WO2008013030A1 - Compound, acid generator, resist composition and method for forming resist pattern - Google Patents

Abstract

Disclosed is a resist composition containing a base component (A) whose alkali solubility is varied by the action of an acid, and an acid generator component (B) which generates an acid when exposed to light. The acid generator component (B) contains an acid generator (B1) composed of a compound represented by the general formula (b1-3) below. In the formula, R41, R42 and R43 independently represent an alkyl group, an acetyl group, an alkoxy group, a carboxy group or a hydroxyalkyl group; n1 represents an integer of 0-3, n2 represents an integer of 0-3 and n3 represents an integer of 0-2, provided that n1, n2 and n3 are not 0 at the same time; and X- represent an anion.

Description

 Specification

 Compound, acid generator, resist composition and resist pattern forming method

 [0001] The present invention relates to a compound suitable as an acid generator for a resist composition, an acid generator comprising the compound, a resist composition containing the acid generator, and a resist pattern using the resist composition. It relates to a forming method.

 This application claims priority based on Japanese Patent Application No. 2006-201007 filed with the Japan Patent Office on July 24, 2006, the contents of which are incorporated herein by reference.

 Background art

 In lithography technology, for example, a resist film having a resist material strength is formed on a substrate, and light, electron beam, or the like is passed through a mask on which a predetermined pattern is formed on the resist film. A step of forming a resist pattern having a predetermined shape on the resist film is performed by performing selective exposure with radiation and developing. Resist material that changes its properties so that the exposed part dissolves in the developer is positive, V does not dissolve the exposed part in the developer, and the resist material that changes in characteristics is negative.

 In recent years, in the manufacture of semiconductor devices and liquid crystal display devices, pattern miniaturization has been rapidly progressing due to advances in lithography technology.

 As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, in the past, ultraviolet rays typified by g-line and i-line were used. Currently, mass production of semiconductor devices using KrF excimer laser and ArF excimer laser has begun. In addition, these excimer lasers have shorter wavelength excimer lasers, electron beams, EUV (

 2

 Extreme ultraviolet rays) and X-rays are also being studied.

[0003] Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. As a resist material satisfying such requirements, a chemically amplified resist containing a base resin whose alkali solubility is changed by the action of an acid and an acid generator that generates an acid upon exposure is used. For example, positive chemically amplified resist has increased alkali solubility due to the action of acid as a base resin. When the resist pattern is formed and an acid is generated from the acid generator upon exposure, the exposed portion becomes alkali-soluble.

 [0004] Until now, as a base resin for chemically amplified resists, it is highly transparent to KrF excimer laser (248 nm), and polyhydroxystyrene (PHS) and its hydroxyl groups are protected with acid dissociable, dissolution inhibiting groups.榭 脂 (PHS 系 榭 脂) has been used. However, since the PHS resin has an aromatic ring such as a benzene ring, the transparency to light having a wavelength shorter than 248 nm, for example, 193 ηm, is not sufficient. For this reason, chemically amplified resists that use PHS-based resin as a base resin component have drawbacks such as low resolution in a process that uses light of 193 nm, for example.

 For this reason, as the base resin of the resist currently used in ArF excimer laser lithography, etc., it is excellent in transparency around 193 nm, and therefore, a structural unit that generally induces (meth) acrylate force is mainly used. A resin (acrylic resin) contained in the chain is used. In the case of the positive type, as a strong coffin, a structural unit from which a (meth) acrylic acid ester having a tertiary alkyl ester type acid dissociable, dissolution inhibiting group containing an aliphatic polycyclic group is also derived, for example, 2-Alkyl-2-adamantyl (meth) atalyte isotonic resin having a structural unit derived mainly is used (for example, patent document)

1).

 [0005] The "(meth) acrylic acid ester" means one or both of an acrylic acid ester having a hydrogen atom bonded to the α-position and a methacrylic acid ester having a methyl group bonded to the a-position. “(Meth) acrylate” means either an acrylate having a hydrogen atom bonded to the α-position or a metatalate having a methyl group bonded to the α-position. “(Meth) acrylic acid” means both acrylic acid having a hydrogen atom bonded to the α-position and methacrylic acid having a methyl group bonded to the α-position !.

[0006] On the other hand, various acid generators used in chemically amplified resists have been proposed so far. For example, onium salt-based acids such as odonium salt and sulfo-um salt are proposed. Generating agents, oxime sulfonate acid generators, diazomethane acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like are known. Currently, as the acid generator, the triphenylsulfo-um skeleton In addition, acid generators containing a dinaphthyl monophenyl sulfone skeleton are used (Patent Document 2).

 Patent Document 1: Japanese Patent Laid-Open No. 2003-241385

 Patent Document 2: JP 2005-100203 A

 Disclosure of the invention

 Problems to be solved by the invention

 [0007] In recent years, the miniaturization of resist patterns has further progressed, and as the demand for high resolution has further increased, improvements in various lithography properties have been demanded.

 At present, as the cations of the acid salt-based acid generator, highly hydrophobic cations such as triphenyl sulfone and dinaphthyl monophenyl sulfone are generally used! In addition, an acid salt-based acid generator having a cation is used to dissolve various components of a resist, and has a low solubility in an organic solvent (resist solvent). is there. Such low solubility in a resist solvent reduces the temporal stability of the resist, and accordingly causes poor lithography properties.

 [0008] The present invention has been made in view of the above circumstances, and is a novel compound suitable as an acid generator for a resist composition, an acid generator comprising the compound, and a resist containing the acid generator. It is an object of the present invention to provide a resist composition and a resist pattern forming method using the resist composition.

 Means for solving the problem

[0009] The present inventors propose the following means in order to solve the above problems.

 That is, the first aspect (aspect) of the present invention is a compound represented by the following general formula (bl-3).

[Chemical 1]

[Wherein R "and R ^4d are each independently an alkyl group, a acetyl group, an alkoxy group, a carboxy group, a hydroxyl group, or a hydroxyalkyl group; n is an integer of 0 to 3, and n is 0 Is an integer from ~ 3, n is an integer from 0 to 2, provided that n, n and n are simultaneously

2 3 1 2 3 is never 0; x_ is key-on. ]

 [0010] The second aspect (aspect) of the present invention is an acid generator comprising a compound represented by the general formula (b1-3).

 [0011] Further, the third aspect (aspect) of the present invention includes a base material component (A) whose alkali solubility is changed by the action of an acid and an acid generator component (B) which generates an acid upon exposure. A resist composition comprising:

 The acid generator component (B) is a resist composition comprising an acid generator (B1) comprising a compound represented by the general formula (bl-3).

Furthermore, the fourth aspect of the present invention includes a step of forming a resist film on a substrate using the resist composition of the third aspect of the present invention, and the resist A resist pattern forming method including a step of exposing a film and a step of developing the resist film to form a resist pattern.

In the present specification and claims, the “structural unit” means a monomer unit (monomer unit) constituting the resin component (polymer).

 “Exposure” is a concept that includes radiation exposure in general.

 Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.

The “lower alkyl group” means an alkyl group having 1 to 5 carbon atoms. "Halony The “lower alkyl group” in the “lower alkyl group” has the same meaning.

 The invention's effect

 [0014] According to the present invention, a novel compound suitable as an acid generator for a resist composition, an acid generator comprising the compound, a resist composition containing the acid generator, and a resist pattern using the resist composition A forming method is provided.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0015] 《Compound》

 The compound of the first aspect (aspect) of the present invention is represented by the general formula (bl-3).

In the general formula (bl-3), R ⁴¹ , R ⁴² and R ⁴³ are each independently an alkyl group, acetyl group, alkoxy group, carboxy group, hydroxyl group or hydroxyalkyl group.

In R ⁴¹ , R ⁴² and R ⁴³ , the alkyl group is preferably a lower alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, a methyl group, an ethyl group, or a propyl group. Particularly preferred is a group, isopropyl group, n-butyl group, or tert-butyl group.

 The alkoxy group is particularly preferably a methoxy group or an ethoxy group, more preferably a linear or branched alkoxy group, particularly preferably an alkoxy group having 1 to 5 carbon atoms.

 Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group, which are preferably groups in which one or more hydrogen atoms of the above alkyl group are substituted with a hydroxy group.

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

 2

 n is an integer of 0 to 2, preferably 0 or 1, and more preferably 1.

 Three

 However, n, n, and n are not 0 at the same time.

 one two Three

[0017] In the general formula (bl-3), it is ΧΊ-on. The key-on part of X— is not particularly limited, and the one known as the key-on part of the form salt acid generator can be used as appropriate. For example, the general formula “R ¹⁴ SO _ (R ¹⁴ is a linear, branched or cyclic alkyl group.

 Three

 Or represents a halogenated alkyl group. ) "Can be used.

[0018] In the general formula "R ¹⁴ SO" j, R ¹⁴ represents a linear, branched or cyclic alkyl. Or a halogenated alkyl group.

The linear or branched alkyl group as R ¹⁴ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. . Most preferably, the cyclic alkyl group as R ¹⁴ has 4 to 15 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

R ¹⁴ is preferably a halogenoalkyl group. That is, in the general formula (bl-3), X— is preferably a halogenated alkyl sulfonate ion. The halogenated alkyl group is one in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. Here, examples of the halogenated alkyl group include those in which a halogen atom is substituted for the same as the “alkyl group” in R ¹⁴ .

 Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the alkyl halide, it is preferred that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferred that all are substituted! /. Here, the halogenated alkyl group is preferably a linear, branched or cyclic fluorinated alkyl group! /.

 The linear or branched fluorinated alkyl group has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Most preferred.

 The cyclic fluorinated alkyl group preferably has 4 to 15 carbon atoms, preferably 4 to carbon atoms, more preferably 6 to LO, and most preferably LO.

 The fluorination rate of the fluorinated alkyl group (the ratio of the number of fluorine atoms substituted by fluorination to the total number of hydrogen atoms in the alkyl group before fluorination, the same shall apply hereinafter) is preferably 10 to 100%, more preferably 50 to 100%, and particularly those in which all hydrogen atoms are substituted with fluorine atoms are most preferable because the strength of the acid is increased.

[0019] In the general formula (bl-3), use an anion represented by the following general formula (b-3), an arion represented by the following general formula (b-4), or the like. Can do.

[0020] [Chemical 2]

[In the formula, X "represents a C 2-6 alkylene group in which at least one hydrogen atom is substituted with a fluorine atom; Υ", Ζ "each independently represents at least one hydrogen Represents an alkyl group having 1 to 10 carbon atoms in which the atom is substituted with a fluorine atom.

 In the general formula (b-3), X ″ is a linear or branched alkylene group in which at least one hydrogen atom is replaced with a fluorine atom, and the alkylene group has a carbon number of , Preferably 2 to 6, more preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms In the general formula (b-4), Y "and Ζ" each independently represent at least 1 A straight-chain or branched alkyl group in which two hydrogen atoms are substituted with fluorine atoms, and the alkyl group preferably has 1 to L0, more preferably 1 to 7 carbon atoms, Most preferably, it has 1 to 3 carbon atoms.

 The carbon number of the alkylene group of X ″ or the carbon number of the alkyl group of Υ ″ and Ζ ″ is preferably as small as possible because the solubility in the resist solvent is good within the above carbon number range.

