# Patent

## Title
Resist composition and method for producing resist pattern

## Abstract

A resist composition having; a resin having a structural unit represented by the formula (I), a resin being insoluble or poorly soluble in alkali aqueous solution, but becoming soluble in an alkali aqueous solution by the action of an acid and not including the structural unit represented by the formula (I), an acid generator, and a salt having an anion represented by the formula (IA).




    
    
        wherein R1, A1, A13, X12, A14, R1A and R2A are defined in the specification.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to Japanese Application No. 2011-157531 filed on Jul. 19, 2011. The entire disclosures of Japanese Application No. 2011-157531 is incorporated hereinto by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a resist composition and a method for producing a resist pattern.
2. Background Information
A resist composition which contains a resin including a polymer having a structural unit (u-A) and a structural unit (u-B), a polymer having a structural unit (u-C), a structural unit (u-D) and a structural unit (u-B), and an acid generator, is described in Patent document of JP-2010-197413A.




However, with the conventional resist composition, the focus margin (DOF) at producing a resist pattern may be not always satisfied with, and number of the defects of the resist pattern to be produced from the resist composition may quite increase.
SUMMARY OF THE INVENTION
The present invention provides following inventions of <1> to <7>.
<1> A resist composition comprising
a resin having a structural unit represented by the formula (I),
a resin being insoluble or poorly soluble in alkali aqueous solution, but becoming soluble in an alkali aqueous solution by the action of an acid and not including the structural unit represented by the formula (I),
an acid generator, and
a salt having an anion represented by the formula (IA).




wherein R1 represents a hydrogen atom or a methyl group;
A1 represents a C1 to C6 alkanediyl group;
A13 represents a C1 to C18 divalent aliphatic hydrocarbon group that optionally has one or more halogen atoms;
X12 represents *-CO—O— or *-O—CO—;
* represents a bond to A13;
A14 represents a C1 to C17 aliphatic hydrocarbon group that optionally has one or more halogen atoms;




wherein R1A and R2A independently represent a hydrogen atom, a C1 to C12 aliphatic hydrocarbon group, a C3 to C20 alicyclic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group or a C7 to C21 aralkyl group, one or more hydrogen atoms contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group and the aralkyl group may be replaced by a hydroxy group, a cyano group, a fluorine atom, trifluoromethyl group or a nitro group, one or more —CH2— contained in the aliphatic hydrocarbon group may be replaced by —O— or —CO—; or R1A and R2A may be bonded to form at least one nitrogen atom-containing C4 to C20 ring.
<2> The resist composition according to <1>, wherein A1 in the formula (I) is an ethylene group.
<3> The resist composition according to <1> or <2>, wherein A13 in the formula (I) is a C1 to C6 perfluoro alkanediyl group.
<4> The resist composition according to any one of <1> to <3>, wherein X12 in the formula (I) is *-CO—O—, * represents a bond to A13.
<5> The resist composition according to any one of <1> to <4>, wherein A14 in the formula (I) is a cyclopropylmethyl, cyclopentyl, cyclohexyl, norbornyl or adamantyl group.
<6> The resist composition according to any one of <1> to <5>, wherein the a salt having an anion represented by the formula (IA) contains a cation represented by the formula (IB);




wherein R3, R4 and R5 in each occurrence independently represent a hydroxy group, a halogen atom, a C1 to C12 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a C1 to C12 alkoxy group, or two of R3, R4 and R5 may be bonded together to form a sulfur-containing ring, one or more hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group and the alkoxy group may be replaced by a halogen atom, a hydroxy group, a C1 to C12 alkoxy group, a C6 to C18 aromatic hydrocarbon group, a C2 to C4 acyl group or a glycidyloxy group,
mx, my and mz independently represent an integer of 0 to 5.
<7> The resist composition according to any one of <1> to <5>, which further comprises a solvent.
<8> A method for producing a resist pattern comprising steps of;
(1) applying the resist composition of any one of <1> to <7> onto a substrate;
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) heating the exposed composition layer, and
(5) developing the heated composition layer.


DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the chemical structure formulas of the present specification, unless otherwise specified, the suitable choice of carbon number made for the exemplified substituent groups are applicable in all of the chemical structure formulas that have those same substituent groups. Unless otherwise specified, these can include any of straight-chain, branched chain, cyclic structure and a combination thereof. When there is a stereoisomeric form, all stereoisomeric forms included.
“(Meth)acrylic monomer” means at least one monomer having a structure of “CH2=CH—CO—” or “CH2=C(CH3)—CO—”, as well as “(meth)acrylate” and “(meth)acrylic acid” mean “at least one acrylate or methacrylate” and “at least one acrylic acid or methacrylic acid,” respectively.
<Resist Composition>
The resist composition of the present invention contains;
a resin (hereinafter is sometimes referred to as “resin (A)”),
an acid generator (hereinafter is sometimes referred to as “acid generator (B)”) and
a salt having an anion represented by the formula (IA) (hereinafter the anion represented by the formula (IA) is sometimes referred to as “anion (IA)”).
Further, the present resist composition preferably contains a solvent (hereinafter is sometimes referred to as “solvent (E)”), as needed.
<Resin (A)>
The resin (A) includes;
a resin having a structural unit represented by the formula (I) (hereinafter is sometimes referred to as “resin (A1)”), and
a resin being insoluble or poorly soluble in alkali aqueous solution, but becoming soluble in an alkali aqueous solution by the action of an acid and not including the structural unit represented by the formula (I) (hereinafter is sometimes referred to as “resin (A2)”).
Also, the resin (A) may contain a structural unit other than the resin (A1) and resin (A2).
<Resin (A1)>
The resin (A1) has a structural unit represented by the formula (I) (hereinafter is sometimes referred to as “structural unit (I)”).




