the like. Examples of the polycycloalkane include adamantane, norbornene, isobornene, tricyclodecane, and tetracyclododecane. Among them, a group in which one or more hydrogen atoms are removed from adamantane is preferred.

R ^b10 and R ^b11 are bonded to each other to form one ring structure. At this time, the oxygen atom to which R ^b10 and R ^b11 and R ^b11 are bonded forms a cyclic group by a carbon atom bonded to the oxygen atom and R ^b10 . The ring base at this time is preferably a 4 to 7 ring, and a 4 to 6 ring is preferred.

The hydrogen atom of the above aryl group is a group which may be substituted, and for -OR ^b7 -C(=O)-(O) _n" -R ^b8 , the alkylene group in R ^b7 is linear or branched. The alkyl group is preferred, and the carbon number is preferably from 1 to 5. As specific examples of the alkylene group, there are methyl group, ethyl group, trimethyl group, tetramethyl group, and 1,1-dimethyl group. Ethyl or the like can be mentioned.

The acid-dissociable group in R ^b8 may be an organic group which can be dissociated by the action of an acid (an acid generated from the component (B) upon exposure), and is not particularly limited, and examples thereof include the above (A). The description of the components is the same as the acid dissociation dissolution inhibiting group. Among them, those having a third-order alkyl ester type are preferred.

Preferred examples of the non-dissociable group of the acid in R ^b8 include a mercapto group, a tricyclodecanyl group, an adamantyl group, a 1-(1-adamantyl)methyl group, a tetracyclododecyl group, an isobornyl group. Bases, norbornene groups and the like can be mentioned.

When R ^b1 to R ^b3 are alkyl groups, it is not particularly limited. Preferable examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. The alkyl group preferably has a carbon number of from 1 to 5 from the viewpoint of a resist composition excellent in modulation resolution. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a decyl group, and癸基等, etc. can be cited. Among these alkyl groups, a methyl group is preferred.

The alkyl group may have a substituent. The "having a substituent" means that a part or all of a hydrogen atom of an alkyl group may be substituted by a substituent. The alkyl group may have a substituent, and the same as those exemplified as the substituent which may have an aryl group may be mentioned.

In the general formula (b1), any one of R ^b1 to R ^b3 may be bonded to a sulfur atom in the formula to form a ring. The ring formed can be saturated or unsaturated. Also, the ring formed may be a single ring or a multiple ring. For example, when one or both of the ring-forming groups are a cyclic group (cyclic alkyl group or aryl group), when combined with these, a polycyclic ring (condensed ring) is formed.

When two of R ^b1 to R ^b3 are combined to form a ring, in the general formula (b1), if one ring containing a sulfur atom in the ring skeleton is a sulfur-containing atom, it is preferably a 3 to 10 member ring, and 5 to 5 The 7-member ring is preferred.

Specific examples of the ring formed by the combination of two of R ^b1 to R ^b3 include benzothiophene, dibenzothiophene, 9H-thioxanthene, thioxanthone, anthracene, phenothiazine, tetrahydrothiophene, tetrahydrogen. Thiol oxime and the like can be mentioned. When any two of R ^b1 to R ^b3 are bonded to each other to form a ring together with a sulfur atom in the formula, the remaining one is preferably an aryl group.

In the cation portion of the compound of the formula (b1), when all of R ^b1 to R ^b3 are a phenyl group which may have a substituent, in other words, a preferred example of the case where the cation moiety has a triphenylsulfonium skeleton is as follows: The cation part shown by b1-1)~(b1-14) is mentioned.

Further, a part or all of the phenyl group in the cationic portion may be substituted by a naphthyl group which may have a substituent, and may be preferably mentioned. Of the three phenyl groups, those substituted by a naphthyl group are preferably 1 or 2.

Further, in the cation portion of the compound of the general formula (b1), as a preferred example in which two of R ^b1 to R ^b3 are bonded to each other to form a ring together with a sulfur atom in the formula, for example, the following general formula (b1) The cation moiety shown by -15) to (b1-18) can be mentioned.

[In the general formulas (b1-15) and (b1-16), R ^b12 is a phenyl group which may have a substituent, a naphthyl group which may have a substituent or an alkyl group having 1 to 5 carbon atoms, and R ^b13 may have a phenyl group of a substituent, a naphthyl group which may have a substituent, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group, and u is an integer of 1 to 3)

[In the general formulas (b1-17) and (b1-18), Z ^b1 is a single bond, a methyl group, a sulfur atom, an oxygen atom, a nitrogen atom, a carbonyl group, -SO-, -SO ₂ -, -SO ₃ -, -COO-, -CONH- or N(R ^b20 )-(R ^b20 is an alkyl group having 1 to 5 carbon atoms), and R ^b14 and R ^b15 to R ^{b19 are} each independently an alkyl group, an ethyl group, an alkoxy group. Base, carboxyl group, hydroxyl group or hydroxyalkyl group, n1~n5 are each an integer of 0~3, and n6 is an integer of 0~2]

In the general formulae (b1-15) to (b1-16), when R ^b12 to R ^b13 are a substituent which may be a phenyl group or a naphthyl group, and R ^b1 to R ^b3 are an aryl group, The substituents which the aryl group may have are the same. Further, examples of the substituent which the alkyl group in R ^b12 to R ^b13 may have, and R ^b1 to R ^b3 are an alkyl group, the same as those which may be a substituent which may be an alkyl group. U is an integer from 1 to 3, preferably 1 or 2.

In the general formulae (b1-17) to (b1-18), for R ^b14 to R ^b19 , the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and a linear or branched alkyl group is preferred. It is particularly preferred as methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, and a linear or branched alkoxy group is preferred, and a methoxy group and an ethoxy group are particularly preferred. The hydroxyalkyl group is preferably a group in which one of the above alkyl groups or a plurality of hydrogen atoms is substituted with a hydroxyl group, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

When the symbols n1 to n6 attached to R ^b14 to R ^b19 are integers of 2 or more, the plural numbers R ^b14 to R ^b19 may be the same or different. N1 is preferably an integer of 0 to 2, preferably 0 or 1, and particularly preferably 0. N2 and n3 are each independently 0 or 1, and 0 is preferred. N4 is preferably an integer of 0 to 2, and preferably 0 or 1. Preferably, n5 is 0 or 1, and 0 is preferred. N6 is preferably 0 or 1, and preferably 1 is preferred.

In the general formulae (b1) to (b2), R ^b4 represents an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent. The alkyl group in R ^b4 may be any of a linear chain, a branched chain, and a cyclic group. The linear or branched chain alkyl group preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

The cyclic alkyl group preferably has 4 to 15 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 6 to 10 carbon atoms.

The halogenated alkyl group in R ^b4 may be a group in which a part or all of a hydrogen atom of the above-mentioned linear, branched or cyclic alkyl group may be substituted by a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferred.

With respect to the halogenated alkyl group, the ratio of the number of halogen atoms (halogenation ratio (%)) is preferably from 10 to 100%, preferably from 50 to 100%, in terms of the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group. 100% is the best. The higher the halogenation rate, the stronger the acid strength produced is.

The aryl group in R ^b4 is preferably an aryl group having 6 to 20 carbon atoms. The alkenyl group in R ^b4 is preferably an alkenyl group having 2 to 10 carbon atoms.

With respect to R ^b4 , the "may have a substituent" means that a part or all of a hydrogen atom in the aforementioned linear, branched or cyclic alkyl group, halogenated alkyl group, aryl group or alkenyl group may be a substituent ( The meaning of substitution with another atom or group other than a hydrogen atom. The number of substituents in R ^b4 may be 1 or may be 2 or more.

Examples of the substituent include a halogen atom, a hetero atom, and an alkyl group: R ^b20 -Q ^b1 - wherein Q ^b1 is a divalent linking group containing an oxygen atom, and R ^b20 is a carbon number which may have a substituent The group represented by the hydrocarbon group of ~30 is exemplified.

The halogen atom or the alkyl group may be the same as those exemplified as the halogen atom or the alkyl group in the halogenated alkyl group in R ^b4 . Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

For the group represented by R ^b20 -Q ^b1 -, Q ^b1 is a divalent linking group containing an oxygen atom. Q ^b1 is an atom other than an oxygen atom. Examples of the atom other than the oxygen atom include a carbon atom, a hydrogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom.

As the divalent linking group containing an oxygen atom, for example, an oxygen atom (ether bond; -O-), an ester bond (-C(=O)-O-), a guanamine bond (-C(=O)-NH- a non-hydrocarbon-based linking group containing an oxygen atom such as a carbonyl group (-C(=O)-) or a carbonate bond (-OC(=O)-O-), and a non-hydrocarbon-based linking group containing an oxygen atom A combination of alkyl groups and the like can be mentioned.

As a combination of a non-hydrocarbon-containing oxygen atom-containing linking group and an alkylene group, for example, -R ^b21 -O-, -R ^b22 -OC(=O)-, -C(=O)-OR ^b23 -, -C (=O)-OR ^b24 -OC(=O)- (wherein, R ^b21 to R ^{b24 are} each independently an alkylene group) and the like can be mentioned. As the alkylene group in R ^b21 to R ^b24 , a linear or branched alkyl group is preferred. The carbon number of the alkyl group is preferably from 1 to 12, preferably from 1 to 5, and particularly preferably from 1 to 3.

Specific examples of the alkylene group include methyl group [-CH ₂ -]; -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 - or the like alkyl-extension methyl; ex-ethyl [- CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -alkaline alkylvinyl; trimethyl (n-propyl)[-CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ CH ₂ -etc. Alkyltrimethylmethyl; tetramethylmethyl[-CH ₂ CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ ) an alkyltetramethyl group such as CH ₂ CH ₂ - or the like; a methyl group [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -] or the like.

As Q ^b1 , a divalent linking group containing an ester bond or an ether bond is preferred, wherein -R ^b21 -O-, -R ^b22 -OC(=O)-, -C(=O)-O-, -C(=O)-OR ^b23 - or -C(=O)-OR ^b24 -OC(=O)- is preferred.

When R ^b20 is a hydrocarbon group for the group represented by R ^b20 -Q ^b1 -, R ^b20 may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The carbon number of the aromatic hydrocarbon group is preferably from 3 to 30, preferably from 5 to 30, more preferably from 5 to 20, most preferably from 6 to 15, and most preferably from 6 to 12. However, among the carbon numbers of the aromatic hydrocarbon group, those having no carbon number in the substituent are included.

Specific examples of the aromatic hydrocarbon group include an aryl group, a benzyl group, and a phenethyl group in which one hydrogen atom is removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group. An arylalkyl group such as 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl or 2-naphthylethyl can be mentioned. The 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.

The aromatic hydrocarbon group may have a substituent. Examples of the substituent which the aromatic hydrocarbon group may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxygen atom (=O).

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

The alkoxy group as a substituent of the aromatic hydrocarbon group is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, and an n-butoxy group. The base and tert-butoxy group are preferred, and the methoxy group and the ethoxy group are particularly preferred.

The halogen atom as a substituent of the aromatic hydrocarbon group may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferred. The halogenated alkyl group as a substituent of the aromatic hydrocarbon group may be a group in which a part or all of a hydrogen atom of the alkyl group may be substituted by the above halogen atom.

Further, a part of a carbon atom constituting an aromatic ring having an aromatic hydrocarbon group may be substituted with a hetero atom. An example in which a part of a carbon atom constituting an aromatic ring of an aromatic hydrocarbon group is substituted by a hetero atom is exemplified a heteroaryl group in which a part of a carbon atom of a ring is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and a part of a carbon atom constituting an aromatic hydrocarbon ring in the arylalkyl group are A heteroarylalkyl group substituted by an atom may, for example, be mentioned.

The aliphatic hydrocarbon group in R ^b20 may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group.

In R ^b20 , the aliphatic hydrocarbon group may be a part of a carbon atom constituting the aliphatic hydrocarbon group, and a part or all of the hydrogen atom constituting the aliphatic hydrocarbon group may be substituted by a substituent containing a hetero atom. Replace.

The "hetero atom" in R ^b20 is not particularly limited as long as it is an atom other than a carbon atom or a hydrogen atom, and examples thereof include a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom.

The "substituent containing a hetero atom" (hereinafter sometimes referred to as a hetero atom-containing substituent) may be a group formed by a hetero atom alone or a group or an atom other than a hetero atom.

As the hetero atom-containing substituent which can replace a part of the carbon atom constituting the aliphatic hydrocarbon group, for example, O-, -C(=O)-O-, -C(=O)-, -OC(=O) )-O-, -C(=O)-NH-, -NH- (H is a substituent which may be substituted by an alkyl group, a thiol group, etc.), -S-, -S(=O) ₂ -, -S( =O) ₂ -O-, etc. can be mentioned. When it is -NH-, the substituent (H, decyl, etc.) which can be substituted for H is preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and 1 to 5 carbon atoms. It is especially good. When the aliphatic hydrocarbon group is cyclic, these substituents may be contained in the ring structure.

The hetero atom-containing substituent which may replace a part or the whole of the hydrogen atom constituting the aliphatic hydrocarbon group, for example, a halogen atom, an alkoxy group, a hydroxyl group, -C(=O)-R ^b25 [R ^b25 is an alkyl group ], -COOR ^b26 [R ^b26 is a hydrogen atom or an alkyl group], a halogenated alkyl group, a halogenated alkoxy group, an amine group, a decylamino group, a nitro group, an oxygen atom (=O), a sulfur atom, a sulfonyl group (SO) ₂ ) etc. can be cited.

Examples of the halogen atom of the hetero atom-containing substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

The alkyl group in the alkoxy group as a hetero atom-containing substituent may be any of a linear chain, a branched chain, and a cyclic group, or may be any combination thereof. The alkyl carbon number in the alkoxy group is preferably from 1 to 30. When the alkyl group is linear or branched, the carbon number is preferably from 1 to 20, preferably from 1 to 17, more preferably from 1 to 15, and particularly preferably from 1 to 10. Specifically, the same as the specific example of the linear or branched chain saturated hydrocarbon group exemplified hereinafter will be mentioned. When the alkyl group is cyclic (when it is a cycloalkyl group), the carbon number is preferably from 3 to 30, preferably from 3 to 20, more preferably from 3 to 15, and particularly preferably from 4 to 12. 5~10 is the best. When the alkyl group is a cyclic group, it may be a monocyclic ring or a polycyclic ring. Specific examples thereof include a group in which one or more hydrogen atoms are removed from a monocycloalkane, a group in which a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane is removed, and one or more hydrogen atoms are removed. Specific examples of the monocycloalkane include cyclopentane, cyclohexane, and the like. Further, specific examples of the polycycloalkane include adamantane, norbornene, isobornene, tricyclodecane, tetracyclododecane, and the like. Some or all of the hydrogen atoms to which the cycloalkyl group is bonded may be substituted or unsubstituted with a substituent such as a fluorine atom or a fluorinated alkyl group.

The -C(=O)-R ^b25 and -COOR ^b26 which are substituents containing a hetero atom, and the alkyl group in R ^b25 and R ^b26 are exemplified by the alkyl group in the alkoxy group described above. The same as the alkyl group.

The alkyl group in the halogenated alkyl group as the hetero atom-containing substituent may be the same as the alkyl group exemplified as the alkyl group in the alkoxy group. As the halogenated alkyl group, a fluorinated alkyl group is particularly preferred.

The halogenated alkoxy group as a hetero atom-containing substituent may be a group in which one or all of hydrogen atoms of the alkoxy group are substituted by the above halogen atom. As the halogenated alkoxy group, a fluorinated alkoxy group is preferred.

The hydroxyalkyl group which is a hetero atom-containing substituent may be a group in which at least one hydrogen atom of the alkyl group exemplified as the alkyl group in the alkoxy group is substituted with a hydroxyl group. The number of hydroxyl groups having a hydroxyalkyl group is preferably from 1 to 3, more preferably from 1.

The aliphatic hydrocarbon group is preferably a linear or branched saturated hydrocarbon group, a linear or branched monovalent unsaturated hydrocarbon group, or a cyclic aliphatic hydrocarbon group (aliphatic cyclic group).

The carbon number of the linear saturated hydrocarbon group (alkyl group) is preferably from 1 to 20, more preferably from 1 to 15, and most preferably from 1 to 10. Specific examples of the linear saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, and a dodecyl group. Tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosane A base, a hexadecyl group, a behenyl group, etc. are mentioned.

The branched chain saturated hydrocarbon group (alkyl group) preferably has a carbon number of 3 to 20, 3~15 is better, and 3~10 is the best. Specific examples of the branched saturated hydrocarbon group are 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methyl. Butyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc. are mentioned.