 In addition, in the alkylene group of X "or the alkyl group of Υ" and Ζ ", the greater the number of hydrogen atoms substituted by fluorine atoms, the stronger the acid strength and the higher the energy of 200 nm or less. The fluorination rate of the alkylene group or alkyl group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms. A perfluoroalkylene group or a perfluoroalkyl group in which an atom is substituted with a fluorine atom.

 [0023] Preferred specific examples of the compound of the first aspect of the present invention are given below.

[0024] [Chemical 3]

 (b1-40) (bl -41) (b1 -42)

Among these, compounds represented by the chemical formulas (bl-31), (bl-34), (bl-37), and (bl-40) are preferable.

<Method for producing compound> The compound (bl-3) of the first aspect (aspect) of the present invention is represented by, for example, a compound represented by the following general formula (bl-0 31) and a general formula (bl-0-32) below. And a compound such as copper (II) benzoate in a solvent such as black benzene and iodine benzene at 80 to 130 ° C, more preferably at 100 to 120 ° C. It can be obtained by reacting for 5 to 3 hours, more preferably 1 to 2 hours.

 [0027] [Chemical 6]

[In the formula, R is the same as R ⁴¹ in the formula (bl-3); n is the same as n in the formula (bl-3); It is the same as X— in the formula. ]

 [0028] [Chemical 7]

Wherein, R ⁴ and R ^4d are the same as R ⁴ and R ^4d in the (BL- 3) formula; n and

 2 n is the same as n and n in the above formula (bl-3). However, n, n and n are the same

3 2 3 1 2 3 is never 0. ]

 [0029] <Acid generator>

The acid generator of the second aspect of the present invention (hereinafter referred to as “acid generator (Bl) t”) may have a compound power represented by the general formula (b 1-3). Wherein R ⁴¹ , R ⁴² and R ⁴³ ; n, n and n; X_ are those mentioned in the compound of the first aspect of the present invention.

twenty three

 It is the same.

[0030] <Resist composition> The resist composition of the third aspect (aspect) of the present invention comprises a substrate component (A) whose alkali solubility is changed by the action of an acid (hereinafter referred to as component (A)) and an acid that generates an acid upon exposure. It contains a generator component (B) (hereinafter referred to as component (B)), and the component (B) contains an acid generator (B1) that also has the compound power represented by the general formula (b 13). It is a waste.

[0031] In the resist composition of the present invention, as the component (A), a polymer material whose alkali solubility is changed by the action of an acid can be used, and a low molecular weight material whose alkali solubility is changed by the action of an acid. Can also be used.

 The resist composition of the present invention may be a negative resist composition or a positive resist composition! / ヽ.

 When the resist composition of the present invention is a negative resist composition, for example, the component (A) is an alkali-soluble resin, and a crosslinking agent (C) is further added to the negative resist composition.

 In a negative resist composition, when an acid is generated from the component (B) by exposure during resist pattern formation, the exposed portion acts to crosslink between the alkali-soluble resin and the crosslinking agent. Occurs and changes to alkali-insoluble.

 As the alkali-soluble coconut resin, the coconut resin having a unit derived from at least one of a- (hydroxyalkyl) acrylic acid or α- (hydroxyalkyl) acrylic acid also having a lower alkyl ester power is selected. It is preferable because a good resist pattern can be formed. In addition, a (hydroxyalkyl) acrylic acid is composed of acrylic acid in which a hydrogen atom is bonded to the α-position carbon atom to which the carboxy group is bonded, and a hydroxyalkyl group (preferably having 1 carbon atom) in the α-position carbon atom. ˜5 hydroxyalkyl groups) to which (X-hydroxyalkylacrylic acid or both) is attached.

 As the crosslinking agent (C), for example, it is usually preferable to use an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, which can form a good resist pattern with little swelling. . The amount of the crosslinking agent (C) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.

[0032] When the resist composition of the present invention is a positive resist composition, component (ii) is V, an alkali-insoluble one having an acid dissociable, dissolution inhibiting group, and resist pattern formation Occasionally, when an acid is generated from the component (B) by exposure, the acid releases the acid dissociable, dissolution inhibiting group, so that the component (A) becomes alkali-soluble. Therefore, in the formation of the resist pattern, when the resist film obtained by applying the positive resist composition on the substrate is selectively exposed, the exposed portion turns to alkali-soluble while the unexposed portion Since it remains insoluble in alkali, it can be developed with alkali.

 In the resist composition of the present invention, the component (A) is preferably a base material component whose alkali solubility is increased by the action of an acid. The resin component (A1) whose alkali solubility is increased by the action of an acid. ) (Hereinafter referred to as the component (A1)) is more preferable. That is, the resist composition of the present invention is preferably a positive resist composition. In addition, the resist composition of the present invention can be suitably used as a resist composition for immersion exposure in a resist pattern forming method including an immersion exposure step, and a step of forming a three-layer resist laminate. The resist pattern forming method can be suitably used as a positive resist composition for forming an upper resist film.

 Next, in the resist pattern forming method including the immersion exposure step and the step of forming a Z or three-layer resist laminate, the (A1) component that is preferably used for the positive resist composition is exemplified. explain.

 [0034] <(A1) component>

 The component (A1) suitably used in a strong positive resist composition preferably has a structural unit (al) derived from an acrylate ester group containing an acid-releasing dissolution inhibiting group.

 The component (A1) preferably further has a structural unit (a2) derived from an acrylate ester containing a latathone-containing cyclic group.

 In addition, the component (A1) preferably further has a structural unit (a3) from which an ester ester acrylate containing a polar group-containing aliphatic hydrocarbon group is also derived.

[0035] Here, in the present specification and claims, the "structural unit derived from an acrylate ester force" means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester. To do.

“Acrylic acid ester” refers to an acrylic acid ester having a hydrogen atom bonded to a carbon atom at the X position. In addition to stealth, the concept also includes those in which a substituent (atom or group other than a hydrogen atom) is bonded to the carbon atom at position a.

 Examples of the substituent include a halogen atom, a lower alkyl group, and a halogenated lower alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. The “halogen lower alkyl group” is a group in which at least one or all of the hydrogen atoms of the lower alkyl group are substituted with the halogen atoms.

 In addition, the α position of the structural unit from which the acrylate power is also derived (the carbon atom at the position) means a carbon atom to which a carbo group is bonded, unless otherwise specified. In the acrylate ester, as the lower alkyl group as the substituent at the α-position, specifically, methyl group, ethyl group, propyl group, isopropyl group, η-butyl group, isopropyl group, tert-butyl group, pentyl group And a linear or branched lower alkyl group such as an isopentyl group and a neopentyl group.

 In the present invention, it is preferable that a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group is bonded to the α-position of the acrylate ester, and a hydrogen atom, a fluorine atom, a lower alkyl group or A fluorinated lower alkyl group is more preferred, and a hydrogen atom or a methyl group is particularly preferred from the viewpoint of industrial availability.

· Unit (al)

 The structural unit (al) is a structural unit derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.

The acid dissociable, dissolution inhibiting group in the structural unit (al) has an alkali dissolution inhibiting property that makes the entire component (A1) insoluble in alkali before dissociation, and after dissociation, the entire (A1) component changes to alkali soluble. As long as it can be used, those proposed so far as the acid dissociable, dissolution inhibiting group of the base resin for chemically amplified resists can be used. In general, a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group in (meth) acrylic acid, etc .; an acetal type acid dissociable, dissolution inhibiting group such as an alkoxyalkyl group is widely known. . “(Meth) acrylic acid” means acrylic acid and It means one or both of tacrylic acid.

 [0037] Here, the "tertiary alkyl ester" is an ester formed by substitution with a hydrogen atom of a carboxy group, a chain or cyclic alkyl group, and the carboxy group ( A structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the terminal oxygen atom of 1 C (O) —0—). In this tertiary alkyl ester, when an acid acts, the bond is broken between the oxygen atom and the tertiary carbon atom.

 The chain or cyclic alkyl group may have a substituent! /. Hereinafter, a group that becomes acid dissociable by constituting a carboxy group and a tertiary alkyl ester will be referred to as a “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience. Examples of the tertiary alkyl ester type acid dissociable, dissolution inhibiting group include aliphatic branched acid dissociable, dissolution inhibiting groups, and acid dissociable, dissolution inhibiting groups containing aliphatic cyclic groups.

[0038] Here, "aliphatic" in the claims and the specification is a relative concept with respect to aromatics, and is defined to mean a group, compound, or the like that does not have aromaticity.

"Aliphatic branched" means that it has no aromaticity and has a branched structure

The structure of the “aliphatic branched acid dissociable, dissolution inhibiting group” is not limited to a group consisting of a carbon atom and a hydrogen atom (hydrocarbon group), but is preferably a hydrocarbon group. Yes.

 The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.

 As the aliphatic branched acid dissociable, dissolution inhibiting group, a tertiary alkyl group having 4 to 8 carbon atoms is preferred. Specifically, a tert-butyl group, a tert-amyl group, a tert-heptyl group, etc. Can be mentioned.

 [0039] "Aliphatic cyclic group" indicates that it has no aromaticity and is a monocyclic group or a polycyclic group.

The “aliphatic cyclic group” in the structural unit (al) 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 with a fluorine atom, an oxygen atom (= 0), and the like. Is mentioned.

 Except for the substituents of the “aliphatic cyclic group”, the basic ring structure is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but may be a hydrocarbon group. Favored ,. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated. The “aliphatic cyclic group” is preferably a polycyclic group.

 Specific examples of the aliphatic cyclic group include, for example, a lower alkyl group, a fluorine atom or a fluorinated alkyl group, which may or may not be substituted, monocycloalkane, bicycloalkane. And a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as tricycloalkane or tetracycloalkane. Specifically, cyclopentane

And monocycloalkanes such as cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

 Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include a group having a tertiary carbon atom on the ring skeleton of a cyclic alkyl group, specifically, 2-methyl 2-adamantyl. Group, 2-ethyl-2-adamantyl group and the like. Or, in a structural unit represented by the following general formula (al "), an aliphatic cyclic group such as an adamantyl group such as a group bonded to an oxygen atom of a carbo-oxy group (-C (O) -0-). And a group having a group and a branched alkylene group having a tertiary carbon atom bonded thereto.

[Chemical 8]

[式中、 Rは水素原子、ハロゲン原子、低級アルキル基またはハロゲン化アルキル基 であり、 R¹⁵、 R¹⁶はアルキル基 (直鎖状、分岐鎖状のいずれでもよぐ好ましくは炭素 数 1〜5である。）を示す。 ]

[In the formula, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated alkyl group, and R ¹⁵ and R ¹⁶ are alkyl groups (both linear and branched, preferably 1 to 5). ]

 The halogen atom, lower alkyl group or halogenated lower alkyl group of R in the above formula is the same as the halogen atom, lower alkyl group or halogenated lower alkyl group which may be bonded to the α-position of the acrylate ester. .

 [0041] "Acetal type acid dissociable, dissolution inhibiting group" is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an alkali-soluble group such as a carboxy group or a hydroxyl group. When an acid is generated by exposure, this acid acts to break the bond between the acetal type acid dissociable, dissolution inhibiting group and the oxygen atom to which the acetal type acid dissociable, dissolution inhibiting group is bonded. . Examples of the acetal type acid dissociable, dissolution inhibiting group include a group represented by the following general formula (pi).