wherein R1 represents a hydrogen atom or a methyl group;
A1 represents a C1 to C6 alkanediyl group;
A13 represents a C1 to C18 divalent aliphatic hydrocarbon group that optionally has one or more halogen atoms;
X12 represents *-CO—O— or *-O—CO—;
* represents a bond to A13;
A14 represents a C1 to C17 aliphatic hydrocarbon group that optionally has one or more halogen atoms.
In the formula (I), examples of the alkanediyl group of A1 include a chain alkanediyl group such as methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl; a branched alkanediyl group such as 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylbutane-1,4-diyl, 2-methylbutane-1,4-diyl groups.
Examples of the halogen atom of A13 include a fluorine, chlorine, bromine and iodine atoms. The fluorine atom is preferable.
The divalent aliphatic hydrocarbon group of A13 may be any of a chain and cyclic aliphatic hydrocarbon groups, and a combination of two or more such groups. The aliphatic hydrocarbon group may include a carbon-carbon double bond, is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkanediyl group and a divalent alicyclic hydrocarbon group.
The aliphatic hydrocarbon group that optionally has one or more halogen atoms of A13 is preferably a saturated aliphatic hydrocarbon group that optionally has one or more fluorine atoms.
Examples of the chain divalent aliphatic hydrocarbon group that optionally has one or more halogen (preferably fluorine) atoms include methylene, difluoromethylene, ethylene, perfluoroethylene, propanediyl, perfluoropropanediyl, butanediyl, perfluorobutanediyl, pentanediyl, perfluoropentanediyl, dichloromethylene and dibromomethylene groups.
The cyclic divalent aliphatic hydrocarbon group that optionally has one or more halogen (preferably fluorine) atoms may be either monocyclic or polycyclic hydrocarbon group. Examples thereof include a monocyclic aliphatic hydrocarbon group such as cyclohexanediyl, perfluorocyclohexanediyl and perchlorocyclohexanediyl; a polycyclic aliphatic hydrocarbon group such as adamantanediyl, norbornanediyl and perfluoro adamantanediyl groups.
The aliphatic hydrocarbon group of A14 may be any of a chain and cyclic aliphatic hydrocarbon groups, and a combination of two or more such groups. The aliphatic hydrocarbon group may include a carbon-carbon double bond, is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkyl group and an alicyclic hydrocarbon group.
The aliphatic hydrocarbon group that optionally has one or more halogen atoms of A14 is preferably a saturated aliphatic hydrocarbon group that optionally has one or more fluorine atoms.
Examples of the chain aliphatic hydrocarbon group that optionally has one or more halogen (preferably fluorine) atoms include difluoromethyl, trifluoromethyl, methyl, 1,1,1-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoroethyl, perfluoropropyl, 1,1,1,2,2-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 1,1,1,2,2,3,3,4,4-nonafluoropentyl, pentyl, hexyl, perfluorohexyl, heptyl, perfluoroheptyl, octyl, perfluorooctyl, trichloromethyl, and tribromomethyl groups.
The cyclic aliphatic hydrocarbon group that optionally has one or more halogen (preferably fluorine) atoms may be either monocyclic or polycyclic hydrocarbon group. Examples thereof include the monocyclic aliphatic hydrocarbon group such as cyclopentyl, cyclohexyl, perfluorocyclohexyl and perchlorocyclohexyl; polycyclic aliphatic hydrocarbon group such as adamantyl, norbornyl and perfluoro adamantyl groups.
Examples of the combination of the chain and cyclic aliphatic hydrocarbon groups include cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, adamantylmethyl and perfluoro adamantylmethyl groups.
A1 in the formula (I) is preferably a C2 to C4 alkanediyl group, and more preferably an ethylene group.
The aliphatic hydrocarbon group of A13 is preferably a C1 to C6 aliphatic hydrocarbon group, and more preferably a C2 to C3 aliphatic hydrocarbon group.
The aliphatic hydrocarbon group of A14 is preferably a C3 to C12 aliphatic hydrocarbon group, and more preferably a C3 to C10 aliphatic hydrocarbon group. Among these, A′′ is preferably a C3 to C12 aliphatic hydrocarbon group which include an alicyclic hydrocarbon group, and still more preferably cyclopropylmethyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl groups.
Specific examples of the structural units (I) include as follows.
















Also, examples of the structural units (I) include structural units in which a methyl group corresponding to R1 in the structural units represented by the above is replaced by a hydrogen atom.
The structural unit (I) is derived from a compound represented by the formula (I′), hereinafter is sometimes referred to as “compound (I′)”.




wherein R1, A1, A13, X12 and A14 have the same definition of the above.
The compound (I′) can be produced by a method below.




wherein R1, A1, A13, X12 and A14 have the same definition of the above.
The compound (I′) can be obtained by reacting a compound represented by the formula (Is-1) with a carboxylic acid represented by the formula (Is-2). This reaction is usually performed in presence of a solvent. Preferred examples of the solvent include tetrahydrofuran and toluene. This reaction may be coexistent with a known esterification catalyst, for example, an acid catalyst, carbodiimide catalyst.
As the compound represented by the formula (Is-1), a marketed product or a compound which is produced by a known method may be used. The known method includes a method condensing (meth)acrylic acid or derivatives thereof, for example, (meth)acrylic chloride, with a suitable diol (HO-A1-OH). The hydroxyethyl methacrylate can be used as a marketed product.
The carboxylic acid represented by the formula (Is-2) can be produced by a known method. Examples of the carboxylic acid represented by the formula (Is-2) include compounds below.