The carbon number of the unsaturated hydrocarbon group is preferably 2 to 10, preferably 2 to 5, more preferably 2 to 4, and most preferably 3. Examples of the linear monovalent unsaturated hydrocarbon group include a vinyl group, a propenyl group (allyl group), and a butenyl group. Examples of the branched monovalent unsaturated hydrocarbon group include a 1-methylpropenyl group and a 2-methylpropenyl group. As the unsaturated hydrocarbon group, a propylene group is particularly preferred.

The aliphatic cyclic group may be a monocyclic group or a polycyclic group. The carbon number of the aliphatic ring group is preferably from 3 to 30, preferably from 5 to 30, more preferably from 5 to 20, most preferably from 6 to 15, and most preferably from 6 to 12.

Specific examples of the aliphatic cyclic group include a group in which one or more hydrogen atoms are removed from a monocycloalkane, and one or more hydrogen atoms are removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. The base can be cited. More specifically, a group in which one or more hydrogen atoms are removed from a monocycloalkane such as cyclopentane or cyclohexane; adamantane, norbornene, isobornene, tricyclodecane, and tetracyclododecane; A group in which one or more hydrogen atoms are removed from the polycycloalkane may be mentioned.

When the aliphatic cyclic group is a substituent which does not contain a hetero atom in the ring structure, as the aliphatic ring group, a polycyclic group is preferred, and the polycycloalkane is used. A group in which one or more hydrogen atoms are removed from the hydrocarbon is preferred, and a group in which one or more hydrogen atoms are removed from adamantane is preferred.

When the aliphatic cyclic group is a substituent containing a hetero atom in the ring structure, as a substituent containing a hetero atom, -O-, -C(=O)-O-, -S-, -S(= O) ₂ -, -S(=O) ² -O- is preferred. Specific examples of the aliphatic cyclic group include, for example, the groups represented by the following formulae (L1) to (L5) and (S1) to (S4).

[In the general formulae (L2), (S3), and (S4), Q ^b2 is an alkyl group, an oxygen atom or a sulfur atom which may contain an oxygen atom or a sulfur atom, and in the general formula (L4), m is 0 or 1 Integer

In the formula, the alkylene group in Q ^b2 is preferably a linear or branched chain, and the carbon number is preferably from 1 to 5. Specifically, there are methyl <-CH ₂ -]; -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 - or the like alkyl-extended methyl; ex-ethyl [-CH ₂ CH ₂ -] An alkyl group 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 - Vinyl; trimethyl (n-propyl) [-CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -, etc. Alkyltrimethylmethyl; tetramethyl [-CH ₂ CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -Alkyltetramethylene; pentamethyl [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -] and the like can be mentioned. Among them, methyl or alkyl methyl groups are preferred, and methyl, -CH(CH ₃ )- or -C(CH ₃ ) ₂ - is particularly preferred.

When Q ^b2 is an alkylene group, the alkyl group may contain an oxygen atom (-O-) or a sulfur atom (-S-). In this specific example, the terminal of the alkyl group or the group between the carbon atoms ^via -O- or S- may be mentioned, for example, OR ^b27 -, ^{-SR b28} -, -R ^b29 -OR ^b30 -, -R ^b31 -SR ^b32 - etc. can be cited. Wherein, R ^b27 to R ^{b32 are} each independently an alkylene group. The alkylene group is the same as the alkylene group exemplified as the alkylene group in the above Q ^b2 . Among them, -O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, and -CH ₂ -S-CH ₂ - are preferable.

These aliphatic cyclic groups are a part or all of a hydrogen atom which may be substituted by a substituent. Examples of the substituent which may have an aliphatic cyclic group include an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group, -C(=O)-R ^b25 [R ^b25 is an alkyl group], and -COOR ^b26 [R ^B26 is a hydrogen atom or an alkyl group], a halogenated alkyl group, a halogenated alkoxy group, an amine group, a decylamino group, a nitro group, an oxygen atom (=O), a sulfur atom, a sulfonyl group (SO ₂ ), or the like.

The alkyl group as a substituent may be the same as the alkyl group as the alkyl group-containing substituent. The carbon number of the alkyl group is particularly preferably from 1 to 6. Further, the alkyl group is preferably a linear chain or a branched chain. Specific examples of the alkyl group 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, a hexyl group, and the like. Can be mentioned. Among them, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.

The halogen atom, the alkoxy group, -C(=O)-R ^b25 , -COOR ^b26 , a halogenated alkyl group or a halogenated alkoxy group as a substituent may each be a hydrogen atom which is a substitutable aliphatic hydrocarbon group. The same as that of some or all of the hetero atom-containing substituents.

The substituent of the hydrogen atom replacing the aliphatic cyclic group is preferably an alkyl group, an oxygen atom (=O) or a hydroxyl group. The number of substituents having an aliphatic cyclic group may be one or two or more. When a plurality of substituents are present, the plural substituents may each be the same or different.

As R ^b20 , a ring group which may have a substituent is preferred. When R ^b20 is a cyclic group, the cyclic group may be an aromatic hydrocarbon group which may have a substituent, or may be an aliphatic cyclic group which may have a substituent. Among them, an aliphatic cyclic group which may have a substituent is preferred.

The aromatic hydrocarbon group is preferably a naphthyl group which may have a substituent or a phenyl group which may have a substituent.

As the aliphatic cyclic group which may have a substituent, a polycyclic aliphatic cyclic group which may have a substituent is preferred. The polycyclic aliphatic cyclic group is a group in which one or more hydrogen atoms are removed from a polycycloalkane such as adamantane, norbornene, isobornene, tricyclodecane or tetracyclododecane. The base represented by L2)~(L5), (S3)~(S4) is preferable.

In the present invention, R ^b4 is preferably a group having R ^b20 -Q ^b1 - as a substituent. In this case, as R ^b4 , R ^b20 -Q ^b1 -Y ^b1 -[wherein, Q ^b1 and R ^{b20 are the} same as defined above, and Y ^b1 is an alkylene group having 1 to 4 carbon atoms which may have a substituent or may have The group represented by the fluorinated alkyl group having 1 to 4 carbon atoms of the substituent is preferred.

The group represented by R ^b20 -Q ^b1 -Y ^b1 -, as the alkylene group of Y ^b1 , may be the same as the carbon number of 1 to 4 in the alkylene group of Q ^b1 .

The fluorinated alkyl group may be a group in which a part or all of a hydrogen atom of an alkyl group is substituted by a fluorine atom.

Specific examples of Y ^b1 include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF(CF ₃ )CF ₂ -, -CF(CF ₂ CF ₃ )-, - C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, -CF(CF ₃ )CF ₂ CF ₂ -, -CF ₂ CF(CF ₃ )CF ₂ -, -CF(CF ₃ )CF (CF ₃ )-, -C(CF ₃ ) ₂ CF ₂ -, -CF(CF ₂ CF ₃ )CF ₂ -, -CF(CF ₂ CF ₂ CF ₃ )-, -C(CF ₃ )(CF ₂ CF ₃ )-;-CHF-, -CH ₂ CF ₂ -, -CH ₂ CH ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ -, -CH(CF ₃ )CH ₂ -, -CH(CF ₂ CF ₃ )-, -C(CH ₃ )(CF ₃ )-, -CH ₂ CH ₂ CH ₂ CF ₂ -, -CH ₂ CH ₂ CF ₂ CF ₂ -, -CH(CF ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CF ₃ )CH ₂ -, -CH(CF ₃ )CH(CF ₃ )-, -C(CF ₃ ) ₂ CH ₂ -; -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ -, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ( CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -CH(CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )- and the like can be mentioned.

As Y ^b1 , a fluorinated alkyl group is preferred, and a fluorinated alkyl group in which a carbon atom to which a sulfur atom is bonded is fluorinated is particularly preferable. Examples of such a fluorinated alkyl group include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF(CF ₃ )CF ₂ -, -CF ₂ CF ₂ CF ₂ CF. ₂ -, -CF(CF ₃ )CF ₂ CF ₂ -, -CF ₂ CF(CF ₃ )CF ₂ -, -CF(CF ₃ )CF(CF ₃ )-, -C(CF ₃ ) ₂ CF ₂ - -CF(CF ₂ CF ₃ )CF ₂ -; -CH ₂ CF ₂ -, -CH ₂ CH ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ -; -CH ₂ CH ₂ CH ₂ CF ₂ -, - CH ₂ CH ₂ CF ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ CF ₂ -, and the like. Among them, -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, or CH ₂ CF ₂ CF ₂ - is preferred, and -CF ₂ -, -CF ₂ CF ₂ - or - CF ₂ CF ₂ CF ₂ - is preferred, and -CF ₂ - is preferred.

The above alkyl or fluorinated alkyl group may have a substituent. The alkyl group or the fluorinated alkyl group is "may have a substituent" means that a part or all of a hydrogen atom or a fluorine atom in an alkylene group or a fluorinated alkyl group may be an atom or a group other than a hydrogen atom and a fluorine atom. The meaning of the replacement. Examples of the substituent which may have an alkylene group or a fluorinated alkyl group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group and the like.

In the general formula (b2), R ^b5 to R ^b6 each independently represent an aryl group or an alkyl group. Further, among R ^b5 ~ R ^b6, at least one of them represents an aryl group, R ^b5 ~ R ^b6 are all aryl group all preferred. ^Examples of the aryl group of R ^b5 to R ^b6 include the same as those of the aryl group of R ^b1 to R ^b3 . The alkyl group of R ^b5 to R ^b6 may be the same as the alkyl group of R ^b1 to R ^b3 . Among them, those in which R ^b5 to R ^{b6 are} all phenyl groups are preferred. R ^b4 in the formula (b2) is the same as R ^b4 of the above formula (b1).

Specific examples of the sulfonium-based acid generator represented by the general formula (b1) or (b2) include diphenyl iodonium trifluoroalkethanesulfonate or nonafluorobutane sulfonate; bis (4-tert) - butylphenyl) iodonium trifluoroalkethanesulfonate or nonafluorobutanesulfonate; triphenylsulfonium trifluoroalkanesulfonate, heptafluoropropanesulfonate or its nonafluorobutanesulfonate Tris(4-methylphenyl)phosphonium trifluoroalkanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate; dimethyl (4- a fluoronaphthalene sulfonium sulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof; a triphenyl sulfonate of monophenyl dimethyl hydrazine, a heptafluoropropane sulfonate or nine thereof Fluorane sulfonate; diphenylmonomethyl hydrazine trifluoroalkethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate; (4-methylphenyl) diphenyl hydrazine a trifluoroalkethanesulfonate, a heptafluoropropanesulfonate or a nonafluorobutanesulfonate thereof; a (3-methoxyphenyl)diphenylphosphonium trifluoroalkanesulfonate, a heptafluoropropanesulfonate thereof or Nonafluorobutane sulfonate; tris(4-tert-butyl)phenylhydrazine strifluorosulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate; diphenyl (1-( a trifluoroalkanesulfonate of 4-methoxy)naphthalene), a heptafluoropropanesulfonate or a nonafluorobutanesulfonate thereof; a trifluoroalkanesulfonate of bis(1-naphthyl)phenylhydrazine; Heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof; a trifluoroalkanesulfonate of 1-phenyltetrahydrothiophene, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof; 1-(4- Methylphenyl) tetrahydrothiophene sulfonate, heptafluoropropane sulfonate a nonafluorobutane sulfonate; a trifluoroalkanesulfonate of 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene, a heptafluoropropanesulfonate or a nonafluorobutanesulfonate thereof Acid salt; 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1-(4-B a fluoronaphthalene-1-yl)tetrahydrothiophene sulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof; 1-(4-n-butoxynaphthalen-1-yl) a trifluoroalkanesulfonate of tetrahydrothiophene, a heptafluoropropanesulfonate thereof or a nonafluorobutanesulfonate thereof; a trifluoroalkanesulfonate of 1-phenyltetrahydrothiopyranium, a heptafluoropropanesulfonate thereof Or a nonafluorobutane sulfonate thereof; a trifluoroalkanesulfonate of 1-(4-hydroxyphenyl)tetrahydrothiopyranium, a heptafluoropropanesulfonate or a nonafluorobutanesulfonate thereof; a trifluoroalkanesulfonate of (3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopyran, a heptafluoropropanesulfonate or a nonafluorobutanesulfonate thereof; 1-(4-methyl The phenyl) tetrahydrothiopyranium trifluoroalkethanesulfonate, the heptafluoropropanesulfonate or the nonafluorobutanesulfonate thereof, and the like are exemplified.

Further, the anion portions of these onium salts are each substituted with an alkanesulfonate, an n-propanesulfonate, an n-butanesulfonate, an n-octanesulfonate, a 1-adamantanesulfonate, and 2- An alkyl sulfonate such as norbornene sulfonate; a sulfonium salt of a sulfonate such as d-camphor-10-sulfonate, benzenesulfonate, perfluorobenzenesulfonate or p-toluenesulfonate be usable.

Further, an anthracene salt in which an anion portion of these onium salts is substituted with an anion portion shown by any one of the following general formulas (bI) to (bVIII) may be used.

[In general formula (bI)~(bIII), v0 is an integer from 0 to 3, q1~q2 are each an integer from 1 to 5, q3 is an integer from 1 to 12, and r1 to r2 are each independently 0 to 3. An integer, i is an integer from 1 to 20, t3 is an integer from 1 to 3, R ^b33 is a substituent, and R ^b34 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

[In general formulas (bIV) to (bVIII), t3, R ^b33 and Q ^{b2 are} the same as described above, m1 to m5 are each independently 0 or 1, and v1 to v5 are each independently an integer of 0 to 3, and w1 to w5 are each Independently an integer from 0 to 3]

^Examples of the substituent of R ^b33 include an alkyl group and a hetero atom-containing substituent. The alkyl group may be the same as the alkyl group exemplified as the substituent which may have an aromatic hydrocarbon group in the description of R ^b20 . Further, examples of the hetero atom-containing substituent include the same as those of the hetero atom-containing substituent which is a part or the whole of the hydrogen atom constituting the aliphatic hydrocarbon group in the description of R ^b20 .

^When the symbol (r1 to r2, w1 to w5) attached to R ^b33 is an integer of 2 or more, it means that the plural R ^{b33 in} the same compound may be the same or different.

^Examples of the alkyl group or the halogenated alkyl group in R ^b34 include the same as those of the alkyl group or the halogenated alkyl group in the above R ^b4 .

R1~r2 and w1~w5 are each preferably an integer of 0~2, preferably 0 or 1. V0~v5 is preferably 0~2, and 0 or 1 is preferred. Preferably, t3 is 1 or 2, and 1 is preferred. Q3 is preferably an integer of 1 to 5, preferably an integer of 1 to 3, and particularly preferably 1.

Further, as the onium salt-based acid generator, the above-described general formula (b1) or (b2) may be used, and the anion salt-based acid obtained by substituting the negative ion moiety with the negative ion represented by the following general formula (b3) or (b4) may be used. The agent (the cation moiety is the same as the general formula (b1) or (b2)).

[In the general formulas (b3) and (b4), X ^b1 represents a hydrogen atom of at least 1 and a C 2 - 6 alkyl group substituted by a fluorine atom; and Y ^b2 and Z ^b2 each independently represent at least one hydrogen atom. Alkyl group having 1 to 10 carbon atoms substituted by a fluorine atom]

X ^b1 is a linear or branched chain alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the carbon number of the alkyl group is 2 to 6, preferably 3 to 5, and more preferably 3.

Y ^b2 and Z ^{b2 are} each a linear or branched chain alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the carbon number of the alkyl group is 1 to 10, preferably 1 to 7 and 1 to 1 3 is preferred.

The carbon number of the alkyl group of X ^b1 or the carbon number of the alkyl group of Y ^b2 and Z ^b2 is preferably smaller in the above carbon number range because of the solubility in the resist solvent.

Further, for the alkyl group of X ^b1 or the alkyl group of Y ^b2 and Z ^b2 , the more the number of hydrogen atoms substituted by the fluorine atom, the stronger the strength of the acid, and the higher the energy light for the wavelength of 200 nm or less. Or the transparency of the electronic wire is better.

The ratio of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate is preferably from 70 to 100%, preferably from 90 to 100%, particularly preferably from 100%. In other words, a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are replaced by a fluorine atom is particularly preferable.

Further, a ruthenium in which the negative ion moiety (R ^b4 SO ₃ ^- ) is substituted with R ^b7 -COO ^- (wherein, R ^b7 is an alkyl group or a fluorinated alkyl group) can be used for the above general formula (b1) or (b2). A salt acid generator (the cation portion is the same as (b1) or (b2)). R ^b7 is the same as the above R ^b4 . Specific examples of the negative ion represented by R ^b7 -COO ^- include trifluoroacetic acid ion, acetic acid ion, and 1-adamantane carboxylate ion.