 [0042] [Chemical 9]

[Wherein, R ¹ ′ and R ² ′ each independently represents a hydrogen atom or a lower alkyl group, n represents an integer of 0 to 3, and Y represents a lower alkyl group or an aliphatic cyclic group. ]

[0043] In the above formula, n is preferably an integer of 0 to 2, 0 or 1 is more preferable, and 0 is most preferable.

Examples of the lower alkyl group for R ¹ ′ and R ² ′ include the same lower alkyl groups as those described above for R, and a methyl group that is preferably a methyl group or an ethyl group is most preferable.

In the present invention, it is preferable that at least one of R ¹ ′ and R ² is a hydrogen atom. That is, the acid dissociable, dissolution inhibiting group (pi) is preferably a group represented by the following general formula (pi-1).

[0044] [Chemical 10]

Wherein, R ¹ ', n, Y is R ¹ in the general formula (pi)', n, it is the same as Y. ]

[0045] Examples of the lower alkyl group of Υ include those similar to the lower alkyl group of R above.

As the aliphatic cyclic group, a large number of conventionally proposed ArF resists and the like can be appropriately selected from monocyclic or polycyclic aliphatic cyclic groups. Examples thereof are the same as the “aliphatic cyclic group”.

[0046] Further, the acetal type acid dissociable, dissolution inhibiting group includes a group represented by the following general formula (p2).

 [0047] [Chemical 11]

[Wherein, R ¹⁷ and R ¹⁸ each independently represent a linear or branched alkyl group or a hydrogen atom, and R ¹⁹ represents a linear, branched or cyclic alkyl group. Or, R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group, and the end of R ^{17 and} the end of R ¹⁹ may be bonded to form a ring. ]

In R ¹⁷ and R ¹⁸ , the alkyl group preferably has 1 to 15 carbon atoms, and is preferably a straight-chain or branched-chain ethyl group or a methyl group with a methyl group being preferred. . In particular, one of R ¹⁷ and R ¹⁸ is preferably a hydrogen atom and the other is a katyl group.

R ¹⁹ is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and may be linear, branched or cyclic.

When R ¹⁹ is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably an ethyl group.

When R ¹⁹ is cyclic, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and further preferably 5 to carbon atoms: LO is most preferable. Specifically, fluorine atom or fluorination A group obtained by removing one or more hydrogen atoms from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, etc., which may or may not be substituted with an alkyl group, etc. It can be illustrated. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. It is done. Among them, a group in which one or more hydrogen atoms are removed from adamantane is preferable.

In the above formula, R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the end of R ^{19 and} the end of R ¹⁷ The end may be bonded.

In this case, a cyclic group is formed by R ¹⁷ and R ¹⁹ , the oxygen atom to which R ¹⁹ is bonded, and the carbon atom to which the oxygen atom and R ¹⁷ are bonded. As the cyclic group, a 4- to 7-membered ring is preferable, and a 4- to 6-membered ring is more preferable. Specific examples of the cyclic group include a tetrahydrobiranyl group and a tetrahydrofuran group.

[0049] As the structural unit (al), a structural unit represented by the following general formula (al-0-1) and a structural unit force represented by the following general formula (al-0-2) are selected. It is preferable to use one or more.

[0050] [Chemical 12]

— 0—1 )

— 0—1)

[Wherein, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; X ¹ represents an acid dissociable, dissolution inhibiting group. ]

[Chemical 13]

[Wherein, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; X ² represents an acid dissociable, dissolution inhibiting group; Y ² represents an alkylene group or an aliphatic cyclic group. . ]

 [0052] In the general formula (al-0-1), the halogen atom, lower alkyl group, or halogenated lower alkyl group of R is a halogen atom, lower alkyl group, or optionally bonded to the α-position of the acrylate ester. This is the same as the halogeno lower alkyl group.

X ¹ is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group, and examples thereof include the above-described tertiary alkyl ester type acid dissociable, dissolution inhibiting group, acetal type acid dissociable, dissolution inhibiting group, and the like. Tertiary alkyl ester type acid dissociable, dissolution inhibiting groups are preferred ヽ

[0053] In general formula (al-0-2),! /, R is the same as R in general formula (al-0-1).

X ² is the same as X ¹ in the formula (al-0-1).

Y ² is preferably an alkylene group having 1 to 4 carbon atoms or a divalent aliphatic cyclic group, and the aliphatic cyclic group is the above except that a group in which two or more hydrogen atoms are removed is used. The same explanation as in the “aliphatic cyclic group” can be used.

[0054] Specific examples of the structural unit (al) include structural units represented by the following general formulas (al-1) to (al-4).

[0055] [Chemical 14]

[In the above formula, X ′ represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group; Y represents a lower alkyl group having 1 to 5 carbon atoms or an aliphatic cyclic group; and η represents 0 to 3 M represents 0 or 1; R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; R ¹ ′ and R ² ′ each independently represent a hydrogen atom or carbon number 1 Represents a lower alkyl group of ~ 5. ]

[0056] R in the above general formulas (al-1) to (al-4) is the same as R in the general formulas (al-0-1) to (al-0-2).

R ¹ ′ and R ² ′ are preferably at least one hydrogen atom, more preferably a hydrogen atom. n is preferably 0 or 1.

[0057] X, is the same as the tertiary alkyl ester-type acid dissociable, dissolution inhibiting group exemplified for X ¹ above.

 Examples of the aliphatic cyclic group for Y include the same groups as those exemplified above in the explanation of the “aliphatic cyclic group”.

[0058] Specific examples of the structural units represented by the general formulas (al-1) to (al-4) are shown below.

6] [0059] [Chemical 15]

6]

(a1-1— 20)

 (a1-1-19)

 (al— 1— 17) (al-1-18)

17]

17]

[] 0062

20]

20]

(a1— 2-34) (al-2-35) 1]

§ [] ^ 0067

5] (a 卜 3-21) (a 1-3-22) (a 1-3-23) (a1-3 4)

Five]

 (a1-4-26) (al-4-27) (a1- 4-28) (a1-4-29) (a 1 -4-30) As the structural unit (al), one type is used alone. You may use 2 or more types in combination.

Among them, the structural unit represented by the general formula (al— 1) is specifically preferred (al— 1 1) to (al— 1— 6) or (al— 1— 35) to (al— It is more preferable to use at least one selected from the structural unit forces represented by 1-41). Furthermore, as the structural unit (al), in particular, those represented by the following general formula (al-1 01) including structural units of the formula (al 1 1) to the formula (al 1-4), and the formula (al — The following general formula (a 1—102) including the structural units of (1 35) to (al— 1 -41) is also preferred.

[0071] [Chemical 26]

■■ -、a，一1— ΟΊ )

■■-, a, 1-1 ΟΊ)

[Wherein, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R ¹¹ represents a lower alkyl group. ]

 [0072] [Chemical 27]

[Wherein, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R ¹² represents a lower alkyl group. h represents an integer of 1 to 3. ]

[0073] In general formula (al-1-01),! / And R! / Are the same as R in general formula (al-1). The lower alkyl group for R ^{11 is the same as} the lower alkyl group for R, and is preferably a methyl group or an ethyl group.

[0074] In general formula (al-1-02),! / And R are the same as R in general formula (al-1) above. The lower alkyl group for R ^{12 is the same as} the lower alkyl group for R, and a methyl group or an ethyl group is preferred, and an ethyl group is most preferred. h is preferably 1 or 2. 2 is most preferred. [0075] the proportion of (Al) structural units within the component (al) is, (A1) relative to the total structural units constituting the component 10-80 Monore _^0/0 force S Preferably, 20-70 Monore _^0/0 force more preferably S, 25 to 50 Monore _^0/0 force S more preferred. By setting it to the lower limit value or more, a pattern can be easily obtained when the positive resist composition is used, and by setting it to the upper limit value or less, it is possible to balance with other structural units.

 [0076] · Structural unit (a2)

 In the present invention, the component (A1) preferably has a structural unit (a2) derived from an acrylate ester containing a latathone-containing cyclic group, in addition to the structural unit (al).

 Here, the ratatone-containing cyclic group refers to a cyclic group containing one ring (lataton ring) containing a -o-c (o) structure. The rataton ring is counted as the first ring, and if it is only a rataton ring, it is called a monocyclic group, and if it has another ring structure, it is called a polycyclic group regardless of the structure.

 The lathetone-containing cyclic group of the structural unit (a2) has an affinity for the resist film to improve the adhesion of the resist film to the substrate or to have an affinity for a developer containing water when the component (A1) is used for forming the resist film. It is effective in enhancing the sex.

As the structural unit (a2), any unit can be used without any particular limitation.

 Specifically, examples of the latatatone-containing monocyclic group include groups in which y-peptidyl latatone force hydrogen atom is removed. In addition, examples of the latathone-containing polycyclic group include groups obtained by removing one hydrogen atom from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane having a latathone ring.

More specifically, examples of the structural unit (a2) include structural units represented by the following general formulas (a2−1) to (a2−5).

[0079] [Chemical 28]

[Wherein, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R ′ is independently a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms. , M is an integer of 0 or 1, and A is an alkylene group having 1 to 5 carbon atoms or an oxygen atom.

 ]

 [0080] R in the general formulas (a2-1) to (a2-5) is the same as R in the general formula (al ") of the structural unit (al).

 The lower alkyl group for R ′ is the same as the lower alkyl group for R in the structural unit (al).

 Specific examples of the alkylene group having 1 to 5 carbon atoms of A include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.

 In general formulas (a2-1) to (a2-5), R ′ is preferably a hydrogen atom in view of industrial availability.

 Specific examples of the structural units of the general formulas (a2-1) to (a2-5) are shown below.

[0081] [Chemical 29]

 3¾-

[§] 00 c

¾ 一一 Ηε _--

OAV

〔〕8003

[] 8003

Among these, it is preferable to use at least one selected from the general formulas (& 2-1) to (& 2-5) V, and the general formulas (a2-1) to (a2— It is more preferable to use at least one selected from 3). Specifically, chemical formulas (a2—1—1), (a2—l—2), (a2—2-1—), (a2—2-2—), (a2—3-1—), (a2—3) — It is preferable to use at least one selected from (2), (a2-3-9) and (a2-3-10).

 In the component (A1), as the structural unit (a2), one type may be used alone, or two or more types may be used in combination.

(A1), the amount of the structural units within the component (a2) is, (A1) based on the combined total of all structural units constituting the component 5 to 60 Monore _^0/0 force S Preferably, 10-50 Monore _^0/0 power S More preferably, it is more preferably 20-50 monole ⁰ / ₀ %. By containing the structural unit (a2) by setting it to the lower limit value or more, the above-described effects can be sufficiently obtained, and by setting it to the upper limit value or less, tolerance with other structural units can be obtained.

 [0088] · Structural unit (a3)

In the present invention, the component (A1) is added to the structural unit (al) or the structural unit. In addition to the positions (al) and (a2), it is preferable to further have _a structural unit (a3) derived from an acrylate ester group containing a polar group-containing aliphatic hydrocarbon group. By having the structural unit (a3), the hydrophilicity of the component (A1) is increased, the affinity with the developer is increased, the alkali solubility in the exposed area is improved, and the resolution is improved.