The resin (A1) may include a structural unit other than the structural unit (I).
Examples of the structural unit other than the structural unit (I) include a structural unit derived from a monomer having an acid labile group described below (hereinafter is sometimes referred to as “acid labile monomer (a1)”), a structural unit derived from a monomer not having an acid labile group described below (hereinafter is sometimes referred to as “acid stable monomer”), a structural unit represented by the formula (III-1) (hereinafter is sometimes referred to as “structural unit (III-1)”) described below, a structural unit represented by the formula (III-2) (hereinafter is sometimes referred to as “structural unit (III-2)”) described below, a structural unit derived from a known monomer in this field. Among these, the structural unit (III-1) and the structural unit (III-2) are preferable.




wherein R11 represents a hydrogen atom or a methyl group;
A11 represents a C1 to C6 alkanediyl group;
R12 represents a C1 to C10 hydrocarbon group having a fluorine atom.




wherein R21 represents a hydrogen atom or a methyl group;
ring W2 represents a C6 to C10 hydrocarbon ring;
A22 represents —O—, *-CO—O— or *-O—CO—, * represents a bond to ring W2;
R22 represents a C1 to C6 alkyl group having a fluorine atom.
In the formula (III-1), examples of the alkanediyl group of A11 include a chain alkanediyl group such as methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl; a branched alkanediyl group such as 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylbutane-1,4-diyl and 2-methylbutane-1,4-diyl groups.
The hydrocarbon group having a fluorine atom of R12 may be an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, iso-butyl, n-pentyl, iso-pentyl, tert-pentyl, neo-pentyl and hexyl groups.
Examples of the alkyl group having a fluorine atom include a fluorinated alkyl group such as, groups described below, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,2,2,3,3-hexafluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, perfluorobutyl, 1,1-bis(trifluoro)methyl-2,2,2-trifluoroethyl, 2-(perfluoropropyl)ethyl, 1,1,2,2,3,3,4,4-octafluoropentyl, perfluoropentyl, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl, 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl, perfluoropentyl, 2-(perfluorobutyl)ethyl, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl, perfluoropentylmethyl and perfluorohexyl groups.




The alicyclic hydrocarbon group is preferably a saturated ring of an aliphatic hydrocarbon group in which a hydrogen atom is removed. Examples of the saturated ring of an aliphatic hydrocarbon group include groups below.




Examples of the alicyclic hydrocarbon group having a fluorine atom include a fluorinated cycloalkyl group such as perfluorocyclohexyl and perfluoroadamantyl groups.
The hydrocarbon ring of ring W2 may be an alicyclic hydrocarbon ring, and preferably a saturated alicyclic hydrocarbon ring. Examples of the saturated alicyclic hydrocarbon ring include adamantane and cyclohexane rings, and adamantane ring is preferable.
Examples of the structural unit (III-1) include structural units below.







Also, examples of the structural units (III-1) include structural units in which a methyl group corresponding to R11 in the structural units represented by the above is replaced by a hydrogen atom.
Examples of the structural unit (III-2) include structural units below.