In the present specification, the sulfonate-based acid generator is a compound having at least one group represented by the following general formula (B1), and has a property of generating an acid by irradiation with radiation. Such a sulfonate-based acid generator can be arbitrarily selected from those used in the past.

[In the general formula (B1), R ^b35 and R ^b36 each independently represent an organic group]

The organic group of R ^b35 and R ^{b36 is} a group containing a carbon atom, and may have an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)).

The organic group of R ^b35 is preferably a linear chain, a branched chain or a cyclic alkyl group or an aryl group. These alkyl groups or aryl groups may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom, a linear one having 1 to 6 carbon atoms, a branched chain group, and a cyclic alkyl group. The term "having a substituent" means that a part or all of a hydrogen atom of an alkyl group or an aryl group is substituted by a substituent.

The carbon number of the alkyl group is preferably from 1 to 20, preferably from 1 to 10, more preferably from 1 to 8, more preferably from 1 to 6, and most preferably from 1 to 4. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is preferred. Further, the partially halogenated alkyl group means an alkyl group in which a part of a hydrogen atom is replaced by a halogen atom, and the alkyl group which is completely halogenated means an alkyl group in which all hydrogen atoms are replaced by a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

The carbon number of the aryl group is preferably 4 to 20, preferably 4 to 10, and particularly preferably 6 to 10. As the aryl group, it is particularly preferred to use an aryl group which is partially or completely halogenated. Further, the partially halogenated aryl group means an aryl group in which a part of a hydrogen atom is replaced by a halogen atom, and the aryl group which is completely halogenated means an aryl group in which all hydrogen atoms are replaced by a halogen atom. .

R ^{b35 is} particularly preferably an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms which does not have a substituent.

The organic group of R ^b36 is preferably a linear chain, a branched chain or a cyclic alkyl group, an aryl group or a cyano group. The alkyl group and the aryl group of R ^b36 are the same as those of the alkyl group and the aryl group mentioned in the above R ^b35 .

R ^{b36 is preferably} a cyano group, an alkyl group having 1 to 8 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

More preferably, the oxime sulfonate-based acid generator is a compound represented by the following general formula (B2) or (B3).

[In the general formula (B2), R ^b37 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group. R ^b38 is an aryl machine. R ^b39 is an alkyl group having no substituent or an alkyl halide;

[In the general formula (B3), R ^b40 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group. R ^b41 is a 2 or 3 valent aromatic hydrocarbon group. R ^b42 is an alkyl group or a halogenated alkyl group having no substituent. p" is 2 or 3]

For the general formula (B2), the alkyl group having a substituent or the alkyl group having a halogenated group of R ^b37 is preferably 1 to 10, more preferably 1 to 8, and most preferably 1 to 6. As R ^b37 , a halogenated alkyl group is preferred, and a fluorinated alkyl group is preferred. The fluorinated alkyl group in R ^b37 is preferably a fluorinated group in which the hydrogen atom of the alkyl group is 50% or more, preferably fluorinated at 70% or more, and particularly preferably fluorinated at 90% or more.

^Examples of the aryl group of R ^b38 include a group in which one hydrogen atom is removed from a ring of an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and a ring constituting these groups. A heteroaryl group in which one of the carbon atoms is replaced by a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom may be mentioned. Among them, the base is preferred.

The aryl group of R ^{b38 is} a substituent which may have an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an alkoxy group. The alkyl group or the halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Further, the halogenated alkyl group is preferably a fluorinated alkyl group.

The alkyl group or the halogenated alkyl group having no substituent of R ^b39 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. As R ^{b39 ,} a halogenated alkyl group is preferred, and a fluorinated alkyl group is preferred.

The fluorinated alkyl group in R ^b39 is preferably one in which 50% or more of the hydrogen atom of the alkyl group is fluorinated, 70% or more of which is fluorinated, and 90% or more of the acid which is fluorinated. Will improve the special good. Most preferred is a fully fluorinated alkyl group in which 100% of the hydrogen atoms are replaced by fluorine.

In the general formula (B3), the alkyl group or the halogenated alkyl group which does not have a substituent of R ^b40 may be the same as the alkyl group or the halogenated alkyl group which does not have a substituent of the above R ^b37 . As R ^b41 is a divalent or trivalent aromatic hydrocarbon group may further include removing one or two hydrogen atoms of the above aryl group R ^b38. The alkyl group or the halogenated alkyl group which does not have a substituent of R ^b42 is the same as the alkyl group or the halogenated alkyl group which does not have a substituent of the above R ^b39 . p" is preferably 2.

Specific examples of the sulfonate-based acid generator include α-(p-toluene) Hydroxyimine)-benzylmethyl cyanide, α-(p-chlorophenylsulfonyloxyimide)-benzyl cyanide, α-(4-nitrophenylsulfonyloxyimide)- Benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimide)-benzyl cyanide, α-(phenylsulfonyloxyimide)-4-chloro Benzyl cyanide, α-(phenylsulfonyloxyimide)-2,4-dichlorobenzyl cyanide, α-(phenylsulfonyloxyimide)-2,6-dichlorobenzene Cyanide, α-(phenylsulfonyloxyimide)-4-methoxybenzyl cyanide, α-(2-chlorophenylsulfonyloxyimide)-4-methoxybenzyl Cyanide, α-(phenylsulfonyloxyimide)-thiophen-2-ylacetonitrile, α-(4-dodecylbenzenesulfonyloxyimide)-benzyl cyanide, α-[( P-toluenesulfonyloxyimine)-4-methoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonyloxyimide)-4-methoxyphenyl]acetonitrile, α- (p-toluenesulfonyl imine)-4-thiophene cyanide, α-(methylsulfonyloxyimine)-1-cyclopentenylacetonitrile, α-(methylsulfonyloxyimine)- 1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimine)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimine)-1-ring Alkenyl acetonitrile, α-(trifluoromethylsulfonyloxyimide)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimine)-cyclohexylacetonitrile, α-(B Alkylsulfonyloxyimine)-ethylacetonitrile, α-(propylsulfonyloxyimide)-propylacetonitrile, α-(cyclohexylsulfonyloxyimide)-cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimine)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimide)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimine)-1 -cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimide)-1-cyclopentenylacetonitrile, α-(n-butylsulfonyloxyimide)-1-cyclopentenyl Acetonitrile, α-(ethylsulfonyloxyimine)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1- Cyclohexenylacetonitrile, α-(n-butylsulfonyloxyimide)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimine)-phenylacetonitrile, α-(A Alkylsulfonyloxyimine)-p-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimide)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimide )-p-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimine)-p-methoxyphenylacetonitrile, α-(propylsulfonyloxyimide)-p-methyl Phenylacetonitrile, α-(methylsulfonyloxyimine)-p-bromophenylacetonitrile and the like can be mentioned.

Moreover, as a preferable example, the following can be illustrated.

Specific examples of the dialkyl or bisarylsulfonyldiazonanes in the diazane acid generator include bis(isopropylsulfonyl)diazide and bis(p-toluenesulfonyl). Azase, bis(1,1-dimethylethylsulfonyl)diazide, bis(cyclohexylsulfonyl)diazide, bis(2,4-dimethylphenylsulfonyl) Diazane and the like can be mentioned.

Further, examples of the poly(bissulfonyl)diazonanes include 1,3-bis(phenylsulfonyldiazomethylsulfonyl)propane and 1,4-bis(phenylsulfonate). Base heavy nitrogen methylsulfonyl) butane, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(phenylsulfonyldiazomethylsulfonate Sulfhydryl, 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane, 1,3-bis(cyclohexylsulfonyldiazomethylsulfonyl)propane, 1 6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl)decane, etc. are mentioned.

As the component (B), one type or a combination of two or more types of acid generators may be used alone. The content of the component (B) in the resist composition is preferably 0.5 to 50 parts by mass, and preferably 1 to 40 parts by mass, per 100 parts by mass of the component (A). When the content of the component (B) is in the above range, it is easy to form a good pattern using the resist composition.

[(C) component]

The resist composition is produced by dissolving a material in a solvent (hereinafter referred to as a component (C)). The component (C) is not particularly limited as long as it can be used as a homogeneous solution, and can be suitably selected from the solvent for a known resist composition.

Specific examples of the solvent include lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentanone, methyl isoamyl ketone, and 2-heptanone. Ketones; polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetic acid a monoalkyl ether or a monophenyl ether having a compound such as an ester bond, a polyhydric alcohol or a compound having an ester bond, a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl ether. Ether bond a derivative of a polyhydric alcohol such as a compound; such as a cyclic ether of dioxane or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, pyruvic acid An ester such as ethyl ester, methyl methoxypropionate or ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, diphenyl methyl ether, An aromatic organic solvent such as phenethyl ether, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, isopropyltoluene or mesitylene Out. These solvents may be used singly or as a mixed solvent of two or more kinds.

Among these solvents, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), γ-butyrolactone, ethyl lactate (EL), and cyclohexanone (CH) are preferred.

Further, a mixed solvent of PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined only by considering the compatibility of PGMEA with a polar solvent, and as PGMEA: the polar solvent is preferably 1:9 to 9:1, and the ratio of 2:8 to 8:2 is preferable. good.

More specifically, when EL is added as a polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, and preferably 2:8 to 8:2. Further, when PGME is added as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, preferably 2:8 to 8:2, and particularly preferably 3:7 to 7:3.

Further, as the component (C), at least one selected from the group consisting of PGMEA, PGME, CH, and EL and a mixed solvent of γ-butyrolactone are also preferable. At this time, as the mixing ratio, the former and the latter are preferably 70:30 to 95:5.

The amount of the component (C) to be used is not particularly limited, and can be suitably set to a solid content concentration at which a resist composition can be applied to a substrate or the like. In general, the solid content concentration of the anticorrosive composition is from 1 to 20% by mass, preferably from 2 to 15% by mass, based on the component (C).

[arbitrary component]

The following describes the optional components which may contain the resist composition.

((D) component (quenching agent)

The anticorrosive composition may contain a quenching agent (hereinafter referred to as a component (D)) as an optional component. The acid diffusion-promoting agent, that is, the acid-diffusing agent, that is, the acid quenching agent which is caused by the exposure of the component (B) is not particularly limited, and may be arbitrarily selected from known ones.

As the component (D), a low molecular compound (non-polymer) is generally used. The component (D) may, for example, be an amine such as an aliphatic amine or an aromatic amine, and more preferably an aliphatic amine, particularly preferably a second-order aliphatic amine or a third-order aliphatic amine. The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group is preferably a carbon number of from 1 to 20.

The aliphatic amine is, for example, an amine (alkylamine or alkylolamine) or a cyclic amine in which at least one hydrogen atom of ammonia (NH ₃ ) is substituted with an alkyl group having 20 or less carbon atoms or a hydroxyalkyl group. Can be mentioned.

Specific examples of the alkylamine and the alkylolamine include a monoalkylamine such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine or n-decylamine; Ethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, bicyclo a dialkylamine such as hexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, three a trialkylamine such as -n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, tri-n-dodecylamine; diethanolamine, three Alkyl alcohol amines such as ethanolamine, diisopropanolamine, triisopropanolamine, bis-n-octanolamine, tri-n-octanolamine, stearyl diol diethanolamine, and lauryl diethanolamine are exemplified. Among them, trialkylamines and/or alkylolamines are preferred.

The cyclic amine may, for example, be a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic one (aliphatic monocyclic amine) or a polycyclic one (aliphatic polycyclic amine).

Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, and specific examples thereof include 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.

As other aliphatic amines, there are ginseng (2-methoxymethoxyethyl)amine, gin {2-(2-methoxyethoxy)ethyl}amine, and {2-(2-methoxy) Ethylethoxymethoxy)ethyl}amine, gin {2-(1-methoxyethoxy)ethyl}amine, gin {2-(1-ethoxyethoxy)ethyl}amine Reference may be made to {2-(1-ethoxypropoxy)ethyl}amine, gin[2-{2-(2-hydroxyethoxy)ethoxy}ethylamine, and the like.

As the aromatic amine, for example, aniline, pyridine, 4-dimethylaminopyridine, pyrrole, hydrazine, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, trityl group Amine, 2,6-diisopropylaniline, 2,2'-double Pyridine, 4,4'-bipyridine and the like can be mentioned.

Further, the cation salt of the onium salt represented by the general formula (b1) and the combination of a hydroxyl ion or a perfluoroalkylcarboxylic acid ion as described in the component (B) can also be used as a quenching agent. The perfluoroalkyl group contained in the perfluoroalkyl carboxylic acid ion preferably has 1 to 6 carbon atoms and preferably 1 to 4 carbon atoms.

These (D) components may be used alone or in combination of two or more. The component (D) is generally used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A). When the amount of the component (D) used is in this range, the shape of the resist pattern, the stability of the argument, and the like can be improved.

((E) component (organic carboxylic acid, or phosphorus oxyacid))

The anticorrosive composition may contain, as an optional component, an oxo acid selected from the group consisting of an organic carboxylic acid and phosphorus, and a derivative thereof, for the purpose of preventing deterioration of sensitivity, shape of a resist pattern, stability over time, and the like. At least one compound (hereinafter also referred to as component (E)) in a group.

Preferred examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. Phosphoric acid, phosphonic acid, phosphonic acid and the like are preferable as the oxyacid of phosphorus, and phosphonic acid is preferable among them. Examples of the oxo acid-containing derivative of phosphorus include an ester in which a hydrogen atom of the above-described oxyacid is substituted with a hydrocarbon group. In this case, examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 15 carbon atoms.

Examples of the phosphoric acid derivative include a phosphate ester such as di-n-butyl phosphate or diphenyl phosphate. As a derivative of phosphonic acid, there are dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, phosphonic acid Phosphonates such as benzhydryl esters and the like can be mentioned. Examples of the phosphonic acid derivative include a phosphonate such as phenylphosphonic acid.

The component (E) may be used alone or in combination of two or more. The component (E) is generally used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A).

((F) component (fluorinated compound)

The anticorrosive composition may further contain an optional component, and may contain a fluorine-containing compound component (F) (hereinafter referred to as a component (F)). In the present invention, the component (F) contains a fluorine-containing polymer compound (F1) having a constituent unit (f) containing an alkali-dissociable group (hereinafter referred to as "(F1) component"). As an example of the structural unit (f) containing an alkali dissociative group, the unit represented by the following general formula (f1) is mentioned.

[In the general formula (f1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Q ⁰ is a single bond or a divalent linking group having a fluorine atom, R ^f1 Is an organic group which may have a fluorine atom]

Examples of the divalent linking group in Q ⁰ include a divalent hydrocarbon group which may have a substituent, and a divalent linking group which contains a hetero atom. The divalent linking group in Q ⁰ may be a "divalent hydrocarbon group having a substituent" or a "divalent linking group containing a hetero atom", and may be a fluorine atom.

The divalent linking group in Q ⁰ is a linear or branched alkyl group, a divalent aromatic ring group or a divalent linking group containing a hetero atom, or a fluorine atom in any of them. It is better. Among them, a divalent linking group having a fluorine atom-containing hetero atom is particularly preferred.

When Q ⁰ is a linear or branched chain alkyl group, the alkyl group is preferably a carbon number of 1 to 10, preferably a carbon number of 1 to 6, preferably a carbon number of 1 to 4, and a carbon number. 1~3 is the best. Specifically, the same as the linear alkylene group or the branched alkyl group which is exemplified as the above-mentioned "divalent hydrocarbon group which may have a substituent" is mentioned.

When Q ⁰ is a divalent aromatic ring group, examples of the aromatic ring group include aroma of a monovalent aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group. a divalent aromatic hydrocarbon group in which one hydrogen atom is further removed from a nucleus of a hydrocarbon; and a part of a carbon atom constituting a ring of a divalent aromatic hydrocarbon group is substituted by a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. a hydrocarbon group; an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., and derived from the core of the aromatic hydrocarbon Further, an aromatic hydrocarbon group or the like of one hydrogen atom is removed.

When Q ⁰ is a divalent linking group containing a hetero atom, the preferred ones as a linking group are -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-. O-, -C(=O)-NH-, -NR ⁰⁴ - (R ⁰⁴ is a substituent such as an alkyl group or a fluorenyl group), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, formula -C(=O)-OR ⁰⁸ - group, formula -OR ⁰⁸ - group, formula -R ⁰⁹ -O-, formula -R ⁰⁹ -OR ⁰⁸ - Bases and the like can be cited.