 Examples of the polar group include a hydroxyalkyl group in which at least one hydrogen atom of a hydroxyl group, cyano group, carboxy group, or alkyl group is substituted with a fluorine atom (hereinafter sometimes referred to as “fluorinated alkyl alcohol”). In particular, a hydroxyl group is preferred.

 Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a polycyclic aliphatic hydrocarbon group (polycyclic group). It is possible. As the polycyclic group, for example, many resins for resist compositions for ArF excimer lasers have been proposed and can be appropriately selected and used.

 Among them, it is derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which at least one hydrogen atom of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a fluorine atom. The structural unit is preferred. Examples of the polycyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as bicycloalkane, tricycloalkane, and tetracycloalkane. Specific examples include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Among these polycyclic groups, a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from norbornane, a group obtained by removing two or more hydrogen atoms from tetracyclododecane, These groups are industrially preferred.

[0089] As the structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a hydroxyethyl ester ester of acrylic acid is used. When the hydrocarbon group is a polycyclic group, a structural unit represented by the following formula (a3-1) and a structural unit represented by (a3-2) are preferred. The structural unit represented by (a3-3) is preferred.

[0090] [Chemical 34]

[Wherein, R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, j is an integer of 1 to 3, k is an integer of 1 to 3, and t ′ is 1 to 3] An integer of 3,

1 is an integer from 1 to 5, and s is an integer from 1 to 3. ]

[0091] The halogen atom, lower alkyl group, or halogeno-lower alkyl group of R in the general formulas (a3-1) to (a3-3) is bonded to the α-position of the above acrylate ester. It is the same as the atom, lower alkyl group or halogenated lower alkyl group. In the formula (a3-1), j is preferably 1 or 2, and more preferably 1! /. When j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group. j

In the case of 1, the hydroxyl group is preferably bonded to the 3rd position of the adamantyl group.

 Among these, j is more preferably 1, particularly a hydroxyl group bonded to the 3rd position of the adamantyl group!

In formula (a3-2), k is preferably 1. The cyan group is the 5-position of the norbornyl group or

I prefer to be in 6th place.

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

[0094] In the component (A1), as the structural unit (a3), one type may be used alone, or two or more types may be used in combination.

The proportion of constituent unit (a3) in component (A1) is based on the total constituent units constituting component (A1). , Preferably from preferred tool 40 mol _^0/0 force 5 to 50 mole _^0/0, preferably by 5 to 25 mole _^0/0 Gasa et al. By containing the structural unit (a3) by setting it to the lower limit value or more, the above-described effects can be sufficiently obtained, and by setting it to the upper limit value or less, it is possible to obtain tolerance with other structural units.

[0095] · Unit (a4)

 The component (Al) includes other structural units (a4) other than the structural units (al) to (a3) as long as the effects of the present invention are not impaired.

 The structural unit (a4) is not classified into the above structural units (al) to (a3)! However, other structural units are not particularly limited. Many of them are known to be used in resist resins such as for ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser). Things can be used.

 As the structural unit (a4), for example, a structural unit derived from an ester acrylate ester containing an acid non-dissociable aliphatic polycyclic group is preferable. Examples of the polycyclic group include those exemplified in the case of the structural unit (al), for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser). A large number of conventionally known strengths can be used as the oil component of the resist composition.

 In particular, at least one kind selected from tricyclodecanyl group, adamantyl group, tetracyclododecyl group, isobornyl group and norbornyl group is preferable in terms of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

 Specifically, as the structural unit (a4), those having the structures of the following general formulas (a4-l) to (a4-5) can be shown in column f.

[0096] [Chemical 35] _{04-3) <a4-4) (4 _} 5)

(34-1) ^(a4 " ² > ()

[Wherein, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group. ]

In the general formulas (a4-1) to (a4-5), the R halogen atom, lower alkyl group or halogenated lower alkyl group is bonded to the _α- position of the acrylate ester to form V, And the same as a norogen atom, a lower alkyl group or a halogenated lower alkyl group.

When the strong structural unit (a4) is contained in the component (A1), the proportion of the structural unit (a4) should be 1 to 30 mol% with respect to the total of all the structural units constituting the component (A1). and more preferably is a preferred tool 10 20 mol _^0/0! /,.

 [0098] In the present invention, the component (A1) is a rosin component (polymer) whose alkali solubility is increased by the action of an acid, and is suitable as such a rosin component (polymer). For example, it is a copolymer having the structural units (al), (a2), and (a3). As such a copolymer, for example, the structural units (al), (a2), and (a3) forces are also included. And copolymers having structural units (al), (a2), (a3) and (a4).

 [0099] In the present invention, the component (A) is particularly preferably a copolymer (A1-1) containing a combination of structural units represented by the following general formula (A1-1). ,.

[0100] [Chemical 36]

[Wherein, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group. R ² is a lower alkyl group. ]

[0101] The halogen atom, lower alkyl group, or halogenated lower alkyl group of R in the formula (A1-1) is a halogen atom, lower alkyl group, or halogen atom that may be bonded to the α-position of the acrylate ester. The same as the lower alkyl group. Among these, R is most preferably a hydrogen atom or a methyl group.

R ² is a lower alkyl group, preferably a methyl group or an ethyl group.

Most preferably, it is a methyl group.

[0102] In component (A), as copolymer (A1-1), one type may be used alone, or two or more types may be used in combination.

 The content of the copolymer (A1-1) in the component (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass. . When it is at least the lower limit of the range, the lithography properties are further improved when a positive resist composition is obtained.

 [0103] The component (A1) is obtained by polymerizing the monomer for deriving each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyl-tolyl (AIBN). Obtainable.

 In addition, the component (A1) includes, for example, HS—CH—CH—CH—C (C

 2 2 2

When a chain transfer agent such as F) —OH is used in combination, one terminal C (CF) — O

3 2 3 2

An H group may be introduced. In this way, copolymers in which a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms are introduced have reduced development defects and LER (Line Edge Roughness: uneven unevenness on the line sidewalls). (roughness)). [0104] The mass average molecular weight (Mw) of the (Al) component (polystyrene conversion standard by gel permeation chromatography) is not particularly limited, but is preferably 2000 to 50000, more preferably 3000 to 30000 force < , 5000 ~ 20000 power is the most preferred! If it is smaller than the upper limit of this range, it is sufficiently soluble in a resist solvent to be used as a resist, and if it is larger than the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.

 Further, the degree of dispersion (Mw / Mn) i is preferably 1.0 to 5.0 force S, more preferably 1.0 to 3.0 force S, and most preferably 1.2 to 2.5. Mn represents a number average molecular weight.

 Further, as the component (A1), an alkali-soluble resin component other than the copolymer (A1-1), for example, other high molecular compounds used in conventional positive resist compositions can be used. .

 In the positive resist composition of the present invention, the content of the component (A1) should be adjusted according to the thickness of the resist film to be formed.

[0105] <(B) component>

In the resist composition of the present invention, the component) includes an acid generator (B1) (hereinafter referred to as the component (B1)) composed of the compound represented by the general formula (bl-3). In which R ⁴¹ , R ⁴² and R ⁴³ ; n, n and n; X_ are the compounds of the first aspect of the present invention

 one two Three

 It is the same as that mentioned in.

 By including the component (B1), the component (B) is soluble in general resist solvents such as propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and lactate ethyl (EL). When the resist pattern forming method including the immersion exposure step and the step of forming the three-layer resist laminate is performed, the resist composition for immersion exposure and the resist composition for forming the upper resist film are obtained. Good lithographic characteristics can be obtained.

Further, the component (B1) can be incorporated in a large amount in a resist composition used in a resist pattern forming method including an immersion exposure step and a step of forming a three-layer resist laminate. This is thought to be due to the high transparency (suppression of light absorption) in the exposure wavelength band (especially the wavelength band of ArF excimer laser). [0106] The component (B) can be used alone or in combination.

 In the resist composition of the present invention, the content of the component (B1) in the total component (B) is preferably 40% by mass or more, and more preferably 70% by mass or more. Preferably it is 100% by mass. By being above the lower limit of the range, the resist pattern shape is good. In particular, when a resist pattern is formed using a resist composition for immersion exposure or a resist composition for forming an upper resist film, the lithography characteristics are improved. When forming a three-layer resist laminate, matching with the lower layer film of the resist is good and footing of the resist pattern can be suppressed, which is preferable.

 In the resist composition of the present invention, the content of the component (B1) is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (A). It is most preferably 7 to 18 parts by mass. When it is at least the lower limit of the range, lithography characteristics are improved particularly when a resist pattern is formed in a resist composition for immersion exposure or a resist composition for forming an upper resist film. On the other hand, when it is below the upper limit, storage stability is good.

 [0107] In component (B), an acid generator (B2) (hereinafter referred to as component (B2)) other than component (B1) may be used in combination with component (B1). Good.

 The component (B2) is not particularly limited as long as it is other than the component (B1), and those that have been proposed as acid generators for chemically amplified resists can be used. Examples of such acid generators include onium salt-based acid generators such as iodine salts and sulfo-um salts; oxime sulfonate-based acid generators; bisalkyl or bisarylsulfol-diazomethanes, There are various known diazomethane acid generators such as (bissulfol) diazomethanes; nitrobenzyl sulfonate acid generators; iminosulfonate acid generators; disulfone acid generators.

 [0108] As the acid salt-based acid generator, for example, an acid generator represented by the following general formula (b-0) can be preferably used.

[0109] [Chemical 37]

[Wherein ¹ represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group; R ⁵² represents a hydrogen atom, a hydroxyl group, A halogen atom, a linear or branched alkyl group, a linear or branched alkyl halide group, or a linear or branched alkoxy group; R ⁵³ has a substituent. And u "is an integer from 1 to 3.]

[0111] In the general formula (b- 0), R ⁵¹ represents a linear, branched or cyclic alkyl group, or a straight, branched or cyclic fluorinated alkyl group.

 The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. Good.

 The cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to carbon atoms: LO.

 The linear or branched fluorinated alkyl group has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Most preferred.

 The cyclic fluorinated alkyl group is preferably 4 to 12 carbon atoms, preferably 5 to carbon atoms, more preferably 6 to LO, most preferably LO.

 The fluorination rate of the fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. In particular, all hydrogen atoms substituted with fluorine atoms are preferred because the strength of the acid is increased.

R ⁵¹ is most preferably a linear alkyl group or a linear fluorinated alkyl group.

[0112] R ⁵² represents a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group. , A linear or branched alkyl halide group, or a linear or branched alkoxy group.

In R ⁵² , examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and among them, a fluorine atom is preferred.

In R ⁵² , the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.

In R ⁵² , the halogenated alkyl group is a group in which at least one or all of the hydrogen atoms in the alkyl group are substituted with a halogen atom. Examples of the alkyl group herein are the same as the “alkyl group” in 2 above. Examples of the halogen atom to be substituted are the same as those described above for the “halogen atom”. In the halogenalkyl group, 50 to 100% of the total number of hydrogen atoms are preferably substituted with halogen atoms, more preferably all are substituted.