Also, examples of the structural units (III-2) include structural units in which a methyl group corresponding to R21 in the structural units represented by the above is replaced by a hydrogen atom.
The proportion of the structural unit (I) in the resin (A1) is generally 5 to 100 mol %, preferably 10 to 100 mol %, with respect to the total structural units (100 mol %) constituting the resin (A1).
When the resin (A1) contains the structural unit (III-1) and/or the structural unit (III-2), the total proportion thereof in the resin (A1) is generally 1 to 95 mol %, preferably 2 to 80 mol %, more preferably 5 to 70 mol %, still more preferably 5 to 50 mol % and in particular preferably 5 to 30 mol %, with respect to the total structural units (100 mol %) constituting the resin (A1).
The weight ratio of the structural unit (III-1):the structural unit (III-2) is preferably, for example, 0:100 to 100:0, more preferably 3:97 to 97:3, still more preferably 50:50 to 95:5.
For achieving the proportion of the structural unit (I), the structural unit (III-1) and/or the structural unit (III-2) in the resin (A1) within the above range, the amount of the compound (I′), a monomer giving the structural unit (III-1) and/or a monomer giving the structural unit (III-2) to be used can be adjusted with respect to the total amount of the monomer to be used when the resin (A1) is produced (the same shall apply hereinafter for corresponding adjustment of the proportion).
The resin (A1) can be produced by a known polymerization method, for example, radical polymerization method, using at least one of the compound (I′), at least one monomer giving the structural unit (III-1) and/or at least one of the monomer giving the structural unit (III-2), as well as optionally at least one of the acid labile monomer (a1), at least one of the acid stable monomer and/or at least one of a known compound, described below.
The weight average molecular weight of the resin (A1) is preferably 5,000 or more (more preferably 7,000 or more, and still more preferably 10,000 or more), and 80,000 or less (more preferably 50,000 or less, and still more preferably 30,000 or less).
The weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as the standard product. The detailed condition of this analysis is described in Examples.
<Resin (A2)>
The resin (A2) is a resin having properties which is insoluble or poorly soluble in alkali aqueous solution, but becomes soluble in an alkali aqueous solution by the action of an acid. Here “a resin becoming soluble in an alkali aqueous solution by the action of an acid” means a resin that has an acid labile group and is insoluble or poorly soluble in aqueous alkali solution before contact with the acid, and becomes soluble in aqueous alkali solution after contact with an acid.
Therefore, the resin (A2) is preferably a resin having at least one structural unit derived from an acid labile monomer (a1).
Also, the resin (A2) may include a structural unit other than the structural unit having the acid labile group as long as the resin (A2) has above properties and does not have the structural unit (I).
Examples of the structural unit other than the structural unit having the acid labile group include a structural unit derived from the acid stable monomer, the structural unit derived from a known monomer in this field, structural unit (III-1) and/or the structural unit (III-2) described above.
<Acid Labile Monomer (a1)>
The “acid labile group” means a group which has an elimination group and in which the elimination group is detached by contacting with an acid resulting in forming a hydrophilic group such as a hydroxy or carboxy group. Examples of the acid labile group include a group represented by the formula (I) and a group represented by the formula (2). Hereinafter a group represented by the formula (1) sometimes refers to as an “acid labile group (1)”, and a group represented by the formula (2) sometimes refers to as an “acid labile group (2)”.




wherein Ra1 to Ra3 independently represent a C1 to C8 alkyl group or a C3 to C20 alicyclic hydrocarbon group, or Ra1 and Ra2 may be bonded together to form a C2 to C20 divalent hydrocarbon group, represents a bond. In particular, the bond here represents a bonding site (the similar shall apply hereinafter for “bond”).




wherein Ra1′ and Ra2′ independently represent a hydrogen atom or a C1 to C12 hydrocarbon group, Ra3′ represents a C1 to C20 hydrocarbon group, or Ra2′ and Ra3′ may be bonded together to form a divalent C2 to C20 hydrocarbon group, and one or more —CH2-contained in the hydrocarbon group or the divalent hydrocarbon group may be replaced by —O— or —S—, * represents a bond.
Examples of the alkyl group of Ra1 to Ra3 include methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
Examples of the alicyclic hydrocarbon group of Ra1 to Ra3 include monocyclic hydrocarbon groups such as a cycloalkyl group, i.e., cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl, norbornyl (i.e., bicyclo[2.2.1]heptyl), and methyl norbornyl groups as well as groups below.




The hydrogen atom contained in the alicyclic hydrocarbon group of Ra1 to Ra3 may be replaced an alkyl group. In this case, the carbon number of the alicyclic hydrocarbon group is comparable to the total carbon number of the alkyl group and the alicyclic hydrocarbon group.
The alicyclic hydrocarbon group of Ra1 to Ra3 preferably has 3 to 16 carbon atoms, and more preferably has 4 to 16 carbon atoms.
When Ra1 and Ra2 is bonded together to form a C2 to C20 divalent hydrocarbon group, examples of the group-C(Ra1)(Ra2)(Ra3) include groups below. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms. * represents a bond to —O—.