R ⁰⁸ is a divalent hydrocarbon group which may have a substituent, and a linear or branched aliphatic hydrocarbon group is preferred, and an alkylene group or an alkylalkyl group is preferred. It is particularly preferred as an alkyl group to form a methyl group and an ethyl group. The alkyl group in the alkylalkylene 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 an ethyl group. These R ⁰⁸ may contain a fluorine atom or may not contain a fluorine atom.

R ⁰⁹ is a divalent aromatic ring group, and it is preferred to further remove one hydrogen atom from the nucleus of the aromatic hydrocarbon of the monovalent aromatic hydrocarbon group, and to remove one hydrogen atom from the naphthyl group. The base is the best.

In the general formula (f1), the structure of R ^f1 may be linear, branched or cyclic, and is preferably a linear or branched chain. For R ^f1 , the carbon number of the organic group is preferably from 1 to 20, preferably from 1 to 15, preferably from 1 to 10, and most preferably from 1 to 5.

R ^f1 is preferably a fluorination ratio of 25% or more, more preferably 50% or more, and particularly preferably 60% or more.

The "fluorination rate" is a ratio (%) of the number of (fluorine atoms) in the organic group (the total number of hydrogen atoms and fluorine atoms).

As R ^f1 , for example, a methyl group, an ethyl group, or a fluorinated hydrocarbon group which may have a substituent may be mentioned.

The fluorinated hydrocarbon group which may have a substituent in R ^f1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferred. As R ^f1 , a fluorinated saturated hydrocarbon group or a fluorinated unsaturated hydrocarbon group is preferred, and a fluorinated saturated hydrocarbon group, i.e., a fluorinated alkyl group, is particularly preferred.

As the fluorinated alkyl group, a group in which a part or all of a hydrogen atom of the unsubstituted alkyl group described above is substituted by a fluorine atom may be mentioned. Fluorinated alkyl group can be no The group in which one of the hydrogen atoms of the alkyl group is substituted by a fluorine atom may be a group in which all of the hydrogen atoms of the unsubstituted alkyl group are substituted by a fluorine atom (perfluoroalkyl group). The unsubstituted alkyl group may be any of a linear chain, a branched chain or a cyclic group, or a combination of a linear or branched alkyl group and a cyclic alkyl group.

The unsubstituted linear alkyl group preferably has a carbon number of 1 to 10 and preferably has a carbon number of 1 to 8. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-fluorenyl group, an n-fluorenyl group, and the like. .

The unsubstituted branched chain alkyl group preferably has a carbon number of 3 to 10 and a carbon number of 3 to 8. As the branched chain alkyl group, a third-order alkyl group is preferred. Examples of the unsubstituted cyclic alkyl group include a monocycloalkane or a group in which one hydrogen atom is removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specific examples thereof include a monocycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a polycycloalkyl group such as an adamantyl group, a norbornene group, an isobornyl group, a tricyclodecyl group or a tetracyclododecyl group. The combination of an unsubstituted linear or branched alkyl group and a cyclic alkyl group may be a linear or branched alkyl group bonded to a cyclic alkyl group as a substituent, and a cyclic alkane. The group is bonded to a group of a linear or branched chain alkyl group as a substituent. Examples of the substituent which may have a fluorinated hydrocarbon group include a lower alkyl group having 1 to 5 carbon atoms.

The fluorine-containing polymer compound (F1-1) having the following constituent unit is particularly preferable as the component (F).

[In the general formula (F1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and the plural R may be the same or different. j" is an integer of 0 to 3, R ³⁰ is an alkyl group having 1 to 5 carbon atoms, and h" is an integer of 1 to 6]

In the formula (F1-1), R is the same as R in the above-mentioned constituent unit (a1). j" is preferably 0 to 2, preferably 0 or 1, and most preferably 0. R ³⁰ is the same as the lower alkyl group in R, particularly preferably methyl or ethyl, and ethyl For the best. h" is better than 3 or 4, with 4 being the best.

The mass average molecular weight (Mw) of the component (F) (based on the polystyrene conversion standard by gel permeation chromatography) is not particularly limited, and is preferably from 2,000 to 100,000, more preferably from 3,000 to 100,000, and from 4,000 to 4,000. 50000 is better, and 5000~50,000 is the best. When the component (F) having the mass average molecular weight (Mw) is used, the component (F) is easily dissolved in the resist composition, and the obtained resist composition is likely to form a pattern having a good cross-sectional shape. Further, the degree of dispersion (Mw/Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and particularly preferably 1.2 to 2.8.

The component (F) may be used alone or in combination of two or more. The content of the component (F) in the resist composition is 100 mass for the component (A) The portion is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, more preferably 0.3 to 30 parts by mass, and most preferably 0.5 to 15 parts by mass. When the component (F) is used in an amount in this range, it is preferable to obtain a resist composition having excellent etching properties while being used for liquid immersion exposure.

(other optional ingredients)

An additive having a miscibility such as an additive resin for improving the properties of the resist film, a surfactant for improving coating properties, a dissolution inhibitor, a plasticizer, a stabilizer, and the like may be appropriately added to the resist composition as necessary. A coloring agent, a halo preventing agent, a dye, or the like.

<Resist film forming method>

The method of forming a resist film will be described with reference to Figs. 1(a) and 1(b). A resist composition containing the components described above is applied onto the substrate 10, and a resist film 11 is formed on the substrate 10. The method of applying the resist composition to the substrate 10 is not particularly limited as long as the resist composition can be favorably applied to the substrate to the desired film thickness. Specific examples of the coating method include a spin coating method, a spray method, a roll coating method, and a dipping method, and a spin coating method is preferred.

After the resist composition is applied onto the substrate 10 to form the resist film 11, the resist film 11 on the substrate is heated (pre-baked) as necessary. Thereby, a film from which an insoluble solvent is removed can be uniformly formed. The temperature of the pre-baking is not particularly limited, and is preferably 50 ° C to 160 ° C, and preferably 60 ° C to 140 ° C.

In the present invention, the type of the substrate 10 on which the film is formed is not particularly limited. As an example of the substrate 10, an inorganic substrate such as ruthenium, SiO ₂ or SiN, a coated inorganic substrate such as SOG, a semiconductor manufacturing step such as IC, a manufacturing step of a circuit substrate such as a liquid crystal or a thermal head, and the like can be used. A commonly used substrate can be used in the etching step of the optical application.

An anti-reflection film (not shown) may be applied to the substrate 10 before the resist film 11 is formed. As the non-reflection preventing film, any of an organic film type such as an inorganic film type such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon or amorphous germanium, or a light absorbing agent and a polymer material can be used. Further, as the organic antireflection film, a commercially available antireflective film such as DUV30 series manufactured by Brewer Science Co., Ltd., DUV-40 series, or AR-2, AR-3, and AR-5 manufactured by Shipley Co., Ltd. can be used.

≪Exposure step≫

The exposure step will be described with reference to Figs. 1(c) and (d). In the exposure step, the resist film 11 formed on the substrate 10 can be selectively exposed by the active energy source line 12 such as ultraviolet rays or electron lines. The exposure method is not particularly limited, and can be appropriately selected from various methods used in the past as a method of exposing the resist film 11. As a suitable method, a method in which the resist film 11 passes through the predetermined mask 13 and is irradiated with an active energy source line 12 such as an ultraviolet ray or an electron beam can be mentioned.

The exposed portion 14 and the unexposed portion 15 are formed in the resist film 11 by the exposure. In the resist film forming step, the solubility of the developing liquid containing the organic solvent is reduced by the use of (A) by the action of an acid. And a resist composition of (B) a compound which generates an acid by irradiation with active light or radiation, and the exposed portion 14 acts on the developing liquid containing the organic solvent by the action of the acid generated by the component (B). Solubility will decrease. On the other hand, since the unexposed portion 15 is irradiated with the active energy source line 12, it is easily dissolved in the developing liquid containing the organic solvent.

Examples of the active energy source line 12 include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, and electron beam. Among them, the wavelength is preferably 250 nm or less, preferably 220 nm or less, more preferably 1 to 200 mm, and far ultraviolet light is preferred. Specific examples of the far-ultraviolet light include an ArF excimer laser, an F ₂ excimer laser, and EUV (13 nm).

In the exposure step, a liquid immersion exposure method in which a liquid immersion medium is filled between the optical lens portion and the resist film and exposed is used as necessary. The liquid immersion medium is not particularly limited as long as it has a refractive index larger than that of air and is smaller than the refractive index of the resist film to be used. As such a liquid immersion medium, there are water (pure water, deionized water), a liquid in which various additives are added to water, a liquid having a high refractive index, a fluorine-based inert liquid, a hydrazine-based inert liquid, a hydrocarbon-based liquid, and the like. Liquid immersion media with high refractive index properties under development can also be used in the future. The fluorine-based inert liquid is a liquid containing a fluorine-based compound such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ or C ₅ H ₃ F ₇ as a main component. Among them, water (pure water, deionized water) is preferred when using 193 nm wavelength exposure light (ArF excimer laser, etc.) from the viewpoints of cost, safety, environmental problems, and general availability. When exposure light (F ₂ excimer laser or the like) is used at a wavelength of 157 nm, a fluorine-based inert solvent is preferred.

After the end of the exposure, baking (PEB) is preferred. The temperature of the PEB is not particularly limited as long as it can obtain a good resist pattern, and is generally 40 ° C to 160 ° C.

≪The first imaging step≫

The second development step will be explained by means of Figs. 1(e), (f) and (g). In the first developing step, the exposed resist film 11 is developed by a developing liquid 16 containing an organic solvent to form a resist pattern 17. As described above, the solubility of the exposure portion 14 in the resist film 11 for the developer containing the organic solvent is lowered, and the unexposed portion 15 is easily dissolved in the developer containing the organic solvent. Therefore, when the exposed resist film 11 is brought into contact with the developing liquid 16, the unexposed portion 15 is dissolved in the developing liquid 16, and the exposed portion 14 is not dissolved in the developing liquid 16, and can be used as the resist pattern 17 Visualization.

The organic solvent contained in the developing solution 16 is only required to dissolve the unexposed portion 15 (component (A) before exposure), and a known organic solvent can be appropriately selected. Specific examples of the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, the ether solvent, and the hydrocarbon solvent.

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 the structure, and the "alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of the aliphatic hydrocarbon group. The guanamine-based solvent is an organic solvent containing a guanamine group in the structure. The ether solvent is an organic solvent containing C-O-C in the structure. Among the organic solvents, there are also a plurality of functional groups in the structure which impart the characteristics of each of the above solvents. The organic solvent should correspond to any solvent species containing a functional group possessed by the organic solvent. For example, diethylene glycol monomethyl ether corresponds to any of an alcohol solvent and an ether solvent in the above classification. Further, the hydrocarbon solvent is a hydrocarbon solvent which is formed of a hydrocarbon and does not have a substituent (a hydrogen atom or a group other than a hydrocarbon group or an atom).

Specific examples of the respective solvents include, as the ketone solvent, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, and 2-hexanone. , diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl ketone, acetone acetone, ionone, diacetone alcohol, acetyl group Methanol, acetophenone, methylnaphthone, isophorone, propyl carbonate, γ-butyrolactone and the like can be mentioned.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, and ethoxylate. Ethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol single Phenyl 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 Acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxy butyl Acetate, 2-methoxypentyl Acid ester, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxy Pentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, formic acid Ethyl ester, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, pyruvate propyl, Butyl pyruvate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, 2-hydroxypropane Ethyl acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionic acid Esters and the like can be mentioned. Further, examples of the cyclic ester solvent include lactones such as γ-butyrolactone.

The ester solvent is preferably a solvent represented by the general formula (S1) described later or a solvent represented by the general formula (S2) described later, and a solvent represented by the general formula (S1) is preferred, and an alkyl acetate is particularly preferred. It is best to use butyl acetate.

Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, and n. a monohydric alcohol such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonanol or 3-methoxy-1-butanol; ethylene glycol, diethylene glycol, triethylene glycol, etc. Glycol solvent; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy methyl butanol, ethylene glycol single ethyl Ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether Examples thereof include a glycol ether solvent containing a hydroxyl group and the like. Among them, glycol ether solvents are also preferred.

Examples of the ether solvent include a glycol ether solvent containing the above hydroxyl group; propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; The glycol ether solvent; dioxane, tetrahydrofuran, anisole, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, etc. are mentioned. Among them, a glycol ether solvent such as a glycol ether solvent containing a hydroxyl group or a glycol ether solvent not containing a hydroxyl group is preferred.

Examples of the amide-based solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, trimethylamine hexamethylphosphate, 1,3. - dimethyl-2-imidazolidinone or the like can be mentioned.

Examples of the hydrocarbon solvent include pentane, hexane, octane, decane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluorocarbon. An aliphatic hydrocarbon solvent such as heptane; toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethyl An aromatic hydrocarbon solvent such as methylbenzene, trimethylbenzene, ethyldimethylbenzene or dipropylbenzene can be mentioned. Among them, aromatic hydrocarbon solvents are also preferred.

These organic solvents may be used singly or in combination of two or more. Further, it can be used after being mixed with an organic solvent other than the above or water.

As the organic solvent to be used in the organic-based developing liquid, a solvent represented by the following general formula (S1) or (S2) is preferred.

R ⁰⁰ -C(=O)-OR ⁰¹ ...(S1)

R ⁰² -C(=O)-OR ⁰³ -OR ⁰⁴ (S2) [In the general formula (S1), R ⁰⁰ and R ^{01 are} each independently a hydrogen atom, an alkyl group, an alkoxy group or an alkoxycarbonyl group. A carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and R ⁰⁰ and R ⁰¹ are bonded to each other to form a ring. In the general formula (S2), R ⁰² and R ^{04 are} each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom, and R ⁰² and R ⁰⁴ are bonded to each other to form a ring. , R ⁰³ is an alkylene group]

In the general formula (S1), the alkyl group in R ⁰⁰ and R ⁰¹ may be linear, branched or cyclic, preferably in a linear or branched chain, and the carbon number is 1 to 5 It is better. The alkyl group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, and a cyano group.

The alkyl group in the alkoxy group or the alkoxycarbonyl group is the same as the above-mentioned alkyl group.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is preferred.

R ⁰⁰ and R ^{01 are} each preferably a hydrogen atom or an alkyl group.

Specific examples of the solvent represented by the general formula (S1) (hereinafter sometimes referred to as the solvent (S1)) include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, and isoamyl acetate. Ester, methyl formic acid, ethyl formic acid, butyl formic acid, propyl formic acid, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, pyruvic acid Ester, propyl pyruvate, butyl pyruvate, methyl acetate, Ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, γ-butyrolactone, etc. Give it.

As the solvent (S1), those in which R ⁰⁰ and R ⁰¹ are unsubstituted alkyl groups are preferred, and alkyl acetate is preferred, and butyl acetate is particularly preferred.

In the general formula (S2), R ⁰² and R ⁰⁴ are the same as those of the above R ⁰⁰ and R ⁰¹ .

The alkylene group in R ⁰³ may be any of a linear chain, a branched chain, and a cyclic chain, and is preferably a linear chain or a branched chain, and preferably has 1 to 5 carbon atoms. The alkylene group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, and a cyano group. Further, when the carbon number of the alkylene group is 2 or more, an oxygen atom (-O-) may be interposed between the carbon atoms of the alkylene group.

Specific examples of the solvent represented by the general formula (S2) (hereinafter sometimes referred to as the solvent (S2)) include, for example, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene. Alcohol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobenzene Ethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol single Propyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxy Propionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutylacetic acid Ester, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-B Oxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetic acid Ester, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate and the like can be mentioned.

The solvent (S1) to (S2) may be used singly or in combination of two or more. Further, the solvent (S1) or the solvent (S2) may be used alone or in combination of two or more. Further, at least one selected from the group consisting of solvents (S1) and (S2) may be used in combination with other solvents.

The other solvent is not particularly limited as long as it can be separated from the solvent (S1) or (S2) to be used, and is not particularly limited. For example, it can be suitably selected from the above-mentioned ester solvent, ketone solvent, alcohol solvent, and hydrazine. An amine solvent, an ether solvent, a hydrocarbon solvent, or the like. Among them, a glycol ether solvent such as a glycol ether solvent containing a hydroxyl group or a glycol ether solvent not containing a hydroxyl group (hereinafter sometimes referred to as a solvent (S3)) is preferred, and a propylene glycol monomethyl group is contained. A glycolic ether solvent such as an ether is preferred.

When the solvent (S1) and the solvent (S2) are mixed, the mass ratio of (S1)/(S2) is preferably 99/1 to 50/50, and 95/5 to 60/40 is preferably 90/10. 70/30 is better.