In R ⁵² , the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.

Of these, hydrogen atom is the most preferred as R ⁵² .

[0113] R ⁵³ is an aryl group which may have a substituent, and the structure of the basic ring (matrix ring) excluding the substituent includes a naphthyl group, a phenyl group, an anthracyl group, and the like. In view of the effects of the present invention and the absorption of exposure light such as an ArF excimer laser, a phenyl group is preferred.

 Examples of the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 1 to 5 carbon atoms, and more preferably a methyl group). Monkey.

As the aryl group for R ⁵³ , those having no substituent are more preferable.

 u "is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0114] Preferred examples of the acid generator represented by the general formula (b-0) include the following.

[0115] [Chemical 38]

[0116] The acid generators represented by the general formula (b-0) can be used singly or in combination.

 [0117] Further, other acid salt-based acid generators of the acid generator represented by the general formula (b-0), for example, represented by the following general formula (b-1) or (b-2) The compound to be used is also preferably used.

[0118] [Chemical 39]

R "S0 ₃ ". (B-2)

[Wherein, ,, to ", R ⁵ " and R ⁶ "each independently represents an aryl group or an alkyl group; R ⁴ " represents a linear, branched or cyclic alkyl group or a fluorinated group. Represents an alkyl group; at least one of R ^{lw to} R ³ ″ represents an aryl group, and at least one of R ⁵ ″ and R ⁶ ″ represents an aryl group.]

[0119] In formula (b-1), "to" each independently represents an aryl group or an alkyl group. At least one of R to “represents an aryl group. Of,, to“, two or more are preferably aryl groups. R ^{lw to} R ³ ”are all aryl groups. Most preferred

The aryl group of R ^{lw to} R ³ "is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, in which at least one or all of the hydrogen atoms are alkyl groups, It may or may not be substituted with an alkoxy group, a halogen atom, etc. As an aryl group, an aryl group having 6 to 10 carbon atoms is preferred because it can be synthesized at low cost. That's right. Specific examples include a phenyl group and a naphthyl group.

 Examples of the alkyl group on which the hydrogen atom of the aryl group may be substituted include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, which are preferably alkyl groups having 1 to 5 carbon atoms. That is the most preferred.

 As the alkoxy group that may be substituted with a hydrogen atom of the aryl group, a methoxy group and an ethoxy group are preferred, with an alkoxy group having 1 to 5 carbon atoms being preferred.

 The halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.

 The “˜” alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nor group, deoxy group, Examples thereof include a force group. Among these, a methyl group is most preferable because it is excellent in resolution from the viewpoint of excellent resolution and is preferably excellent in resolution and can be synthesized at low cost.

Among these, R ^{lw to} R ³ ″ are most preferably a phenyl group or a naphthyl group, respectively.

R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.

The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. The cyclic alkyl group is a cyclic group as shown by the above R ¹ ″, preferably a carbon number of 4 to 15 carbon atoms, more preferably a carbon number of 4 to 10 carbon atoms. Most preferably, the number is from 6 to 10.

 The linear or branched fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Most preferred.

The cyclic fluorinated alkyl group preferably has 4 to 15 carbon atoms, preferably 4 to carbon atoms, more preferably 6 to LO, and most preferably LO. Further, the fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. Those substituted with a nitrogen atom are preferred because the strength of the acid increases.

R ⁴ ″ is most preferably a linear or cyclic alkyl group, or a linear or cyclic fluorinated alkyl group.

In formula (b-2), R ⁵ ″ and R ⁶ ″ each independently represent an aryl group or an alkyl group.

At least one of R ⁵ "and R ⁶ " represents an aryl group. All of R ⁵ "and R ⁶ " are preferably aryl groups! /.

Examples of the aryl group of R ⁵ "and R ⁶ " include those similar to the aryl groups of,, ~.

As the alkyl group for R ⁵ ″ and R ⁶ ″, the same as the alkyl groups for R ^{1w to} R ³ ″ can be used.

Of these, R ⁵ ″ and R ⁶ ″ are most preferably a phenol group. Those similar to - "(1 b) R ⁴ in the formula is as" the like R ⁴ of formula (b-2) in.

[0122] Specific examples of the sodium salt acid generator represented by the formulas (b-1) and (b-2) include difluoro-rhodonium trifluoromethanesulfonate or nonafluorobutanesulfonate. Bis (4-tert-butylphenol) trifluoromethanesulfonate or nonafluorobutanesulfonate, trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorolob Tansusulfonate, tri (4 methylphenol) sulfurium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfotrifluoromethane Lomethanesulfonate and its heptafluoropropanesulfonate Or its nonafluorobutane sulfonate, monophenyl dimethyl sulfone trifluoromethane sulfonate, its heptafluoropropane sulphonate or its nonafluorobutane sulfonate, diphenyl mono methinores noreform trifno leo Lomomethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of (4 methylphenol) diphenyl sulfone, its heptafluoropropanesulfone Or its nonafluorobutane sulfonate, (4-methoxyphenol) diphenyl trifonoleolomethane sulphonate of snorephonium, its heptafluororeopropane sulphonate or its nonafluorobutane sulphonate, tri (4 tert —Butyl) phenolsulfurium trifanololomethanesulphonate, its heptafluororenopropane sulphonate or its nonafluorobutane sulphonate, diphenol (1 (4-methoxy) naphthyl) sulphononium Trifluoromethanesulfonate, its heptafluoromethane sulfonate, its heptafluororenopropane sulphonate or its nonafluorobutane sulfonate, di (1 naphthyl) phenol sulfone trifluoromethane sulfonate, its heptafluoro Propanesulfonate or so Nonafluorobutane sulfonate and the like. In addition, ohmic salts in which the ionic part of these ohmic salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.

 [0123] In addition, in the general formula (b-1) or (b-2), the anion part is replaced with a caron part represented by the general formula (b-3) or (b-4). A -um salt-based acid generator can also be used (the cation moiety is the same as (b-1) or (b-2)).

 [0124] In this specification, the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and generates an acid upon irradiation with radiation. It is what has. Such oxime sulfonate acid generators are widely used for chemically amplified resist compositions, and can be arbitrarily selected and used.

[0125] [Chemical 40]

— C = N ~ Q― S0 ₂ —— R ³¹

R ³² -"(B—1)

[In the formula (B-1), R ³¹ and R ³² each independently represents an organic group. ]

[0126] The organic group of R ³¹ and R ^{32 is} a group containing a carbon atom, and 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. ) Etc.).

The organic group for R ³¹ is preferably a linear, branched or cyclic alkyl group or aryl group. These alkyl groups and aryl groups may have a substituent. The place The substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Here, “having a substituent” means that at least one or all of the hydrogen atoms of the alkyl group or aryl group as the organic group of R ³¹ are substituted with a substituent.

As the alkyl group as the organic group of R ³¹ , carbon number 1 to 20 is preferable: LO power 1 to 8 carbon is more preferable 1 to 6 is more preferable A preferred carbon number of 1-4 is most preferred. Among these, as the alkyl group as the organic group for R ³¹ , a partially or completely halogenated alkyl group is particularly preferable. The partially halogenated alkyl group means an alkyl group in which at least one of the hydrogen atoms is replaced by a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogenated. An alkyl group substituted with an atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

The aryl group as the organic group of R ³¹ is preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to LO, or more preferably LO. Among these, as the aryl group as the organic group of R ³¹ , a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which at least one of the hydrogen atoms is replaced with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms. An aryl group substituted with an atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.

R ³¹ is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.

As the organic group for R ^32, a linear, branched, or cyclic alkyl group, aryl group, or cyan group is preferable. Examples of the alkyl group and aryl group for R ³² include the same alkyl groups and aryl groups as those described above for R ³¹ .

R ³² is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms. [0128] As the oxime sulfonate-based acid generator, more preferred are those represented by the following general formula (

Examples thereof include compounds represented by B-2) or (B-3).

[0129] [Chemical 41]

[In the formula (B-2), R ³³ represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group. R ³⁴ is an aryl group. R ³⁵ represents an alkyl group having no substituent or a halogenated alkyl group. ]

 [0130] [Chemical 42]

,

[In the formula (B-3), R ³⁶ represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. R ³⁸ is an alkyl group having no substituent or a halogenated alkyl group. p "is 2 or 3.]

[0131] In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent for R ³³ preferably has 1 to 8 carbon atoms and 1 to 8 carbon atoms. Is more preferred. Carbon number 1 to 6 is most preferred. Examples of the halogen atom in the halogenoalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ³³ is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.

The fluorinated alkyl group in R ³³ is preferably 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, more preferably 90% or more. preferable.

[0132] The aryl group of R ³⁴ includes an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and the like. Ring force A group in which one hydrogen atom has been removed, and part of the carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. And a roaryl group. Among these, a fluorenyl group is preferable.

The aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Examples of the halogen atom in the halogenalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group or halogenialkyl group in the substituent is more preferably 1 to 4 carbon atoms, preferably having a carbon number strength of 8 to 8. The halogenated alkyl group is preferably a fluorinated alkyl group! /.

[0133] The alkyl group or halogenated alkyl group having no substituent of R ³⁵ preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Most preferred. Examples of the halogen atom in the halogenated alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ³⁵ is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.

The fluorinated alkyl group in R ³⁵ is preferably fluorinated with 50% or more of the hydrogen atoms of the alkyl group being preferred, more preferably 70% or more, and even more preferably 90% or more. Force This is preferable because the strength of the acid generated increases. Most preferred is a fully fluorinated alkyl group in which the hydrogen atom is 100% fluorine-substituted.

In the general formula (B-3), the alkyl group or halogenated alkyl group having no substituent of R ³⁶ is an alkyl group or a substituent having no substituent of R ^33. Examples thereof are the same as the halogenalkyl group.

Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁷ include groups in which the aryl group strength of R ³⁴ is one or two hydrogen atoms removed.

Do no substituent of R ^38, the alkyl group or Harogeni spoon alkyl group, the same alkyl group or Harogeni spoon alkyl group containing no substituent group of the ⁵ like et be.

 P "is preferably 2.