Specific examples of the acid labile group (1) include, for example,
1,1-dialkylalkoxycarbonyl group (a group in which Ra1 to Ra3 are alkyl groups, preferably tert-butoxycarbonyl group, in the formula (1)),
2-alkyladamantane-2-yloxycarbonyl group (a group in which Ra1, Ra2 and a carbon atom form adamantyl group, and Ra3 is alkyl group, in the formula (1)), and
1-(adamantane-1-yl)-1-alkylalkoxycarbonyl group (a group in which Ra1 and Ra2 are alkyl group, and Ra3 is adamantyl group, in the formula (1)).
The hydrocarbon group of Ra1′ to Ra3′ includes any of an alkyl group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
Examples of the aromatic hydrocarbon group include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.
Examples of the divalent hydrocarbon group which is formed by bonding with Ra2′ and Ra3′ include a divalent aliphatic hydrocarbon group.
At least one of Ra1′ and Ra2′ is preferably a hydrogen atom.
Specific examples of the acid labile group (2) include a group below.




The acid labile monomer (a1) is preferably a monomer having an acid labile group and a carbon-carbon double bond, and more preferably a (meth)acrylic monomer having the acid labile group.
Among the (meth)acrylic monomer having an acid labile group, it is preferably a monomer having a C5 to C20 alicyclic hydrocarbon group. When a resin which can be obtained by polymerizing monomers having bulky structure such as the alicyclic hydrocarbon group is used, the resist composition having excellent resolution tends to be obtained during the production of a resist pattern.
Examples of the (meth)acrylic monomer having the acid labile group (1) and a carbon-carbon double bond preferably include a monomer represented by the formula (a1-1) and a monomer represented by the formula (a1-2), below (hereinafter are sometimes referred to as a “monomer (a1-1)” and a “monomer (a1-2)”). These may be used as a single monomer or as a combination of two or more monomers.




wherein La1 and La2 independently represent *-O— or *-O—(CH2)k1—CO—O—, k1 represents an integer of 1 to 7, * represents a bond to the carbonyl group;
Ra4 and Ra5 independently represent a hydrogen atom or a methyl group;
Ra6 and Ra7 independently represent a C1 to C8 alkyl group or a C3 to C10 alicyclic hydrocarbon group;
m1 represents an integer 0 to 14;
n1 represents an integer 0 to 10; and
n1′ represents an integer 0 to 3.
In the formula (a1-1) and the formula (a1-2), La1 and La2 are preferably *-O— or *-O—(CH2)k1′—CO—O—, here k1′ represents an integer of 1 to 4 and more preferably 1, and more preferably *-O—.
Ra4 and Ra5 are preferably a methyl group.
Examples of the alkyl group of Ra6 and Ra7 include methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl groups. Among these, the alkyl group of Ra6 and Ra7 is preferably a C1 to C6 alkyl group.
Examples of the alicyclic hydrocarbon group of Ra6 and Ra7 include monocyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl, norbornyl (i.e., bicyclo[2.2.1]heptyl), and methyl norbornyl groups as well as groups above. Among these, the alicyclic hydrocarbon group of Ra6 and Ra7 is preferably a C3 to C8 alicyclic hydrocarbon group, and more preferably a C3 to C6 alicyclic hydrocarbon group.
m1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1′ is preferably 0 or 1, and more preferably 1.
Examples of the monomer (a1-1) include monomers described in JP 2010-204646A. Among these, the monomers are preferably monomers represented by the formula (a1-1-1) to the formula (a1-1-8), and more preferably monomers represented by the formula (a1-1-1) to the formula (a1-1-4) below.







Examples of the monomer (a1-2) include 1-ethyl-1-cyclopentane-1-yl (meth)acrylate, 1-ethyl-1-cyclohexane-1-yl (meth)acrylate, 1-ethyl-1-cycloheptane-1-yl (meth)acrylate, 1-methyl-1-cyclopentane-1-yl (meth)acrylate and 1-isopropyl-1-cyclopentane-1-yl (meth)acrylate. Among these, the monomers are preferably monomers represented by the formula (a1-2-1) to the formula (a1-2-12), and more preferably monomers represented by the formula (a1-2-3), the formula (a1-2-4), the formula (a1-2-9) and the formula (a1-2-10), and still more preferably monomers represented by the formula (a1-2-3) and the formula (a1-2-9) below.