When the solvent (S1) and the solvent (S3) are mixed, the mass ratio of (S1)/(S3) is preferably 99/1 to 50/50, and 95/5 to 60/40 is preferably 90/10. 70/30 is better.

When the solvent (S1) is mixed with the solvent (S2) and the solvent (S3), the mass ratio of (S1)/(S2)/(S3) is 90/0.1/9.9 to 50/15/35. Preferably, it is preferably 85/0.5/14.5~60/10/30, and more preferably 80/1/19~70/5/25.

When two or more solvents (S1) are mixed, it is preferred to mix a chain ester solvent and a cyclic ester solvent. The mass ratio (chain/ring) at this time is preferably 99.9/0.1 to 80/20, preferably 99/1 to 85/15, and more preferably 98/2 to 90/10.

As the organic solvent used in the developing solution 16, it is preferable to use an organic solvent not containing a halogen atom from the viewpoint that the cost of the solvent used for development can be lowered. The content of the organic solvent which does not contain a halogen atom in the total weight of the organic-based developing solution is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. 100% by mass. The organic solvent used in the organic-based developing solution has a boiling point of 50 ° C or higher and preferably less than 250 ° C. The ignition point of the organic solvent used in the organic-based developing solution is preferably 200 ° C or higher.

A known additive can be added to the developing solution 16 as necessary. As an additive, a surfactant is mentioned, for example. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or lanthanoid surfactant can be used.

Examples of commercially available commercial surfactants include Eftop EF 301, EF 303, (New Akita Chemical Co., Ltd.), Fluorad FC 430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, and R08 (large). Fluorine system such as Japan Ink Chemical Industry Co., Ltd., Surflon S-382, SC101, 102, 103, 104, 105, 106 (made by Asahi Glass Co., Ltd.) and Troysol S-366 (made by Troychemical Co., Ltd.) Surfactant or lanthanide surfactant. Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

Further, as the surfactant, in addition to the above-mentioned known ones, the following surfactants may be used, and the surfactant is a polymer which is subjected to a thermal telomerization reaction (also referred to as a telomer). A fluoroaliphatic group-derived polymer derived from a fluoroaliphatic compound produced by an oligomer reaction method (also referred to as an oligomer method).

As a polymer having a fluoroaliphatic group, copolymerization of a monomer having a fluoroaliphatic group with (poly(oxyalkylene)) acrylate and/or (poly(oxyalkylene)) methacrylate Preferably, the material may be irregularly distributed or may be block copolymerized. Further, examples of the poly(oxyalkylene) group include a poly(ethylene oxide) group, a poly(propylene oxide) group, a poly(butylene oxide) group, and the like, and poly(ethylene oxide and a unit of a stretched alkyl group having a different chain length in the same chain length, such as a block linker of propylene oxide and ethylene oxide) or a base of a poly(ethylene oxide and propylene oxide block link) . And the copolymer having a fluoroaliphatic group and a (poly(oxyalkylene)) acrylate (or methacrylate) is not only a 2-membered copolymer, but may also have a difference at the same time. A monomer having a fluoroaliphatic group or more, or a ternary or higher copolymer having two or more kinds of (poly(oxyalkylene)) acrylate (or methacrylate).

For example, commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by Dainippon Ink Chemical Industries Co., Ltd.). And a copolymer of a C ₆ F ₁₃ -based acrylate (or methacrylate) and (poly(oxyalkylene)) acrylate (or methacrylate), an acrylate having a C ₆ F ₁₃ group (or methacrylate) and (poly(ethylene oxide)) acrylate (or methacrylate) and (poly(propylene oxide)) acrylate (or methacrylate) copolymer, having a copolymer of a C ₈ F ₁₇ -based acrylate (or methacrylate) with (poly(oxyalkylene)) acrylate (or methacrylate), a C ₈ F ₁₇ -based acrylate (or a copolymer of (methacrylate) and (poly(ethylene oxide)) acrylate (or methacrylate) and (poly(propylene oxide)) acrylate (or methacrylate).

As the surfactant, a nonionic surfactant is preferred, and a fluorine-based surfactant or a quinone-based surfactant is preferred.

When the surfactant is added, the amount of the surfactant is generally 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and preferably 0.01 to 0.5% by mass, based on the total mass of the developing solution 16.

The method of developing the resist pattern 17 by the developing liquid 16 is not particularly limited, and can be carried out by appropriately selecting a known developing method. As a preferred development method, for example, a method in which the substrate 10 including the post-exposure resist film 11 is immersed in the developing solution 16 for a predetermined period of time (dipping method), and a developing solution on the surface of the resist film 11 after exposure is used. a method of spraying a developing solution by a surface tension by a surface tension for a certain period of time (paddle method), spraying a developing solution on the surface of the exposed resist film 11 (spraying method), and rotating the substrate 10 at a constant speed. A method of applying the developing liquid 16 while scanning the developing liquid coating nozzle at a constant speed against the resist film 11 after exposure (dynamic Dispersion method) and the like can be mentioned.

Further, after the development step, a step of stopping the development by replacing the development liquid 16 with another solvent can be carried out.

After the first development step, the resist pattern 17 can be washed using a rinse solution containing an organic solvent.

The rinse liquid used in the rinsing step is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing an organic solvent can be generally used. The organic solvent which can be used as the rinsing liquid is the same as the organic solvent which can be contained in the developing liquid 16 . The rinsing liquid may contain a plurality of the above organic solvents, and may contain an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the water content is 10% by mass or less, good development characteristics can be obtained.

In the rinse solution, an appropriate amount of a surfactant may be added and used.

For the rinsing step, the resist pattern 17 on the substrate 10 after development is subjected to a cleaning treatment using a rinsing liquid containing the above organic solvent. The washing treatment method is not particularly limited, and can be carried out in the same manner as the development by the developing liquid 16.

≪First coating film formation step≫

The first coating film forming step will be described with reference to Figs. 1(f) and (g). In the first coating film forming step, a resin containing (A ¹ ) a decrease in solubility in an organic solvent by the action of an acid is applied to the resist pattern 17 (hereinafter also referred to as "(A ¹ ) component"). The first coating film 18 is formed after the first coating forming agent of the (C ¹ ) solvent (hereinafter also referred to as "(C ¹ ) component)".

As a method of forming the first coating film 18 after applying the first coating forming agent on the resist pattern 17, the same method as the method of forming the resist film 11 on the substrate 10 can be used for the resist film forming step.

Further, the resin (A ¹ ) contained in the first coating forming agent can be used as the resin having a reduced solubility in an organic solvent by the action of an acid, and the (A) component contained in the resist composition used in the resist film forming step can be used. The same resin. Examples of the resin (A ¹ ) having a reduced solubility in an organic solvent by the action of an acid include an acrylate-derived resin containing a constituent unit derived from an acrylate or a hydroxyl group containing a constituent unit derived from a hydroxystyrene derivative. A styrene-derived resin etc. are mentioned.

Further, as the (C ¹ ) solvent contained in the first coating forming agent, the same solvent as the component (C) contained in the resist composition used in the resist film forming step can be used.

Further, the first coating forming agent may be contained in various components other than the component (A) and the component (B) contained in the resist composition, as long as it does not inhibit the object of the present invention.

Further, as the first coating forming agent, a resist composition used in the resist film forming step can be used. When a first coating forming agent having a composition different from that of the resist composition is used, an apparatus for supplying a resist composition to the surface of the substrate and an apparatus for supplying the first covering forming agent to the surface of the substrate are necessary for forming a fine pattern. The composition of the production equipment of the type becomes complicated. However, when the resist composition is used as the first coating forming agent, the first coating forming agent is supplied The apparatus for the surface of the substrate becomes unnecessary, and the constitution for the production apparatus for forming a fine pattern can be simplified. At this time, since the frequency of troubles such as failure of the production equipment can be reduced, the maintenance cost can improve the operation rate of the production equipment used for forming the fine pattern.

≪First thickening step≫

The first thickening step will be described with reference to Figs. 1(g) and (h). In the first thickening step, the resist pattern 17 coated with the first coating forming agent is added to the first coating film forming step, and the surface of the resist pattern 17 is not formed with the high molecular weight. The resist pattern 17 is thickened by the first hardly soluble layer 19 (hereinafter also referred to as a poorly soluble layer) which is insoluble in the liquid.

In the resist composition, as the component (B), an acid which generates an acid after irradiation with active light or radiation is present in the resist pattern 17 corresponding to the exposed portion 14, and the acid generated by the component (B) remains. . Therefore, when the resist pattern 17 of the first coating forming agent is heated and applied, the acid existing in the resist pattern 17 is diffused to the first by the interface between the resist pattern 17 and the first coating film 18. Cover film 18.

And forming a first coating formed by the first coating agent of 18, comprising (A ¹⁾ by action of an acid resin to reduce the solubility of the organic solvent. Therefore, in the first coating film 18, the solubility in the organic solvent is lowered in the vicinity of the interface between the first coating film 18 and the resist pattern 17 by the action of the acid diffused by the resist pattern 17. The first hardly soluble layer 19 is formed on the surface of the resist pattern 17, and the resist pattern 17 is thickened.

The temperature at which the resist pattern 17 is heated can only form the first hardly soluble layer 19 well. It is not particularly limited. The heating temperature and the heating time can be appropriately selected in accordance with the type of the resist composition to be used, the type of the first covering agent, and the amount of refining of the resist pattern. The heating temperature is preferably 30 ° C to 200 ° C, preferably 60 ° C to 180 ° C, and more preferably 80 ° C to 160 ° C.

After the first thickening step, a fine resist pattern 17 (containing the first hardly soluble layer 19) is formed on the substrate 10. The resist pattern 17 after the first thickening step remains on the surface of the soluble portion of the first coating film 18 in which the first hard layer 19 is not changed. Therefore, the soluble portion remaining in the first coating film 18 on the resist pattern 17 is removed from the resist pattern surface as needed for the second developing step.

≪Second imaging step≫

The second development step will be described with reference to FIGS. 1(h) and (i). As shown in FIG. 1(h), the soluble portion in the first coating film 18 remains on the resist pattern 17 (including the first hard layer 19) after the first thickening step. The soluble portion in the first coating film 18 can be removed by development using a developing solution containing an organic solvent.

In the second developing step, the developing method and the developing liquid are the same as those of the first developing step. Further, in the second developing step, it is preferable to wash the resist pattern 17 by using a rinse liquid containing an organic solvent in the same manner as in the first developing step after development.

The fine pattern forming method of the present invention described above can further refine the resist pattern formed by the negative developing process.

In the method for forming a fine pattern described above, as the first coating forming agent used in the first coating film forming step, a resin containing (A ¹ ) having a reduced solubility in an organic solvent by the action of an acid, (B ^{1 ) is used.} It is preferred that the compound which generates an acid after heating (hereinafter also referred to as "(B ¹ ) component)" and (C ¹ ) solvent. The first coating agent is formed in addition to containing a (A ¹⁾ component and the (C ¹⁾ component containing (B ¹⁾ component, to perform a fine pattern by the method described above, applying a second coating of a specific composition The forming agent can further refine the pattern which is refined by the above method by applying the predetermined treatment. When the first coating layer formed of the first coating forming agent contains the component (B ¹ ), the first coating layer is heated at a predetermined temperature to be described later, and the first coating layer can be produced from the (B ¹ ) component. acid. Since the acid acts on the (A ² ) component in the second coating layer, the first coating forming agent containing the (A ¹ ) component, the (B ¹ ) component, and the (C ¹ ) component can be used. The resist pattern is coated under a plurality of layers to be miniaturized.

The (B ¹ ) component to be used in the first coating forming agent is not particularly limited as long as it does not inhibit the refinement of the resist pattern by the first coating forming agent because the acid is generated by heating. The acid generation start temperature (T _A ) at which the (B ¹ ) component starts to generate an acid upon heating is not particularly limited, and is preferably 80 ° C to 200, and preferably 100 ° C to 180 ° C. When the (B ¹ ) component having the starting temperature (T _A ) of the acid having this range is generated, even if it is heated to generate an acid, the resist pattern is not easily deteriorated by heating. transsexual.

The acid generation start temperature (T _A ) of the component (B ¹ ) is a heat generation curve which can be measured by a differential scanning calorimeter (DSC), and the acid generation start temperature (T _A ) of the component (B ¹ ) is obtained. Further, the junction temperature at the turning point in the turning point at the start of the heat generation by the low temperature side bottom line of the exothermic peak and the low temperature side curve of the exothermic peak is taken as the acid generation starting temperature (T _A ).

Preferred examples of the component (B ¹ ) include an oxime ester compound of an organic sulfonic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin p-toluenesulfonic acid, and 2-nitro group. Benzyl p-toluenesulfonic acid, alkyl esters of other organic sulfonic acids, and the like. Further, an onium salt such as an onium salt, an iodonium salt, a benzothiazolium salt, an ammonium salt or a phosphonium salt can be applied to the (B ¹ ) component. Among them, an oxime ester compound of an organic sulfonic acid is preferred from the viewpoint of excellent stability in a state of no heating or excellent solubility stability in the first coating forming agent.

Preferred examples of the oxime ester compound of the organic sulfonic acid include compounds represented by the following formulas (TAG-1) to (TAG-4).

[In the formula (TAG-1) to (TAG-4), R ^b1-1 is an alkyl group having 1 to 10 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, a fluorinated alkyl group having 1 to 10 carbon atoms, or The group represented by the following formula (R ^b1-3 ). R ^b1-2 is a ^group represented by -(CF ₂ ) _f1 -H, and f1 is an integer of 1 to 10]

[*" in the group of the formula (R ^b1-3 ) indicates a bond with a sulfur atom]

When R ^b1-1 is an alkyl group, the alkyl group may be linear, branched or cyclic, and is preferably a linear chain. Preferred examples of the case where R ^b1-1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. The base, n-fluorenyl group, and n-fluorenyl group are exemplified.

When R ^b1-1 is a fluoroalkyl group, the number of fluorine atoms contained in the fluoroalkyl group is not particularly limited, and the fluoroalkyl group is preferably a perfluoroalkyl group. When R ^b1-1 is a fluoroalkyl group, the fluoroalkyl group may be linear, branched or cyclic, and is preferably a linear chain. The preferred group when R ^b1-1 is a fluoroalkyl group, and the preferred group when R ^b1-1 is an alkyl group is a group in which a hydrogen atom is completely substituted by a fluorine atom.

Further, when R ^b1-1 is a tolyl group, the tolyl group is preferably a p-tolyl group.

R ^b1-2 is a ^group represented by -(CF ₂ ) _f1 -H, and f1 is an integer of 1 to 10. F1 is preferably an integer from 3 to 6.

Among the compounds represented by the formula (TAG-1) to (TAG-4), the following TAG-a to TAG-g may be mentioned as a particularly preferable compound.

In the method of using the first coating forming agent containing the (A ¹ ) component, the (B ¹ ) component, and the (C ¹ ) component, the first thickening step and the second developing step will be described below.

≪First thickening step≫

The first thickening step will be described with reference to Figs. 1(g) and (h). In the first thickening step, for the first coating film forming step, the resist pattern 17 coated with the first coating forming agent is produced in an acid which does not reach (B ¹ ) a compound which generates an acid by heating. Heating is performed at a temperature of the starting temperature (T _A ), and a first layer 19 (hereinafter also referred to as a first hardly soluble layer) which is insoluble to the developing liquid is formed on the surface of the resist pattern 17 without being subjected to high molecular weight. The resist pattern 17 is thickened.

In the resist composition, as the component (B), a compound which generates an acid after irradiation with active light or radiation is present in the resist pattern 17 corresponding to the exposed portion 14 and remains by the component (B). acid. Therefore, when the resist pattern 17 coated with the coating forming agent is heated at a temperature that does not reach the acid generation starting temperature (T _A ) of the (B ¹ ) component, the resist pattern 17 is passed through and the first coating is applied. At the interface of the film 18, the acid present in the resist pattern 17 is diffused to the first coating film 18.

And, forming a first agent is a first coating film 18 formed of, comprising (A ¹⁾ by action of an acid to reduce the solubility of the organic solvent of the resin. Therefore, in the first coating film 18, the solubility in the organic solvent is reduced in the vicinity of the interface between the first coating film 18 and the resist pattern 17 by the action of the acid diffused by the resist pattern 17. A first hardly soluble layer 19 is formed on the surface of the resist pattern 17, and the resist pattern 17 is thickened.