[0135] Specific examples of oxime sulfonate-based acid generators include α- (p-toluenesulfo-oxyximino) monobenzyl cyanide, ex- (ρ-black benzenesulfo-oxyoximino) —Benzyl cyanide, α- (4-Nitrobenzenesulfo-ruximino) —Benzyl cyanide, 4-trotro 2 trifluoromethylbenzenesulfo-ruximino) Benzyl cyanide, α- (Benzenesulfo-ruximino) —4—Chloro Oral bendyl cyanide, α (Benzenesulfo-loxyimino) — 2, 4 Dicndiyl cyanide, α — (Benzenesulfo-Luoxyimino) — 2, 6 Dicndiyl cyanide, α (Benzenesulfo-Luximinomino) 4-methoxybenzyl Cyanide, α- (2-Chronobenzosulfo-Luximino) —4-Methoxybenzyl cyanide, α- (Benzenesulfo-Luximino) —Chen—2-Ilacetonitrile, at- (4-Dodecyl) Benzenesulfo-roximino))-benzyl cyanide, α- [(ρ Toluenesulfo-roximino) -4 Xyphenyl] acetonitrile, α [(dodecylbenzenesulfo-oxyximino) -4-methoxymethoxy] acetonitrile, at- (toxiximino) -4-cercia-do, α (methylsulfo-luoximino) — 1 —Cyclopenteracetonitrile, α- (methylsulfo-ruximino) — 1-Cyclohexylacetonitrile, OC-(methylsulfo-ruximino) 1-cyclohepturacetonitrile, α (methylsulfo-ruximino) — 1-cyclooctatur Asetonitoriru, at - (triflate Ruo Russia methyl sul e - Ruokishiimino) - 1-cyclopent - Ruasetonitoriru, α - _(triflate Ruo Russia methyl sulfo - Ruokishiimino) Shikuro hexyl § Seto nitrile, α (Echirusuruho - Ruoki Shiimino) - Ethylacetonitrile, OC-(propyl Sulfo - Ruokishiimino) - Puropirua Seto - tolyl, _alpha - (cyclohexane Kishirusuruho - Ruokishiimino) - cyclopentyl Rua Seto nitrile, a - (cyclohexane Kishirusuruho - Ruokishiimino) - hexyl § Seto nitrile cyclohexane, a - (cyclohexane Kishirusuruho - Ruokishiimino ) — 1-Cyclopentylacetonitrile, a- (Ethylsulfo-Luoxyimino) — 1-Cyclopenterulacetonitrile, α (Isopropylsulfo-Luoxyimino) — 1-Cyclopenteru-Lucetonitrile, a- (η-Butylsulfonyloximino) 1-Cyclopentenylacetonitrile, α (Ethylsulfo-Luoxyimino) — 1-Cyclohexyl-Lucetonitrile, α- (Isopropylsulfo-Luoxyimino) 1-Cyclohexeluceronitrile, ( _η -Butylsulfo-Luoxy) Mino) 1-cyclohex-l-acetonitrile, α (methylsulfo-loxyimino) -phenolacetonitrile, α- (methylsulfo-loxyimino) -ρ-methoxyph Acetylacetononitrile, α- (trifluoromethylsulfo-ruximino) -phenylaceto-tolyl, _α- (trifluoromethylsulfo-ruximino) -p-methoxyphenylacetonitrile, at- (ethylsulfonyloxy) Cimino) -p-methoxyphenylacetotril, α- (propylsulfo-hydroxyimino) p-methylphenylacetonitrile, α (methylsulfo-ruxiimino) ρ bromophenolacetonitrile, and the like.

Also disclosed in JP-A-9-208554 (paragraphs [0012] to [0014], [Chemical Formula 18] to [Chemical Formula 19]) !, Ruoxime sulfonate acid generator, WO2004Z074242A2 (65 to 85) The oxime sulfonate acid generators disclosed in Examples 1 to 40) on the page can also be suitably used.

 Moreover, the following can be illustrated as a suitable thing.

[Chemical 43]

[0137] Further, as the more preferable examples of the oxime sulfonate acid generator, the following four compounds are preferable.

[0138] [Chemical 44]

H ₃ C— C = ― OS0 ₂ —— (CH ₂ ) ₃ CH ₃

H ₃ C—— C = —— OS0 ₂ (CH ₂ ) ₃ CH ₃

[0139] Among the diazomethane acid generators, specific examples of bisalkyl or bisarylsulfol diazomethanes include bis (isopropylsulfol) diazomethane, bis (p toluenesulfol) diazomethane, bis (1 , 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane, and the like.

 Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used. Examples of poly (bissulfol) diazomethanes include 1,3 bis (phenylsulfol diazomethylsulfol) pronone, 1, 4 disclosed in JP-A-11 322707. Bis (phenylsulfodiazomethylsulfol) butane, 1,6-bis (phenolsulfodiazomethylsulfol) hexane, 1,10-bis (phenolsulfoldiol) Zomethylsulfo) decane, 1,2-bis (cyclohexylsulfo-diazomethylsulfo) ethane, 1,3 bis (cyclohexylsulfo-diazomethylsulfo) propane, 1,6 bis (cyclohexylsulfo-) (Luazomethylsulfol) hexane, 1,10-bis (cyclohexylsulfoldiazomethylsulfol) decane, and the like.

 [0140] As the component (B2), one type of acid generator may be used alone, or two or more types may be used in combination.

[0141] The content of the component (B) in the resist composition of the present invention is 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). When the content falls within the above range, pattern formation is sufficiently performed. Further, it is preferable because a uniform solution can be obtained and the storage stability becomes good. <(D) component>

 The resist composition of the present invention may further include any desired resist pattern shape, post ex posure stability of the latent image rormed by the pattern-wise exposure of the resist layer, etc. It is preferable to contain a nitrogen-containing organic compound (D) (hereinafter referred to as “component (D)”) as a component.

 Since a wide variety of components (D) have already been proposed, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines, can be used arbitrarily from known ones. Is preferred. Here, “aliphatic” in the claims and the specification is a relative concept with respect to aromatics, and is defined to mean a group, a compound, or the like that does not have aromaticity.

 The “aliphatic cyclic group” means a monocyclic group or polycyclic group having no aromaticity. As an aliphatic amine, at least one hydrogen atom of ammonia NH has 1 or more carbon atoms.

 Three

Examples include amines substituted with up to 12 alkyl groups or hydroxyalkyl groups (alkylamines or alkylalcoholamines) or cyclic amines.

 Specific examples of alkylamines and alkylalcoholamines include monoalkylamines such as n-xylamine, n-ptylamine, n-octylamine, n-norlamin, n-decylamine; jetylamine, di-n-propylamine, di-n Dialkylamines such as ptylamine, di-n-octylamine, dicyclohexylamine; —Trialkylamines such as otylamine, tri-n-noramine, tri-n-de-ramine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine Emissions, di one n- O click pentanol § Min, alkyl alcohols § Min and triethylene one n- Okutanoru Amin like. Among these, tri-n-pentylamine having 5 to 10 carbon atoms is more preferred, tri-n-pentylamine force S is still more preferred, and tri-n-pentylamine is most preferred.

Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound is a monocyclic compound (aliphatic monocyclic amine). May also be polycyclic (aliphatic polycyclic ammine).

 Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. Aliphatic polycyclic amines having 6 to 10 carbon atoms are preferred. Specifically, 1, 5 — diazabicyclo [4. 3. 0] — 5 — nonene, 1, 8 — diazabicyclo [5 4. 0] — 7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane.

 These can be used alone or in combination of two or more.

 Component (D) is usually used in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).

<Optional component>

 The resist composition of the present invention prevents sensitivity deterioration, resist pattern shape, and placement. ) Stable stability \ post exposure stability of the latent image formed by the pattern-wishes exposure of the resist layer), etc., as optional components, organic carboxylic acids, phosphorus oxoacids and their derivatives Powerful group force It is possible to contain at least one compound (E) (hereinafter referred to as component (E)) to be selected.

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

 Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferred.

 Examples of derivatives of phosphorus oxoacids include esters in which the hydrogen atom of the oxoacid is substituted with a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and a carbon number of 6 ˜15 aryl groups and the like.

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

 Examples of the phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid diol n-butenoresestenole, phenolinophosphonic acid, phosphonic acid diphenolinoestenole, and phosphonic acid dibenzyl ester.

Derivatives of phosphinic acid include phosphinic acid esters such as phenol phosphinic acid Is mentioned.

 As the component (E), one type may be used alone, or two or more types may be used in combination.

 As the component (E), an organic carboxylic acid is preferred, and salicylic acid is particularly preferred. Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).

[0144] The resist composition of the present invention further contains, if desired, miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, and dissolution. An inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added.

[0145] The resist composition of the third aspect (aspect) of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as (S) component).

 As the component (S), it is sufficient if each component to be used can be dissolved into a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be used. Two or more kinds can be appropriately selected and used.

For example, latones such as γ-butyrolatatane; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-η-amyl ketone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene Polyhydric alcohols such as glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate; the polyhydric alcohols or having the ester bond Monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., or ethers such as monophenyl ether Derivatives of polyhydric alcohols such as compounds having a combination [in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane Esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; Ether, Cresylmethinoleateoret, Dipheninoleetenole, Dipenzinoleetenore, Fuenet-Nore, Butinorefei Examples thereof include aromatic organic solvents such as ether, ethylbenzene, jetylbenzene, amylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene.

 These organic solvents can be used alone or as a mixed solvent of two or more. Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), lactic acid ethyl (EL), and y-butyrolatone are preferred.

 A mixed solvent in which PGMEA and a polar solvent are mixed is preferable. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Preferably within range! /.

 More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. When PGM E is blended as a polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: Three.

 In addition, as the component (S), a mixed solvent of at least one selected from among PGMEA and EL and γ-petit-mouth rataton is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70: 30-95: 5.

 Furthermore, as the component (S), the above-mentioned mixed solvent of PGMEA and PGME and the mixed solvent of γ-butyrolattone are also preferred.

 The amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate, etc., and can be appropriately set according to the coating film thickness. It is used so as to be in the range of 20% by mass, preferably 5 to 15% by mass.

 The resist composition of the present invention can be suitably used as a resist composition for immersion exposure in a resist pattern forming method including an immersion exposure step, and good lithography characteristics can be obtained. In addition, the resist composition of the present invention can be suitably used as a positive resist composition for forming an upper resist film in a resist pattern forming method including a step of forming a three-layer resist laminate. Good lithographic properties can be obtained.

The reason for this is that the compound represented by the general formula (bl-3) used in the present invention is used. A compound acid generator (B1) is used to effectively suppress light absorption in the exposure wavelength band (especially the ArF excimer laser wavelength band) and to dissolve various components of the resist. In other words, the solubility in organic solvents (resist solvents) is excellent. Therefore, in the resist composition of the present invention, it is considered that the light absorption is suppressed by blending the component (B1) and the transparency of the resist composition is increased.

 Further, it is considered that the component (B1) has good dispersibility in the resist film and is more uniformly distributed in the resist film than a conventional acid generator. For this reason, it is presumed that the acid generated from the component (B1) by exposure can diffuse more uniformly in the resist film than when a conventional acid generator is used.

 For the above reasons, the resist composition of the present invention can be suitably used as a resist composition for immersion exposure in a resist pattern forming method including an immersion exposure step, and good lithography characteristics can be obtained. In a resist pattern forming method including a step of forming a three-layer resist laminate, it can be suitably used as a positive resist composition for forming an upper resist film, and good lithographic properties are expected to be obtained. .

 According to the resist composition of the present invention, lithography such as line width roughness (LWR), resist pattern shape (especially resist pattern surface roughness), mask error factor (ME F), exposure margin (EL margin), etc. Resist patterns with good characteristics can be formed.

 The MEF is a parameter that indicates how faithfully a mask pattern of different size can be reproduced when the mask size (line width and space width) is changed with the same exposure amount and a fixed pitch. Yes, the closer the MEF value is to 1, the better the mask reproducibility.

 The EL margin is a parameter indicating the amount of change in the pattern size accompanying the change in exposure amount. The larger the value, the smaller the amount of change.

«Resist pattern formation method

Next, the resist pattern forming method of the fourth aspect (aspect) of the present invention will be described. The resist pattern forming method of the present invention is the resist of the third aspect (aspect) of the present invention. Forming a resist film on a substrate using a composition, exposing the resist film, and developing the resist film to form a resist pattern.