The temperature at which the resist pattern 17 is heated is a temperature that does not reach the acid generation start temperature (T _A ) of the component (B ¹ ), and the first hardly soluble layer 19 can be formed well, and is not particularly limited. The heating temperature and the heating time are appropriately selected in accordance with the type of the resist composition to be used, the type of the first coating forming agent, and the amount of refining of the resist pattern. The heating temperature is preferably 30 ° C to 200 ° C, preferably 60 ° C to 180 ° C, and more preferably 80 ° C to 160 ° C.

When the resist pattern is heated at the acid generation start temperature (T _A ) of the component (B ¹ ), an acid is generated in the entire first coating film 18 by the (B ¹ ) component, and the acid acts. The entire first coating film 18 is made insoluble to the developing liquid. In this case, in the first coating film 18, as far as possible, the fine space is hardly melted in the fine space after development, and thus the predetermined fine space cannot be set in the resist pattern.

Thus, after the first thickening step, the refining resist pattern 17 (containing the first hardly soluble layer 19) is formed on the substrate 10. The resist pattern 17 after the first thickening step is a soluble portion remaining in the first coating film 18 having no change in the first hard-melting layer 19 on the surface. Therefore, the soluble portion remaining in the first coating film 18 on the resist pattern 17 is removed by the resist pattern surface in the second developing step.

≪Second imaging step≫

The second development step will be described with reference to FIGS. 1(h) and (i). As shown in FIG. 1(h), the soluble portion in the first coating film 18 remains on the resist pattern 17 (including the first hard layer 19) after the first thickening step. The soluble portion in the first coating film 18 can be removed by development using a developing solution containing an organic solvent.

The developing method and the developing liquid in the second developing step can be applied to the same as the first developing step. Further, in the second developing step, it is preferable to use the same organic solvent-containing rinsing liquid as in the first developing step after the development, and to clean the resist pattern 17.

The refined resist pattern formed by the method described above can be Further miniaturization is carried out by the method described below.

微The refinement method of the resist pattern by multiple layers of insoluble layers≫

In the method for forming the fine pattern, the first coating forming agent containing (B ¹ ) a compound which generates an acid after heating is used to increase the thickness (refinement) of the resist pattern 17 . Accordingly, the method of forming a so-called fine pattern, the acid is generated by the first layer 19 containing a soluble (B ¹⁾ component, by heating the layer 19 to the first soluble.

Therefore, on the surface of the first poorly soluble layer 19 having the surface of the resist pattern 17, the resin containing (A ² ) having a reduced solubility in an organic solvent by the action of an acid is applied. (hereinafter also referred to as a specific second coating forming agent of the component (A ² )), the acid generated in the first poorly-soluble layer 19 and the (A ² ) component act on the surface of the first poorly-soluble layer 19 After the second insoluble layer 22 is formed, the resist pattern can be further refined.

Further, when the second coating forming agent contains (B ² ) a compound which generates an acid by heating, an acid may be generated in the second poorly soluble layer by heating, and the surface of the second poorly soluble layer may be coated. (a ³⁾ by action of an acid to the resin to reduce the solubility of the organic solvent (hereinafter also referred to as (a ³⁾ component) of the specific third covering forming agent, on the second layer may be further formed a third insoluble insoluble Floor.

In this way, by repeating the operation of refining the pattern of formation of the insoluble layer, it is possible to refine the pattern of the resist pattern several times in the presence of the refinement of the resist pattern. At this time, in the miniaturization operation of one time, The resist pattern can be refined to a difficult level.

As a preferred method of the refining method of the resist pattern by the plurality of insoluble layers, the first miniaturization method and the second miniaturization method described below are exemplified.

<First miniaturization method>

[Refinement method of resist pattern by two layers of insoluble layers]

Hereinafter, a method of refining the resist pattern by the two-layer poorly soluble layer for the first miniaturization method will be described with reference to FIGS. 2(a) to 2(g).

In the method, after the second developing step is carried out, a resin containing (A ² ) having a reduced solubility in an organic solvent by an action of an acid, and a (C ² ) solvent are applied on the surface of the first hardly-soluble layer 19 . (hereinafter also referred to as "(C ² ) component") second coating forming agent, forming a second coating film forming step of the second coating film 20, and forming a second surface on the surface of the first poorly-soluble layer 19 The resist pattern 17 of the coating film 20 is heated at a temperature equal to or higher than the acid generation start temperature (T _A ) of the component (B ¹ ), and is not accompanied by the polymerization on the surface of the first hardly soluble layer 19 Forming a second insoluble layer 22 which is insoluble to the developing solution containing the organic solvent, a second thickening step for thickening the resist pattern 17 and a second thickening step, and then containing the organic layer The developing solution of the solvent removes the third developing step of the soluble portion in the second coating film 20.

(Second coating film forming step)

As the (A ² ) component and the (C ² ) component contained in the second coating forming agent, each of the components (A) and (C) contained in the resist composition used in the resist film forming step can be used. The same material as the ingredients.

Further, the second coating forming agent may contain various components other than the components (A) to (C) contained in the resist composition, as long as it does not inhibit the object of the present invention.

As a method of forming the second coating film 20 after applying the second coating forming agent on the first poorly-soluble layer 19, a method of forming the resist film 11 on the substrate 10 can be used for the resist film forming step. The same method.

Further, as the second coating forming agent, the above-described resist composition can be used.

(second thickening step)

After the second coating film 20 is formed on the surface of the first insoluble layer 19, the resist is heated at a temperature higher than the acid generation starting temperature (T _A ) of the (B ¹ ) component contained in the first insoluble layer 19 Pattern 17, produces acid 21 in the first poorly soluble layer 19. As shown in FIG. 2(c) and FIG. 2(d), the acid 21 thus produced is diffused to the first of the second coating films 20 through the interface between the first poorly soluble layer 19 and the second coating film 20. The area near the insoluble layer 19.

Further, as shown in FIG. 2(d) and FIG. 2(e), the acid 21 diffused into the second coating film 20 and the (A ² ) component in the second coating film 20 act, which is difficult in the first A second insoluble layer 22 is formed on the solution layer 19 to thicken the resist pattern 17.

In the second thickening step, the temperature of the resist pattern 17 having the second coating film 20 is not limited to the acid generation starting temperature (T _A ) of the component (B ¹ ), and is not particularly limited. It is preferably 30 ° C to 200 ° C, preferably 60 ° C to 180 ° C, and more preferably 80 ° C to 160 ° C.

Further, the heating temperature is preferably from 0 ° C to 100 ° C higher than the acid generation start temperature (T _A ) of the component (B ¹ ), and preferably from 5 ° C to 80 ° C. When the resist pattern 17 having the second coating film 20 is heated at this temperature, a good acid 21 can be generated in the first hardly soluble layer 19, and the second poorly soluble layer 22 having a desired thickness can be easily formed.

(third imaging step)

As shown in FIG. 2(e), the soluble portion in the second coating film 20 remains on the resist pattern 17 (including the second poorly soluble layer 22) after the second thickening step. As shown in Fig. 2 (f) and Fig. 2 (g), the soluble portion in the second coating film 20 is removed by development using a developing liquid 16 containing an organic solvent.

In the third developing step, the developing method and the developing liquid 16 can be applied to the same as the first developing step. Further, in the third developing step, after the development, in the same manner as in the first developing step, the etching solution containing the organic solvent can be used to wash the resist pattern having the second poorly-soluble layer 22 on the outermost surface. It is better.

[Refinement method of resist pattern by multiple layers of poorly soluble layers]

As described above, the second coating forming agent further contains (B ² ) a compound which generates an acid by heating in the resist pattern miniaturization method of the insoluble layer of the two layers (hereinafter also referred to as "(B) ² ) In the case of the component "", as described later, a plurality of hard-to-soluble layers are further formed, and the resist pattern can be made fine.

In this case, the second heating step of thickening the resist pattern 17 is, an acid (B ¹⁾ less than the component of generation start temperature (T _A) or more and less than (B ²⁾ of the acid component generated The temperature is started at the temperature (T _B ). When the resist pattern 17 is heated at this temperature, the (B ² ) component in the second coating film 20 can be maintained in the original state, and the (B ¹ ) component contained in the first poorly soluble layer 19 can be produced. Good acid.

Hereinafter, a method of refining the resist pattern by three or more layers of the hardly soluble layers will be described for the first miniaturization method.

In this method, after the third development step, the steps of the following I) to III) are repeated at a predetermined number of times of one or more times.

I) A coating film forming step of forming a coating film after coating a coating forming agent on the surface of the most difficult-to-surface layer on the outermost surface of the two or more insoluble layers formed on the surface of the resist pattern 17.

The coating forming agent contains (A ^a ) ^a resin having a reduced solubility in an organic solvent by an action of an acid (hereinafter also referred to as "(A ^a ) component)", and having a ratio (B ^a ) to generate an acid by heating, The acid contained in the coating film used for the formation of the most insoluble layer on the surface is formed by heating the acid-producing compound to produce an acid starting temperature (T _D ) at which the starting temperature (T _C ) is high (hereinafter also It is referred to as "(B ^a ) component") and (C ^a ) solvent (hereinafter also referred to as "(C ^a ) component)".

II) a resist pattern 17 in which a coating film is formed on the surface of the insoluble layer of two or more layers, and heating is performed at a temperature not exceeding the above (T _D ) only at the above (T _C ), and is on the outermost surface. On the surface of the insoluble layer, a new insoluble layer which is insoluble to the developing solution containing the organic solvent is formed without a high molecular weight, a thickening step for thickening the pattern, and III) after the thickening step A developing step of removing a soluble portion in a coating film by a developing solution containing an organic solvent.

(coating film forming step)

As the component (A ^a ) and the component (C ^a ) contained in the coating forming agent, each of the components (A) and (C) contained in the resist composition used in the resist film forming step can be used. The same material.

Further, as the component (B ^a ) contained in the coating forming agent, the acid generation start temperature (T _D ) is used as the acid generation starting temperature (Tc) of the compound which generates an acid by heating in the most surface poorly soluble layer. Also high in compounds. The difference between (T _D ) and (Tc) is not particularly limited as long as the resist pattern can be finely refined, and is preferably 0° C. to 100° C., and preferably 5° C. to 80° C. When the difference between (T _D ) and (Tc) is in this range, it is difficult to simultaneously generate an acid from the compound which generates an acid and the component (B ^a ) which are contained by the most surface poorly soluble layer by heating in the thickening step described later. It is easy to perform fine refinement of the resist pattern.

Further, the coating forming agent may contain various components other than the components (A) to (C) contained in the resist composition, as long as the object of the present invention is not inhibited.

As a method of forming a coating film by coating a coating agent on the surface of the most difficult-to-solve layer of the two or more insoluble layers formed on the surface of the resist pattern 17, the resist film forming step can be used. Formed on the substrate 10 The same method of the method of resist film 11.

Further, if the steps of I) to III) are not repeated, the coating forming agent may be ^a component containing no (B ^a ) component. When the coating forming agent does not contain the component (B ^a ), the heating temperature of the resist pattern in the thickening step is an acid starting temperature higher than that of the compound which generates an acid by heating in the outermost hard layer. (Tc) is also high temperature.

(thickening step)

An acid which forms a coating film on the surface of the most difficult-to-soluble layer which is formed on the surface of the resist pattern 17 and which is formed on the surface of the most insoluble layer When the temperature above the onset temperature (T _C ) is generated and the acid generation start temperature (T _D ) of the component (B ^a ) contained in the coating agent is not reached, the resist pattern 17 is heated and is hardly soluble on the outermost surface. An acid is produced in the layer. The acid thus produced is diffused to the region near the most surface of the hard coat layer in the coating film through the interface between the most surface poorly soluble layer and the coating film.

Further, the acid diffused into the coating film acts on the (A ^a ) component in the coating film to form a new insoluble layer on the most surface-difficult layer, and the resist pattern 17 is thickened.

In the thickening step, the temperature at which the resist pattern 17 having the coating film is heated is not limited to the above (T _C ) and not (T _D ), and is not particularly limited, and is basically 30 ° C. 200 ° C is preferred, preferably 60 ° C ~ 180 ° C, preferably 80 ° C ~ 160 ° C.

Further, the heating temperature is preferably from 0 ° C to 100 ° C higher than the acid generation start temperature (T _A ) of the component (B ¹ ), and preferably from 5 ° C to 80 ° C. By heating at this temperature, the resist pattern 17 having the coating film can generate acid well in the hard-to-soluble layer on the outermost surface, and it is easy to form a new insoluble layer on the most difficult-soluble layer on the outermost surface. Floor.

(development step)

On the resist pattern 17 (including the new poorly soluble layer) after the thickening step, the soluble portion in the coating film remains. The soluble portion in the coating film is removed by development of a developing solution containing an organic solvent.

For the developing step, the developing method and the developing solution can be applied to the same as the first developing step. Further, in the development step, it is preferable to use a rinse liquid containing an organic solvent in the same manner as in the first development step after the development, and to clean the resist pattern 17 having the new poorly soluble layer on the outermost surface.

By repeating the operations of I) to III) above, the newly insoluble layer can be sequentially laminated on the surface of the second poorly soluble layer, and the etching pattern can be refined to form the first insoluble layer. The level that is difficult to achieve.

<Second refinement method>

[Refinement method of resist pattern by two layers of insoluble layers]

Hereinafter, the second miniaturization method will be described with reference to FIGS. 3(a) to 3(f) by a method of refining the resist pattern of the two-layer poorly soluble layer.

The method includes the following steps: after the second developing step, the resist pattern 17 having the first hardly soluble layer 19 is heated at a temperature equal to or higher than the acid generation starting temperature (T _A ) of the (B ¹ ) component. a thermal acid generating step of generating an acid 21 in the first poorly soluble layer 19, after the hot acid generating step, coating the surface of the first poorly soluble layer 19 with an (A ² )-based action on the organic solvent a resin having a reduced solubility and a second coating forming agent of (C ² ) solvent (hereinafter also referred to as "(C ² ) component)), forming a second coating film forming step of the second coating film 20, and The resist pattern 17 of the second coating film 20 is formed on the surface of the first insoluble layer 19 and heated to form an image for the organic solvent in the surface of the first insoluble layer 19 without being subjected to high molecular weight. The liquid is a second insoluble layer 22 which is difficult to dissolve, a second thickening step for thickening the resist pattern 17 and a second thickening step, and then the second liquid is removed by a developing solution containing an organic solvent. A third developing step of the soluble portion in the coating film 20.

(thermal acid production step)

In the thermal acid generating step, as shown in Fig. 3 (a), the acid pattern of the (B ¹ ) component contained in the first hardly soluble layer 19 formed on the surface of the resist pattern 17 is started. Heating is carried out at a temperature higher than the temperature (T _A ) to generate an acid 21 in the first poorly soluble layer 19.

In the hot acid generating step, the temperature at which the resist pattern 17 is heated is only a temperature equal to or higher than the acid generation starting temperature (T _A ) of the component (B ¹ ), and is not particularly limited, and is basically 30 ° C to 200 ° C. Preferably, 60 ° C ~ 180 ° C is preferred, and 80 ° C ~ 160 ° C is more preferred. When heating at this temperature, the acid 21 can be easily and favorably produced in the first poorly-soluble layer 19, and deterioration due to heat of the resist pattern 17 can be easily suppressed. transsexual.

Further, the heating temperature is preferably from 0 ° C to 100 ° C higher than the acid generation start temperature (T _A ) of the component (B ¹ ), and preferably from 5 ° C to 80 ° C. When the resist pattern 17 including the first hardly soluble layer 19 is heated at this temperature, the acid 21 can be favorably generated in the first poorly soluble layer 19.

(Second coating film forming step)

As the (A ² ) component and the (C ² ) component contained in the second coating forming agent, each of the components (A) and (C) contained in the resist composition used in the resist film forming step can be used. The same material.

Further, the second coating forming agent may contain various components other than the components (A) to (C) contained in the resist composition, as long as it does not inhibit the object of the present invention.

As a method of forming the second coating film 20 on the first poorly-soluble layer 19, the same method as the method of forming the resist film 11 on the substrate 10 can be used for the resist film forming step. .

Further, as the second coating forming agent, the above-described resist composition can be used.

(second thickening step)

After the second coating film 20 is formed on the surface of the first insoluble layer 19, the resist pattern 17 of the second coating film 20 is formed on the surface of the first insoluble layer 19, as shown in FIG. 3(b). As shown in FIG. 3(c), the acid 21 in the first poorly soluble layer 19 is diffused through the interface between the first hardly soluble layer 19 and the second coated film 20 A region in the vicinity of the first poorly soluble layer 19 in the second coating film 20.

Further, as shown in FIG. 3(d), the acid 21 diffused into the second coating film 20 and the (A ² ) component in the second coating film 20 act to form the first poorly soluble layer 19 The hardly soluble layer 22 thickens the resist pattern 17 .

In the second thickening step, the temperature at which the resist pattern 17 having the second coating film 20 is heated is not particularly limited, and is preferably 30° C. to 200° C., and preferably 60° C. to 180° C. It is preferably from 80 ° C to 160 ° C.

(third imaging step)

As shown in FIG. 3(d), the soluble portion in the second coating film 20 remains on the resist pattern 17 (including the second poorly soluble layer 22) after the second thickening step. The soluble portion in the second coating film 20 is removed by development using a developing liquid 16 containing an organic solvent as shown in Figs. 3(e) and 3(f).

In the third developing step, the developing method and the developing liquid 16 can be applied to the same as the first developing step. Further, in the third developing step, after the development, the etching pattern containing the organic solvent is used, and the resist pattern 17 having the second poorly soluble layer 22 on the outermost surface is washed as in the first developing step. good.

[Refinement method of resist pattern by multiple layers of poorly soluble layers]

As described above, in the method for miniaturizing the resist pattern of the two-layer hard-to-dissolve layer, the second coating-forming agent further contains (B ² ) a compound which generates an acid by heating (hereinafter also When it is "(B ² ) component"), as described later, a plurality of hard-dissolved layers are further formed, and the resist pattern can be made fine.

Hereinafter, a method of refining the resist pattern by three or more layers of the hardly soluble layers will be described for the second miniaturization method.

In this method, after the third development step, the following steps i) to iv) are repeated at a predetermined number of times of one or more times.

i) The resist pattern 17 is contained in the most hard-to-solve layer on the outermost surface of the two or more insoluble layers formed on the surface of the resist pattern 17, and (B ^b ) is produced by acid which generates an acid compound after heating Heating at a temperature above the onset temperature (T _E ), generating a hot acid generating step of acid in the most insoluble layer on the outermost surface, ii) on the surface of the most insoluble layer on the outermost surface, coating containing (A ^c ) A resin which has a reduced solubility in an organic solvent (hereinafter also referred to as "(A ^c ) component)" and (B ^c ) a compound which generates an acid by heating (hereinafter also referred to as "(B ^c ) component") And a coating film forming step of forming a coating film after the coating agent of (C ^c ) solvent (hereinafter also referred to as "(C ^c ) component"), and iii) on the surface of the most difficult-soluble layer on the outermost surface The resist pattern 17 forming the coating film is heated at a temperature at which the acid generation starting temperature (T _F ) of the (B ^c ) component is not reached, and is not accompanied by high molecular weight on the surface of the most surface hardly soluble layer. Then, a new hard-to-dissolve layer which is insoluble to the developing solution containing the organic solvent, a thickening step for thickening the pattern, and iv) after the thickening step are formed The developing step of the organic solvent removes the developing portion of the coating film.

(thermal acid production step)

In the hot acid generating step, the resist pattern 17 is contained in the most difficult-to-solve layer on the outermost surface of the two or more insoluble layers formed on the surface of the resist pattern 17, and the acid generation of the (B ^b ) component is started. Heating is carried out at a temperature equal to or higher than the temperature (T _B ) to generate an acid in the hard-to-soluble layer on the outermost surface.

In the hot acid generating step, the temperature at which the resist pattern 17 is heated is only a temperature equal to or higher than the acid generation starting temperature (T _B ) of the component B ^b ), and is not particularly limited, and is basically 30 ° C to 200 ° C. Preferably, 60 ° C ~ 180 ° C is preferred, and 80 ° C ~ 160 ° C is more preferred. When heating at this temperature, acid can be easily and favorably produced in the most difficult-to-soluble layer on the outermost surface, and deterioration due to heat of the resist pattern 17 can be easily suppressed. transsexual.

Further, the heating temperature is preferably from 0 ° C to 100 ° C higher than the acid generation start temperature (T _B ) of the component (B ^b ), and preferably from 5 ° C to 80 ° C. When the resist pattern 17 is heated at this temperature, an acid can be favorably generated in the most difficult layer on the outermost surface.

(coating film forming step)

The (A ^c ) component and the (C ^c ) component contained in the coating forming agent can be used in the same manner as the components (A) and (C) contained in the resist composition used in the resist film forming step. material.

Further, as the component (B ^c ) contained in the coating forming agent, the same as the component (B ¹ ) contained in the first coating forming agent can be used.

Further, the coating forming agent may contain various kinds of components other than the components (A) to (C) contained in the resist composition, as long as it does not inhibit the object of the present invention. ingredient.

As a method of forming a coating film by coating a coating forming agent on the surface of the most difficult-to-solve layer on the outermost surface of the two or more insoluble layers formed on the surface of the resist pattern 17, the resist film forming step may be The same method as the method of forming the resist film 11 on the substrate 10 is used.

Further, when the steps of i) to iii) are not further repeated, the coating forming agent may be a component containing no (B ^c ) component.

(thickening step)

On the surface of the most insoluble layer on the outermost surface of the two or more insoluble layers formed on the surface of the resist pattern 17, after the coating film is formed, a coating film is formed on the surface of the most difficult-soluble layer on the outermost surface. The resist pattern 17 is heated to diffuse the acid in the insoluble layer on the outermost surface to the region near the hardly soluble layer on the outermost surface of the coating film through the interface between the hardly soluble layer on the outermost surface and the coating film.

Further, the acid diffused into the coating film acts on the (A ^c ) component in the coating film, and a new poorly soluble layer is formed on the most hardly soluble layer on the outermost surface to thicken the resist pattern 17 .

In the thickening step, the temperature at which the resist pattern 17 having the coating film is heated is not limited to the above (T _C ) and not (T _D ), and is not particularly limited, and is basically 30 ° C. 200 ° C is preferred, 60 ° C to 180 ° C is preferred, and 80 ° C to 160 ° C is more preferred.

(development step)

On the resist pattern 17 (containing the new insoluble layer) after the thickening step, The soluble portion in the coating film remains. The soluble portion in the coating film can be removed by development using a developing solution containing an organic solvent.

In the developing step, the developing method and the developing liquid can be applied to the same as the first developing step. Further, in the development step, it is preferable to use a rinse liquid containing an organic solvent in the same manner as in the first development step after the development, and to clean the resist pattern 17 having the new poorly soluble layer on the outermost surface.

By repeating the operations of the above i) to iii), the newly insoluble layer can be sequentially laminated on the surface of the second insoluble layer, and the resist pattern can be refined to the formation of the insoluble layer. The level of difficulty is reached.

[Examples]

The invention is described in more detail below by way of examples, but the invention is not limited by the examples.

[Examples 1 to 7 and Reference Example 1]

Hereinafter, the components contained in the resist composition will be described using Examples 1 to 7 and Reference Example 1.

<(A) component>

As the component (A) contained in the resist composition, a resin composed of the following constituent units is used. Further, the numbers described in the respective constituent units mean the % of the total constituent units contained in the resin of each constituent unit. And the mass average molecular weight of the resin composed of the following constituent units is 7000.

<(B) component>

As the photoacid generator of the component (B) contained in the resist composition, a compound of the following formula is used.

<(C) component>

The solvent of the component (C) contained in the resist composition, the content of propylene glycol monomethyl ether acetate (PGMEA) is 90% by mass, and the content of cyclohexanone (CH) is 10% by mass, and PGMEA is used. Mixed solvent with CH.

<(D) component>

As the quenching agent of the component (D) contained in the resist composition, a compound of the following formula is used.

<(E) component>

Salicylic acid is used as the organic carboxylic acid as the component (E) contained in the resist composition.

<(F) component>

The alkali-dissociable group-containing resin as the component (F) contained in the resist composition contains a resin composed of the following constituent units. Further, the numbers described in the respective constituent units mean the % of the total constituent units contained in the resin of each constituent unit. Further, the mass average molecular weight of the resin composed of the following constituent units was 23,000.

Further, as a component other than the above, gammatine lactone was added to the resist composition. The compositions of the respective components of the resist compositions used in Examples 1 to 7 and Reference Example 1 are shown in Table 7 below.

[Example 1]

The resist composition was roll-coated on a tantalum wafer having a film thickness of 82 nm "ARC29A (Brewer Science)", and baked at 105 ° C for 60 seconds to form a film thickness of 100 nm. Resist film. Then, the obtained photoresist film was exposed to a predetermined pattern by using an exposure apparatus (manufactured by Nikon Co., Ltd., trade name "NSR-S302A"), and a mask having a space width of 130 nm and a width of 260 nm. The temperature was heated for 60 seconds at °C. Next, using a butyl acetate, a line and space pattern was formed after performing a first development process at 23 ° C for 16 seconds.

Next, on the line and space pattern, a first coating forming agent formed by 100 parts by mass of the same resin as the component (A) contained in the resist composition and 5000 parts by mass of butyl acetate is formed by rolling coating. The first coating film having a film thickness of 175 nm. The pattern of the first coating film was formed, and after heating at 130 ° C for 60 seconds, butyl acetate was used, and a second development treatment was performed at 23 ° C for 16 seconds to form a fine pattern. For Example 1, the spatial width of the pattern after the first development step and the spatial width reduction of the pattern after the second development step were obtained. The evaluation results are shown in Table 3.

[Examples 2 to 7]

A refining resist pattern was formed in the same manner as in Example 1 except that the resin contained in the first coating forming agent was changed to the following resin composed of constituent units.

The mass average molecular weight of the resins used in the first coating forming agents of Examples 2 to 7 is shown in Table 2 below.

In each of the examples, as in the first embodiment, the spatial width of the pattern after the first development step and the reduction in the width of the pattern space after the second development step were obtained. The evaluation results of the respective examples are shown in Table 3.

[Reference Example 1]

A first thickening step and a second developing step were carried out in the same manner as in Example 1 except that the first coating forming agent was not used, and a resist pattern was formed. In Reference Example 1, as in the first embodiment, the spatial width of the pattern after the first development step and the spatial width reduction amount of the pattern after the second development step were obtained. The evaluation results of Reference Example 1 are shown in Table 3.

From the results of Examples 1 to 7 described in Table 3, it is known that (A) the substrate having a reduced solubility in the developing solution containing an organic solvent by the action of an acid, (B) by active rays or After the irradiation of the radiation, the acid-producing compound and the resist composition of the solvent (C) are applied onto the substrate to form a resist film, and after the resist film is exposed, the resist pattern is developed and the image is developed. In the etching pattern, a first coating film is formed by coating a resin containing (A ¹ ) a solubility in an organic solvent by an action of an acid and a first coating forming agent of a (B ¹ ) solvent, by heating The resist pattern applied by the first coating forming agent can refine the resist pattern finely.

Further, in the first and second embodiments, when the acrylate-derived resin containing a constituent unit of a predetermined structure is used as a component of the first coating-forming agent, the resist pattern can be finely formed.

[Examples 8 to 20 and Reference Examples 2 to 4]

Hereinafter, the components contained in the resist composition will be described using Examples 8 to 20 and Reference Examples 2 to 4.

<(A) component>

As the component (A) contained in the resist composition, a resin composed of the following constituent units is used. Further, the number described in each constituent unit indicates the mole % of the total constituent unit contained in the resin of each constituent unit. Further, the resin composed of the following constituent units had a mass average molecular weight of 8,500 and a degree of dispersion of 1.81.

<(B) component>

As the photoacid generator of the component (B) contained in the resist composition, a compound of the following formula is used.

<(C) component>

The solvent of the component (C) contained in the resist composition, the content of propylene glycol monomethyl ether acetate (PGMEA) was 90% by mass, and the content of cyclohexanone (CH) was 10% by mass, and PGMEA was used. Mixed solvent with CH.

<(D) component>

As a quenching agent for the component (D) contained in the resist composition, use Compound.

<(E) component>

As the organic carboxylic acid as the component (E) contained in the resist composition, salicylic acid is used.

<(F) component>

As the resin containing an alkali dissociable group as the component (F) contained in the resist composition, a resin composed of the following constituent units is used. Further, the number described in each constituent unit indicates the mole % of the total constituent unit contained in the resin of each constituent unit. Further, the resin composed of the following constituent units had a mass average molecular weight of 23,000 and a degree of dispersion of 1.30.

Using Examples 8 to 20 and Reference Examples 2 to 4, the composition of each component of the resist composition was as shown in Table 4 below.

[Example 8]

The resist composition was roll-coated on a tantalum wafer having a film thickness of 90 nm "ARC295 (manufactured by Brewer Science)", and baked at 105 ° C for 60 seconds to form a film thickness of 100 nm. Resist film. Then, the obtained photoresist film was exposed to a predetermined pattern by using an exposure apparatus (manufactured by Nikon Co., Ltd., trade name "NSR-S609B") through a color mask having a pore diameter of 70 nm and a space between holes of 140 nm. Heat treatment was carried out at 85 ° C for 60 seconds. Next, using a butyl acetate, a hole pattern was formed after the first development treatment at 23 ° C for 16 seconds.

Next, on the hole pattern, a first coating forming agent of 100 parts by mass of a resin (mass average molecular weight: 10,000) composed of the following constituent units and 5000 parts by mass of butyl acetate was applied by rolling to form a film thickness of 60 nm. The first coating film. The pattern of the first coating film was formed, and after heating at 120 ° C for 60 seconds, butyl acetate (BuOAc) was used, and a second development treatment was performed at 23 ° C for 16 seconds to form a micropattern. For Example 8, the aperture of the pattern after the first development step and the reduction of the aperture of the pattern after the second development step were obtained. The evaluation results are shown in Table 6.

[Examples 9 to 20]

In Examples 9 to 13, the same first coating forming agent as in Example 8 was used. Further, in Examples 14 to 20, the resin contained in the first coating forming agent was changed to a resin composed of the following constituent units.

The mass average molecular weight of the resin contained in the first coating forming agent used in Examples 14 to 20 is shown in Table 5 below.

In the examples 9 to 20, the heating temperature of the first coating film was set to the temperature shown in Table 6, and the solvent was the same as that of Example 8 except that the solvent described in Table 6 was used in the second development process. The ground forms a refined resist pattern. Further, MAK shown in Table 6 represents 2-heptanone. For Examples 9 to 20, the aperture of the pattern after the first development step and the reduction of the aperture of the pattern after the second development step were obtained. The evaluation results are shown in Table 6.

[Reference Example 2~4]

In the same manner as in Example 8, a pore pattern which was not miniaturized was formed. The formed pore pattern which was not refined was heated at the temperature shown in Table 6 for 60 seconds. For Reference Examples 2 to 4, the reduction in the aperture diameter of the pattern after heating for the aperture of the pattern before heating was obtained. The evaluation results are shown in Table 6.

From the results of Examples 8 to 20 described in Table 6, it is known that (A) the substrate having a reduced solubility in an organic solvent-containing developing solution by the action of an acid, (B) by active rays or After the irradiation of the radiation, the acid-producing compound and the resist composition of the solvent (C) are applied onto the substrate to form a resist film, and the resist film is exposed to light to develop a resist pattern. On the etching pattern, a resin containing (A ¹ ) a resin having a reduced solubility in an organic solvent by an action of an acid and a first coating forming agent of a (B ¹ ) solvent are applied to form a first coating film by heating The resist pattern of the first coating forming agent can also finely refine the resist pattern for the hole pattern.

Further, as a result of the examples described in Table 6, it was found that the resist pattern can be finely refined and the first coating forming agent can be coated by heating without changing the type of the solvent used for the second development. The temperature of the resist pattern makes it easier to refine the resist pattern.

According to Reference Examples 2 to 4, when the predetermined first coating forming agent was not applied, even if the resist pattern was heated, the resist pattern could not be made fine.

In the following, in Example 21, a surface containing a (A ¹ ) resin having a reduced solubility in an organic solvent by an action of an acid, and (B ¹ ) a compound which generates an acid by heating, and (C) are coated on the surface of the resist pattern. ¹ ) after forming the first coating film after the first coating forming agent of the solvent, the resist pattern coated with the first coating forming agent is generated by an acid which does not reach (B ¹ ) by heating the compound which generates an acid. Heating at a temperature of the starting temperature (T _A ) forms a first hardly soluble layer which is insoluble to the developing solution on the surface of the resist pattern, and secondarily removes the soluble portion in the first coating film by the developing solution to form a soluble portion. Fine pattern.

Further, in Example 22, a second coating forming agent having the same composition as that of the first covering forming agent used in Example 1 was applied to the surface of the fine pattern formed in the same manner as in Example 21 to form a second. After the coating layer was heated to form a pattern of the second coating layer, the heated second coating layer was developed to further refine the fine pattern formed by the method of Example 21.