. Examples of the resist pattern forming method of the present invention include a resist pattern forming method including a liquid immersion exposure (immersion lithography) step and a resist pattern forming method including a step of forming a three-layer resist laminate. is there. These will be described next.

 <Resist pattern formation method including immersion exposure process>

 First, the resist composition according to the third aspect (aspect) of the present invention (hereinafter sometimes referred to as a resist composition for immersion exposure) on a substrate such as silicon wafer is used as a spinner or the like. After the coating, a pre-beta (post-apply beta (PAB) treatment) is performed to form a resist film.

 At this time, an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the resist composition to form a two-layer laminate.

 A top coat can also be provided on the resist film.

[0150] The topcoat is not particularly limited, and those usually used for immersion exposure can be used. For example, a protective film disclosed in WO2005 / 019937 and WO2004 / 074937; Q—NH—SO—R ⁵ (where Q is a straight chain or branched chain having 1 to 5 carbon atoms)

 2

A chain alkylene group, and R ⁵ is a fluorinated alkyl group. ), CO—O—R ⁷ (where R ⁷ is a fluorinated alkyl group), a main chain cyclic type resin containing the group represented by organic solvent (alcohol solvent such as isobutanol) And a protective film formed from a composition dissolved in the aqueous solution.

 Here, the “main-chain cyclic type of resin” means that the structural unit constituting the resin has a monocyclic or polycyclic ring structure, and preferably at least one on the ring of the ring structure, preferably Means that two or more carbon atoms have a constituent unit constituting the main chain (hereinafter referred to as “main-chain cyclic constituent unit”).

Examples of the main chain cyclic structural unit include a structural unit derived from polycycloolefin (polycyclic olefin), a dicarboxylic acid anhydride-containing structural unit, and the like. Among them, it is preferable to have a structural unit derived from polycycloolefin (polycyclic olefin, preferably norbornene, etc.) in the main chain. [0151] The topcoat provided on the resist film is preferably soluble in an alkali developer. The steps so far can be performed using a known method. The operating conditions and the like are preferably set as appropriate according to the composition and characteristics of the resist composition for immersion exposure to be used.

[0152] In the resist pattern forming method including the immersion exposure step, the resist film obtained above is selectively subjected to immersion exposure (Liquid exposure) via a desired mask pattern. Immersion Lithography). At this time, the solvent between the resist film (or top coat) and the lens at the lowest position of the exposure apparatus is larger than the refractive index of air and has a refractive index.

Fill with (immersion medium) and perform exposure (immersion exposure) in this state.

 The wavelength used for the exposure is not particularly limited, and can be performed using radiation such as an ArF excimer laser, a KrF excimer laser, or an F laser. Immersion exposure according to the present invention

2

 The resist yarn composition is effective for KrF excimer laser or ArF excimer laser, especially ArF excimer laser.

[0153] As described above, in the resist pattern forming method of the present invention, during exposure, the space between the resist film (or top coat) and the lens at the lowest position of the exposure apparatus is filled with the immersion medium, and exposure is performed in this state ( Immersion exposure) is performed.

 At this time, as the immersion medium, a solvent having a refractive index larger than that of air and having a refractive index of a resist film formed by using a resist composition for immersion exposure is preferable. The refractive index of the solvent is not particularly limited as long as it is within the above range.

 Examples of the solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and the like.

[0154] Specific examples of the fluorinated inert liquid include C HC1 F

 3 2 5, C F OCH

 4 9 3, C F OC H

 4 9 2 5, C

Examples include liquids mainly composed of fluorine-based compounds such as HF, and boiling point of 70 to 180 ° C.

5 3 7

 The thing of 80-160 degreeC is more preferable. If the fluorinated inert liquid has a boiling point within the above range, it is preferable that the medium used for immersion can be removed by a simple method after the exposure is completed.

As the fluorinated inert liquid, a perfluorinated alkyl compound in which all the hydrogen atoms of the alkyl group are replaced with fluorine atoms is particularly preferred! /. Specific examples of perfluorinated alkyl compounds include perfluoroalkyl ether compounds and perfluoroalkyl compounds. And amine compounds.

 More specifically, examples of the perfluoroalkyl ether compound include perfluoro (2-butyl monotetrahydrofuran) (boiling point: 102 ° C.). Examples of the perfluoroalkylamine compound include perfluoroalkylamine compounds. Fluorotributylamine (boiling point 174 ° C).

 [0155] Since the resist composition of the present invention is particularly sensitive to water and has excellent sensitivity and resist pattern profile shape, water is preferably used as a solvent having a refractive index greater than the refractive index of air. It is done. Water is also preferable from the viewpoints of cost, safety, environmental problems, and versatility.

 [0156] Next, after the immersion exposure step is completed, post-exposure heating (post exposure beta (PEB) treatment) is performed, followed by development using an alkaline developer composed of an alkaline aqueous solution. And preferably, water rinsing is performed using pure water. In the water rinse, for example, water is dropped or sprayed on the surface of the substrate while rotating the substrate to wash away the developing solution on the substrate and the resist composition for immersion exposure dissolved by the image solution. Then, drying is performed to obtain a resist pattern in which a resist film (a coating film of a resist composition for immersion exposure) is patterned in a shape corresponding to the mask pattern.

 [0157] <Method for forming resist pattern including a step of forming a three-layer resist laminate>

 In the resist pattern forming method including the step of forming a three-layer resist laminate, a lower organic film that can be dry-etched is formed on a substrate, and a material containing an S source element is applied to the lower organic film and heated. Forming an intermediate layer on the intermediate layer, forming an upper resist film on the intermediate layer using the resist composition according to the third aspect of the present invention, and forming a three-layer resist laminate; and Exposing the resist film, developing the upper resist film, and forming a resist pattern.

 Example

 [0158] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.

[0159] (Example 1) (Synthesis of Compound (bl-31))

[Chemical 45]

[0160] 12.5 g of Di-t-Butylphenyliodonium Perfluorobutanesulfonate, 3.20 g of benzothiophene, 0.17 g of copper (II) benzoate, 22.5 g It was dissolved in black benzene and reacted at 110 ° C for 2 hours. After completion of the reaction, the mixture was concentrated to dryness and dissolved in 30 g of dichloromethane. The dichloromethane solution was washed with water, and 130 g of hexane was added as a poor solvent to the solution to obtain crystals. The crystals were dried under reduced pressure at room temperature to obtain 6.5 g of the target compound.

This compound was analyzed by ¹ H-NMR and ¹⁹ F-NMR. 'H-NMRCCDCl, 600MHz, internal standard: tetramethylsilane): δ (ppm) = 8.06 (dd,

 Three

ΙΗ, Ηί), 8.04 (d, lH, Hd), 8.01 (d, lH, Hg), 7.79 (t, lH, Hl), 7.69 (dd, lH, Hh), 7.63 (t, l H, He) , 7.62 (dd, 2H, Hc), 7.53 (dd, 2H, Hb), 1.27 (s, 9H, Ha) ₀

1 ⁹ F—NMR (CDC1, 376 MHz): δ (ppm) = 80.9, 114.5, 121.4, 125.8.

 Three

 From the above results, it was confirmed that the compound had the structure shown below.

[0161] [Chem 46]

6.92gのジー t—ブチルフエ-ルョードニゥムパーフルォロブタンスルフォネート（Di- t-Butylphenyliodonium Perfluorobutanesulfonateリ、 1.94gの 2—ァセテノレベンゾチォ フェン、 0.08gの安息香酸銅 (II)を 10.38gのクロ口ベンゼンに溶解し、 110°Cで 1時間反 応させた。反応終了後、 51.90gのジブチルエーテルを添加して粗結晶を取り出した。 これを 13gのジクロロメタンに溶解し、このジクロロメタン溶液を水洗いした後、この溶 液中へ 90gのジブチルエーテルを貧溶媒として添加し、結晶を得た。この結晶を室温 にて減圧乾燥することによって目的化合物 0.9gを得た。 この化合物につ 、て、 H— NMR及び F— NMRによる分析を行った。

6.92 g of di-t-butylphenol perfluorobutanesulfonate, 1.94 g of 2-acethenolebenzothiophene, 0.08 g of copper (II) benzoate Was dissolved in 10.38 g of black benzene and reacted for 1 hour at 110 ° C. After the reaction was completed, 51.90 g of dibutyl ether was added to take out crude crystals, which were dissolved in 13 g of dichloromethane, The dichloromethane solution was washed with water, and 90 g of dibutyl ether was added as a poor solvent to the solution to obtain crystals, which were dried under reduced pressure at room temperature to obtain 0.9 g of the target compound. This compound was analyzed by H-NMR and F-NMR.

 'H-NMRCCDCl, 600MHz, internal standard: tetramethylsilane): δ (ppm) = 9.13 (s, lH

 Three

 , Hh), 8.37 (d'lH'Hd), 8.09 (d, lH, Hg), 7.86 (t, lH, Hl), 7.78 (t, lH, He), 7.56 (d, 2H, He), 7.52 (d, 2H, Hb), 2.69 (s, 3H, Hi), 1.29 (s, 9H, Ha).

1 ⁹ F—NMR (CDC1, 376 MHz): δ (ppm) = 80.9, 114.5, 121.5, 125.9.

 Three

 From the above results, it was confirmed that the compound had the structure shown below.

 [Chemical 48]

[0164] (Example 3) (Synthesis of compound (bl-40))

 [Chemical 49]

[0165] 4.15 g of di-t-butylphenol perfluorobutane sulfonate (Di- t-Butylphenyliodonium Perfluorobutanesulfonate), 0.89 g of 2-methylolbenzobenzothiophene, and 0.05 g of copper (II) benzoate were dissolved in 6.5 g of black benzene and reacted at 100 ° C for 1 hour and 30 minutes. After completion of the reaction, dibutyl ether (45.5 g) was added to take out crude crystals. This was dissolved in llg of dichloromethane, and this dichloromethane solution was washed with water, and 35 g of dibutyl ether and 15.0 g of hexane were added as poor solvents to this solution to obtain crystals. The crystals were dried under reduced pressure at room temperature to obtain 2.20 g of the target compound.

 The compound was analyzed by ¾ NMR.

¹ H—NMR (CDC1, 400 MHz, internal standard: tetramethylsilane): δ (ppm) = 8.05 (d,

 Three

 IH, Hi), 7.87 (d, IH, Hi), 7.74 (t, IH, Hh), 7.65 (s, IH, He), 7.60 (m, 4H, Hd + He), 7.54 (t, IH, Hg ), 2.41 (s, IH, Hb), 1.31 (s, 9H, Ha).

1 ⁹ F-NMR (CDC1, 376 MHz): δ (ppm) = 80.9, 114.5, 121.5, 125.9.

 Three

 From the above results, it was confirmed that the compound had the structure shown below.

 [0166] [Chemical 50]

[0167] Solubility Evaluation>

Solubility of the above compounds (bl-31), (bl-34), (bl-40) and di (1 naphthyl) phenol rufomunonafluorobutanesulfonate ((B) -2) Was evaluated as follows. The propylene glycol monomethyl ether acetate (PGMEA) solution, propylene glycol monomethyl ether (PGME) solution, and ethyl lactate (EL) solution of each compound were prepared by changing the concentration. After the adjustment, each solution was stirred to measure the concentration at which each acid generator was completely dissolved.