Further, in Examples 23 to 25, on the surface of the fine pattern formed in the same manner as in Example 21, the component (A) and the acetic acid contained in the resist composition used for the formation of the resist pattern were applied. a second coating forming agent formed by butyl ester forms a second coating layer, and after heating to form a pattern of the second coating layer, the heated second coating layer is developed, and further formed by the method of Example 21. The fine pattern is refined.

The resist composition used in Examples 21 to 25 and the components contained in the first coating forming agent will be described below.

<(A) component>

As the component (A) contained in the resist composition, a resin composed of the following constituent units is used. Further, the numbers described in the respective constituent units mean the % of the total constituent units contained in the resin of each constituent unit. Further, the resin composed of the following constituent units had a mass average molecular weight of 7,000 and a degree of dispersion of 1.66.

<(B) component>

As the photoacid generator of the component (B) contained in the resist composition, a compound of the following formula is used.

<(C) component>

The solvent of the component (C) contained in the resist composition, the content of propylene glycol monomethyl ether acetate (PGMEA) is 90% by mass, and cyclohexanone The content of (CH) was 10% by mass, and a mixed solvent of PGMEA and CH was used.

<(D) component>

As the quenching agent of the component (D) contained in the resist composition, a compound of the following formula is used.

<(E) component>

Salicylic acid is used as the organic carboxylic acid as the component (E) contained in the resist composition.

<(F) component>

The alkali-dissociable group-containing resin as the component (F) contained in the resist composition contains a resin composed of the following constituent units. Further, the numbers described in the respective constituent units mean the % of the total constituent units contained in the resin of each constituent unit. Further, the resin composed of the following constituent units had a mass average molecular weight of 23,000 and a degree of dispersion of 1.30.

Further, as a component other than the above, gammatine lactone was added to the resist composition. The composition of each component of the resist composition used in the examples is shown in Table 7 below.

<Thermal acid generator>

As a thermal acid generator containing a compound which generates an acid by heating in the first coating forming agent and the second coating forming agent, a compound having the following structure (acid generation starting temperature: 155 ° C) was used.

[Example 21]

The resist composition was roll-coated on a tantalum wafer having a film thickness of 82 nm "ARC29A (manufactured by Brewer Science)", and baked at 105 ° C for 60 seconds to form a film thickness of 100 nm. Resist film. Then, the obtained photoresist film was exposed to a predetermined pattern by using an exposure apparatus (manufactured by Nikon Co., Ltd., trade name "NSR-S302A") through a mask having a space width of 130 nm and a width of 260 nm. Heat treatment was carried out at 95 ° C for 60 seconds. Next, using butyl acetate, a development process of 16 seconds at 23 ° C was applied to form a line and space pattern.

Next, in the line and space pattern, 100 parts by mass of the resin equivalent to the component (A) contained in the resist composition, 2 parts by mass of the above thermal acid generator, and 5000 parts by mass of butyl acetate are applied by rolling coating. The first coating forming agent was formed to form a first coating film having a film thickness of 60 nm. The pattern of the first coating film was formed, and after heating at 130 ° C for 60 seconds, butyl acetate was used, and a second development treatment was performed at 23 ° C for 16 seconds to form a fine pattern. For Example 1, the spatial width of the pattern after the first development step and the spatial width reduction of the pattern after the second development step were obtained. The evaluation results are shown in Table 8.

[Example 22]

After the same procedure as in Example 21 was carried out until the second development process, the second coating forming agent having the same composition as that of the first coating forming agent used in Example 1 was applied by rolling to form a second film thickness of 60 nm. Covered layer. The pattern of the second coating layer will be formed at the temperature as shown in Table 8. After heating for 60 seconds, a third development treatment was carried out for 16 seconds at 23 ° C using butyl acetate to form a micronized pattern. For Example 22, the spatial width of the pattern after the first development step and the reduction in the spatial width of the pattern after the third development step were obtained. The evaluation results are shown in Table 2.

[Examples 23 to 25]

The same procedure as in Example 21 was carried out until the second development process, and then rolling was applied to 100 parts by mass of the same resin as the component (A) contained in the resist composition and 5000 parts by mass of butyl acetate. The second coating forming agent forms a second coating layer having a film thickness of 60 nm. The pattern in which the second coating layer was formed was heated at the temperature shown in Table 2 for 60 seconds, and then subjected to a third development treatment at 23 ° C for 16 seconds using butyl acetate to form a fine pattern. For Examples 23 to 25, the spatial width of the pattern after the first development step and the reduction in the spatial width of the pattern after the third development step were obtained. The evaluation results are shown in Table 8.

It is known from Examples 21 to 23 that (A) a substrate having a reduced solubility in a developing solution containing an organic solvent by an action of an acid, and (B) an acid generated by irradiation with active rays or radiation. The resist composition of the compound and the solvent (C) is applied onto the substrate to form a resist film, and after the resist film is exposed, the resist pattern is developed, and the pattern is formed on the etched pattern of the development image. (a ¹⁾ by action of an acid to reduce the solubility of the organic solvent, a resin, and (C ¹⁾ forming a first coating agent of a solvent to form a first coating film, by heating the coating agent is formed of a first coating The resist pattern allows the resist pattern to be finely refined.

In the examples 22 and 23, the second coating forming agent of a predetermined composition is further coated on the finened pattern by the method of the first embodiment, and after the second coating film is formed, the second coating film is formed. An example of heating at 130 ° C or 140 ° C. At this time, it is known that the space width of the pattern after the first development step is reduced to the same extent as in the first embodiment. In other words, it is known from the examples 22 and 23 that the temperature at which the temperature of the second coating film is heated is less than 155 ° C of the acid generation starting temperature of the thermal acid generator contained in the first coating film. The pattern refining effect of the interaction between the resist composition and the first coating film, and the fact that the first coating film is almost free of acid, so that the second coating film contains acid The resin having a reduced solubility in a developing solution containing an organic solvent is not hardly soluble in the developing solution, and is almost dissolved in the developing solution.

In Examples 24 and 25, a second coating forming agent having a predetermined composition was further applied to the pattern further refined by the method of Example 21, and a second coating film was formed, and then the second coating film was formed. An example of heating at 160 ° C or 180 ° C. At this point, the figure after the first development step is known. The space of the type is wide, and the space width of the pattern after the third development step is more reduced than that of the embodiment 21. In other words, it is known from the examples 24 and 25 that when the temperature of the second coating film is heated to a temperature of 155 ° C or higher of the acid generation starting temperature of the thermal acid generator contained in the first coating film, The thermal acid generator contained in the coating film generates a large amount of acid, and the resin contained in the second coating film which reduces the solubility of the developing solution containing the organic solvent by the action of the acid is difficult for the developing solution. melt.

10‧‧‧Substrate

11‧‧‧Resist film

12‧‧‧Active Energy Line

13‧‧‧Photomask

14‧‧‧Exposure Department

15‧‧‧Unexposed Department

16‧‧‧ imaging solution

17‧‧‧Resist pattern

18‧‧‧First coating

19‧‧‧The first insoluble layer

20‧‧‧Second coating

21‧‧‧ Acid

22‧‧‧Second insoluble layer

Fig. 1 is a schematic view showing a method of forming a fine pattern of the present invention.

Fig. 2 is a schematic view showing a method of forming a fine pattern by forming a two-layer insoluble layer.

Fig. 3 is a schematic view showing a method of forming a fine pattern by forming a two-layer poorly soluble layer.

10‧‧‧Substrate

11‧‧‧Resist film

12‧‧‧Active Energy Line

13‧‧‧Photomask

14‧‧‧Exposure Department

15‧‧‧Unexposed Department

16‧‧‧ imaging solution

17‧‧‧Resist pattern

18‧‧‧First coating

19‧‧‧The first insoluble layer

Claims (23)

A fine pattern forming method characterized by comprising the following steps; (A) a substrate having reduced solubility in an imaging solution containing an organic solvent by an action of an acid, (B) by active light or radiation After the irradiation, the acid-producing compound and the resist composition of the solvent (C) are applied onto the substrate to form a resist film forming step of the resist film, the exposure step of exposing the resist film, and the exposure step. a first developing step of forming a resist pattern by developing the resist film, and coating the (A ¹ ) solubility in an organic solvent by an action of an acid on the resist pattern a coating film forming step of forming a first coating film after reducing the resin and the first coating forming agent of the (C ¹ ) solvent, and heating the resist pattern applied by the first coating forming agent to the resist On the surface of the etched pattern, a first thickening step for thickening the pattern is formed without the use of high molecular weight to form a first hardly soluble layer which is insoluble to the above-mentioned developing solution. The method for forming a fine pattern according to the first aspect of the invention, wherein the first thickening step further comprises removing the second image of the soluble portion in the first coating film by the developing liquid. step. The method for forming a fine pattern according to the first aspect of the invention, wherein the (A ¹ ) component is a resin containing a repeating unit having a protecting group deprotected by an action of an acid, and for the first thickening step, The first poorly soluble layer is formed by a deprotection reaction of the (A ¹ ) component in the coating film. The fine pattern forming method according to claim 1, wherein the resist composition is used as the first covering forming agent. The fine pattern forming method according to claim 1, wherein the first coating forming agent further contains (B ¹ ) a compound which generates an acid by heating, and the first thickening step is performed by the first coating. The resist pattern coated with the forming agent is heated at a temperature that does not reach the above (B ¹ ) acid generation start temperature (T _A ) of the compound which generates an acid by heating, and is not accompanied by the resist pattern surface. Under the high molecular weight, a first poorly soluble layer which is insoluble to the above-mentioned developing solution is formed. The method for forming a fine pattern according to the fifth aspect of the invention, wherein after the first thickening step, the second display of the soluble portion in the first coating film is removed by the developing liquid Like steps. The method for forming a fine pattern according to item 6 of the patent application, wherein after the second developing step, further comprising the surface of the first poorly soluble layer, the coating contains (A ² ) by an action of an acid a second coating film forming step of forming a second coating film after the resin having a reduced solubility of the organic solvent and the second coating forming agent of the (C ² ) solvent, forming the first surface on the surface of the first poorly soluble layer The resist pattern of the second coating film is heated at a temperature equal to or higher than the acid generation start temperature (T _A ) of the component (B ¹ ), and is not accompanied by the polymerization on the surface of the first poorly soluble layer. Forming a second poorly soluble layer which is insoluble to the developing liquid, a second thickening step for thickening the pattern, and a second thickening step, and removing the aforementioned by the developing liquid A third developing step of the soluble portion in the second coating film. The fine pattern forming method of claim 7, wherein the second coating forming agent further comprises (B ² ) a compound which generates an acid by heating, and the resist pattern in the second thickening step The heating temperature is not higher than the above (T _A ), and does not reach the acid generation starting temperature (T _B ) of the component (B ² ). The method for forming a fine pattern according to Item 8 of the patent application, wherein the steps of the following I) to III) are further repeated at a predetermined number of times or more after the third developing step; a surface containing a (A ^a ) resin having ^a reduced solubility in an organic solvent by an action of an acid, (B ^a ) by coating the surface of the most difficult-to-surface layer of the most difficult-to-solve layer of the two or more insoluble layers formed on the surface of the pattern The acid is generated by heating, and has an acid generation start temperature (T _C ) higher than the acid generation start temperature (T _C ) of the compound which generates an acid contained in the coating film used for the formation of the insoluble layer on the outermost surface. _D) compound, and the coating-forming agent (C ^a) is formed by a solvent coating film-forming step, II) formed will be the two or more layers of the film is on the surface of the resist layer insoluble pattern at the (T _C) or more, less than the lower (T _D) of the heating temperature, the insoluble layer on the surface of the outermost surface, not accompanied by the molecular weight, the developing solution for the formation of difficult a new insoluble layer dissolved, a thickening step for thickening the pattern, III) After the thickening step, a developing step of removing the soluble portion in the coating film by the developing liquid is performed. The fine pattern forming method according to claim 6, wherein after the second developing step, the resist pattern having the first hardly soluble layer is further included, and the (B ¹ ) is heated by the (B ¹ ) Heating the acid generating compound at a temperature higher than the onset temperature (T _A ) to cause an acid generating step in the first poorly soluble layer, and after the hot acid generating step, the first poorly soluble in the first The surface of the layer is coated with a second coating film containing (A ² ) a resin having a reduced solubility in an organic solvent by an action of an acid, and a second coating forming agent with a (C ² ) solvent to form a second coating film. a forming step of heating the second resist film on the surface of the first hardly-dissolved layer to form the resist pattern on the surface of the first hardly-dissolved layer without forming a polymer a second thickening step in which the liquid is insoluble, a second thickening step for thickening the pattern, and a second thickening step, wherein the second coating film is formed by the developing liquid The third imaging step of the soluble portion is removed. The method for forming a fine pattern according to the seventh aspect of the invention, wherein the second coating forming agent further comprises (B ² ) a compound which generates an acid by heating, and the resist pattern in the second thickening step. The heating temperature of the type is an acid generation starting temperature (T _B ) which does not reach the above-mentioned (B ² ) component. The fine pattern forming method of claim 11, wherein after the third developing step, the following steps i) to iv) are further repeated at a predetermined number of revolutions; i) The resist pattern is contained in an insoluble layer which is formed on the outermost surface of the hard coat layer of two or more layers of the surface of the resist pattern, and (C ^b ) an acid generation start temperature of a compound which generates an acid by heating (T _E ) heating at a temperature above, a thermal acid generating step of generating an acid in the insoluble layer on the outermost surface, ii) on the surface of the most insoluble layer on the outermost surface, coating containing (A ^c ) a resin film having a reduced solubility in an organic solvent by the action of an acid, (B ^c ) a coating film forming step of forming a coating film by a compound which generates an acid by heating, and a coating forming agent of (C ^c ) solvent, iii) Forming the resist pattern of the coating film on the surface of the insoluble layer on the outermost surface, and heating at a temperature that does not reach the acid generation start temperature (T _F ) of the component (B ^c ), On the surface of the insoluble layer on the surface, without the aid of high molecular weight, a step of thickening the pattern to form a new hard-to-dissolve layer, and iv) removing the soluble portion of the coating film by the developing solution after the thickening step Development steps. The fine pattern forming method according to claim 5, wherein the (A ¹ ) component is a resin containing a repeating unit having a protecting group deprotected by an action of the acid, and the first thickening step is performed. The first poorly soluble layer is formed by a deprotection reaction of the (A ¹ ) component in the first coating film. The fine pattern forming method according to claim 7, wherein the (A ² ) component is a resin containing a repeating unit having a protecting group which is deprotected by an action of the acid, and the second thickening step is performed. The second poorly soluble layer is formed by a deprotection reaction of the (A ² ) component in the second coating film. The fine pattern forming method according to claim 10, wherein the (A ² ) component is a resin containing a repeating unit having a protecting group deprotected by an action of the acid, and the second thickening step is performed. The second poorly soluble layer is formed by a deprotection reaction of the (A ² ) component in the second coating film. The fine pattern forming method of claim 7, wherein the resist composition is used as the second covering forming agent. The fine pattern forming method according to claim 10, wherein the resist composition is used as the second coating forming agent. Fine a pattern which is formed by coating agent characterized in using as a method of forming a fine pattern patent range, Paragraph 1, comprising (A ¹⁾ by action of an acid to decrease the solubility of the organic solvents resin, (C ¹ ) Solvent. A pattern which is formed with a coating agent miniaturized, wherein the covering is formed as a first agent a method of forming a fine pattern patented scope of the item as the first 5, comprising (A ¹⁾ by action of an acid organic solvent The solubility-reducing resin, (B ¹ ) a compound which generates an acid by heating, and (C ¹ ) a solvent. A coating forming agent for pattern miniaturization, which is characterized in that it is used as a second coating forming agent in a method for forming a fine pattern according to Item 7 of the application patent, and contains (A ² ) an organic solvent by an action of an acid Solubility-reducing resin, and (C ² ) solvent. A coating forming agent for pattern miniaturization, which is characterized in that it is used as a second coating forming agent in a method for forming a fine pattern according to claim 10 of the patent application, and contains (A ² ) an organic solvent by an action of an acid Solubility-reducing resin, and (C ² ) solvent. A coating forming agent for pattern miniaturization, which is characterized in that it is used as a second coating forming agent in a method for forming a fine pattern of the eighth aspect of the patent application, and contains (A ² ) an organic solvent by an action of an acid The solubility-reduced resin, (B ² ) a compound which generates an acid by heating, and (C ² ) a solvent. A coating forming agent for pattern miniaturization, which is characterized in that it is used as a second coating forming agent in a method for forming a fine pattern according to Item 11 of the patent application, and contains (A ² ) an organic solvent by an action of an acid The solubility-reduced resin, (B ² ) a compound which generates an acid by heating, and (C ² ) a solvent.