 The results are shown in Table 1. The solubility of the above compounds (bl-34) and (bl-40) according to the first aspect of the present invention in general resist solvents PGMEA, PGME, and EL is di (1 naphthyl). ) It was confirmed that it was superior to the fuel sulfo-munonafluorobutane sulfonate ((B) -2).

[0168] [Table 1]

[0169] (Example 4) (Synthesis of compound (bl-37))

 [Chemical 51]

2.85 g of Di-Phenyliodonium Perfluorobutanesulfonate, 0.80 g of 2-methylbenzo [b] thiophene, 0.04 g of copper (II) benzoate, 4.3 g of chlorine It was dissolved in benzene and reacted at 110 ° C for 1 hour. After completion of the reaction, hexane was added as a poor solvent to obtain crystals. The crystals were dried under reduced pressure at room temperature to obtain 0.5 g of the target compound. This compound was analyzed by H-NMR and F-NMR.

 'H-NMRCCDCl, 400MHz, internal standard: tetramethylsilane): δ (ppm) = 8.25 (d, H

 Three

d), 7.96 (d, Hg), 7.87-7.75 (m, He, Hf, Hh), 7.69-7.63 (m, Ha, Hb, Hc), 2.40 (s, Hi) _o ¹⁹ F-NMR (CDC1 376 MHz): δ (ppm) = 75.9, 110.1, 116.8, 121.1.

 Three

 From the above results, it was confirmed that the compound had the structure shown below.

 [Chemical 52]

Ha

(実施例 5〜7、比較例 1) <榭脂成分 (A) >

(Examples 5-7, Comparative Example 1) <Oxidized component (A)>

 Polymer (A) -1 of component (A) used in Examples 5 to 7 and Comparative Example 1 is shown below. Polymer (A) -1 was synthesized by the following procedure. That is, PGMEA was placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer under a nitrogen atmosphere, and the temperature of the hot water bath was raised to 80 ° C while stirring.

 Next, 2, 2, 1-azobisisobutyryl-tolyl (AIBN) as a polymerization initiator, PGMEA, and a monomer (2-methyl-2-adamantyl methacrylate) / α that derives each constituent unit of polymer (A) -1 —Methacryloyloxy γ-butyrolataton / 3 hydroxy 1-adamantyl acrylate = 3-5 5 (molar ratio)) was added dropwise to the flask over 6 hours at a constant rate using a dropping device. Thereafter, it was kept at 80 ° C for 1 hour. Thereafter, the reaction solution was returned to room temperature.

The resulting reaction solution was then added dropwise to about 30 times the amount of methanol with stirring to give a colorless precipitate. The resulting precipitate was filtered off and the precipitate was used as a single unit for the polymerization. The body was washed in about 30 times the amount of methanol. The precipitate was filtered off and dried under reduced pressure at 50 ° C. for about 40 hours to obtain polymer (A) -1.

 The mass average molecular weight (Mw) and dispersity (MwZMn) of the following polymer (A) -1 are also shown. The mass average molecular weight (Mw) and dispersity (MwZMn) were determined on the basis of polystyrene conversion by gel permeation chromatography (GPC).

 The composition ratio was calculated by carbon NMR. In the chemical formula, the number attached to the lower right of the structural unit indicates the ratio (mol%) of each structural unit in the polymer.

[0173] [Chemical 53]

■■(A) - 1

■■ (A)-1

(Mw: 10000 MwZMn: 2.0)

[0174] Preparation of a positive resist composition solution>

 Each component shown in Table 2 was mixed and dissolved to prepare a positive resist composition solution.

[0175] [Table 2]

 [0176] Each abbreviation in Table 2 has the following meaning. The numerical value in [] is the blending amount (part by mass).

 (B) —1: An acid generator (compound of Example 1) represented by the following chemical formula (bl-31).

(B) -3: An acid generator (compound of Example 3) represented by the following chemical formula (b 1 -40). (B) -4: An acid generator (compound of Example 2) represented by the following chemical formula (b1 34).

[0177] [Chemical 54]

[0178] (B) —2: Di (1-naphthyl) phenolsulfo-munonafluorobutanesulfonate.

 (D) —1: Tri-n-pentylamine.

 (E) — 1: Salicylic acid.

 (S) —l: γ—petit rataton.

 (S) — 2: Mixed solvent of PGMEA / PGME = 6/4 (mass ratio).

 [0179] <Evaluation of lithography properties>

 A resist pattern was formed using the obtained positive resist composition solution, and the following lithographic characteristics were evaluated.

 [0180] [Resist pattern formation]

 An organic antireflective coating composition “ARC29A” (trade name, manufactured by Brew Science Co., Ltd.) was applied onto an 8-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds. Then, an organic antireflection film having a thickness of 77 nm was formed. Then, the positive resist composition solution obtained above is applied onto the antireflection film using a spinner, and the plate is exposed on a hot plate at 110 ° C. for 60 seconds. A PAB) treatment was performed and dried to form a resist film with a thickness of 150 nm.

[0181] Next, an ArF excimer laser (193 nm) is selectively passed through the mask pattern using an ArF exposure system NSR-S302 (Nikon; NA (numerical aperture) = 0.60, 2/3 annular illumination). Irradiated. Then, perform post-exposure heating (PEB) treatment at 110 ° C for 60 seconds, Further 2.38 mass _^0/0 tetramethylammonium at 23 ° C - developed with Umuhidorokishido (TMAH) for 30 seconds in an aqueous solution, then 30 seconds, rinsed with pure water, by performing shaken dry A line-and-space (1: 1) resist pattern (LZS pattern) was formed, and an LZS pattern with a line width of 120 nm and a pitch of 240 nm could be formed.

 [0182] It was confirmed that the resist compositions of Examples 5 to 7 according to the present invention can form a fine resist pattern.

 [0183] (Evaluation on hard mask)

 The resist compositions of Examples 5 to 6 and Comparative Example 1 were applied to a resist pattern forming method including the step of forming a three-layer resist laminate and evaluated.

 [0184] [Resist pattern formation]

 A resist laminate was manufactured by the following procedure, and a resist pattern was formed using the resist laminate.

 First, a base material solution containing novolak resin is applied onto an 8-inch silicon wafer using a spinner, and soft beta is applied at 230 ° C for 90 seconds to form a lower organic film with a thickness of 270 nm. Formed.

Next, a composition for forming a hard mask (feryl silsesquioxane Z hydrogen silsesquioxane / methyl silsesquioxane / methyl silsesquioxane propionate copolymer) on the lower layer is mixed with PGMEA and EL (mass the ratio 6Z4) by dissolving the ones (solid content concentration 2.5 wt _^0/0) was applied using a spinner, soft 90 seconds at 90 ° C and beta treatment, followed by 90 seconds at 250 ° C beta By processing, a hard mask layer (intermediate layer) with a thickness of 30 nm was formed.

 Next, the positive resist composition solutions of Examples 5 to 6 and Comparative Example 1 were applied to the intermediate layer using a spinner, and were applied on a hot plate at 110 ° C. for 60 seconds. A positive resist layer (upper layer resist film) with a film thickness of 150 nm is formed by performing a beta (PAB) treatment and drying to obtain a resist layered body in which a three-layer resist layer is laminated on the substrate. It was.

[0185] Next, ArF excimer laser (193nm) is selectively passed through the mask pattern by ArF exposure system NSR-S302 (Nikon; NA (numerical aperture) = 0.60, 2Z3 annular illumination) Irradiated. Then, at 110 ° C, subjected to post exposure bake (PEB) treatment was for 60 seconds, further 2.38 mass _^0/0 tetramethylammonium at 23 ° C - Umuhidorokishido (TMAH) for 30 seconds in an aqueous solution The film was rinsed with pure water for 30 seconds and then shaken and dried to form a line-and-space (1: 1) resist pattern (LZS pattern) with a line width of 120 nm and a pitch of 240 nm. .

As a result, the resist pattern obtained by applying the resist composition of Examples 5 and 6 according to the present invention to a resist pattern forming method including the step of forming a three-layer resist laminate was obtained by It was confirmed that the xantine hard mask forming yarn and the mating with the intermediate layer having a good strength were good and the footing of the resist pattern was suppressed. Industrial applicability

[0187] According to the present invention, a novel compound suitable as an acid generator for a resist composition, an acid generator comprising the compound, a resist composition containing the acid generator, and a resist pattern using the resist composition A forming method is provided. Therefore, the present invention is extremely useful in industry.

Claims

The scope of the claims  A compound represented by the following general formula (bl-3).

[Wherein, R ⁴¹ , R ⁴² and R ⁴³ each independently represents an alkyl group, a acetyl group, an alkoxy group, a carboxy group, a hydroxyl group, or a hydroxyalkyl group; n is an integer of 0 to 3; Is an integer from 0 to 3, and n is an integer from 0 to 2, provided that n, n and n are simultaneously 2 3 1 2 3 is never 0; x_ is key-on. ] 2. The compound according to claim 1, wherein the X— is a halogenated alkyl sulfonate ion. [3] The acid generator (Bl) having a compound strength according to claim 1 or 2.  [4] A resist composition comprising a base component (A) whose alkali solubility is changed by the action of an acid and an acid generator component (B) that generates an acid upon exposure,  The acid generator component (B) is a resist composition containing an acid generator (B1) comprising a compound represented by the following general formula (bl-3).  [Chemical 2]

[Wherein, R ⁴¹ , R ⁴² and R ⁴³ each independently represents an alkyl group, a acetyl group, an alkoxy group, a carboxy group, a hydroxyl group or a hydroxyalkyl group; n is an integer of 0 to 3, and n is 0 Is an integer of ~ 3, and n is each independently an integer of 0 ~ 2, where n, n 2 3 1 2 and n are not 0 at the same time; X_ is key-on. ]  Three  5. The resist composition according to claim 4, wherein the X— is a halogenated alkyl sulfonate ion.  [6] The resist composition according to claim 4, wherein the content of the acid generator (B1) is in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the base component (A). 7. The resist composition according to claim 4, wherein the base material component (A) is a base material component whose alkali solubility is increased by the action of an acid. 8. The resist composition according to claim 7, wherein the base material component (A) is a resin component (A1) whose alkali solubility is increased by the action of an acid. [9] The resist composition according to claim 8, wherein the resin component (A1) has a structural unit (al) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group. [10] The resist composition according to claim 9, wherein the rosin component (A1) further has a structural unit (a2) that also induces an acrylate ester-containing force containing a latathone-containing cyclic group. [11] The resist composition according to claim 9, wherein the resin component (A1) further comprises a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group. [12] The resist composition according to claim 10, wherein the resin component (A1) further comprises a structural unit (a3) from which an acrylate esterka containing a polar group-containing aliphatic hydrocarbon group is also derived. 13. The resist composition according to claim 4, comprising a nitrogen-containing organic compound (D). [14] A step of forming a resist film on a substrate using the resist composition according to any one of claims 4 to 13, a step of exposing the resist film, and developing and developing the resist film. Forming a pattern. A resist pattern forming method.