When the resin (A2) contains the structural unit (a1-1) and/or the structural unit (a1-2), the total proportion thereof is generally 10 to 95 mol %, preferably 15 to 90 mol %, more preferably 20 to 85 mol %, with respect to the total structural units (100 mol %) of the resin (A2).
Examples of a monomer having an acid-labile group (2) and a carbon-carbon double bond include a monomer represented by the formula (a1-5). Such monomer is sometimes hereinafter referred to as “monomer (a1-5)”. When the resin (A2) has the structural unit derived from the monomer (a1-5), a resist pattern tends to be obtained with less defects.




wherein R31 represents a hydrogen atom, a halogen atom or a C1 to C6 alkyl group that optionally has a halogen atom;
Z1 represents a single bond or *-O—(CH2)k4—CO-L4-, k4 represents an integer of 1 to 4, * represents a bond to L1;
L1, L2, L3 and L4 independently represent *-O— or *-S—.
s1 represents an integer of 1 to 3;
s1′ represents an integer of 0 to 3.
In the formula (a1-5), R31 is preferably a hydrogen atom, a methyl group or trifluoromethyl group;
L1 is preferably —O—;
L2 and L3 are independently preferably *-O— or *-S—, and more preferably —O— for one and —S— for another;
s1 is preferably 1;
s1′ is preferably an integer of 0 to 2;
Z1 is preferably a single bond or —CH2—CO—O—.
Examples of the monomer (a1-5) include monomers below.










When the resin (A2) contains the structural unit derived from the monomer (a1-5), the proportion thereof is generally 1 to 50 mol %, preferably 3 to 45 mol %, and more preferably 5 to 40 mol %, with respect to the total structural units (100 mol %) constituting the resin (A2).
<Acid Stable Monomer>
As the acid stable monomer, a monomer having a hydroxy group or a lactone ring is preferable. When a resin containing the structural unit derived from a monomer having hydroxy group (hereinafter such acid stable monomer is sometimes referred to as “acid stable monomer (a2)”) or a acid stable monomer having a lactone ring (hereinafter such acid stable monomer is sometimes referred to as “acid stable monomer (a3)”) is used, the adhesiveness of resist pattern to a substrate and resolution of resist pattern tend to be improved.
<Acid Stable Monomer (a2)>
The acid stable monomer (a2), which has a hydroxy group, is preferably selected depending on the kinds of an exposure light source at producing the resist pattern.
When KrF excimer laser lithography (248 nm), or high-energy irradiation such as electron beam or EUV light is used for the resist composition, using the acid stable monomer having a phenolic hydroxy group such as hydroxystyrene as the acid stable monomer (a2) is preferable.
When ArF excimer laser lithography (193 nm), i.e., short wavelength excimer laser lithography is used, using the acid stable monomer having a hydroxy adamantyl group represented by the formula (a2-1) as the acid stable monomer (a2) is preferable.
The acid stable monomer (a2) having the hydroxy group may be used as a single monomer or as a combination of two or more monomers.
Examples of the acid stable monomer having hydroxy adamantyl include the monomer represented by the formula (a2-1).




wherein La3 represents —O— or *-O—(CH2)k2—CO—O—;
k2 represents an integer of 1 to 7;
* represents a bind to —CO—;
Ra14 represents a hydrogen atom or a methyl group;
Ra15 and Ra16 independently represent a hydrogen atom, a methyl group or a hydroxy group;
o1 represents an integer of 0 to 10.
In the formula (a2-1), La3 is preferably —O—, —O—(CH2)f1—CO—O—, here f1 represents an integer of 1 to 4, and more preferably —O—.
Ra14 is preferably a methyl group.
Ra15 is preferably a hydrogen atom.
Ra16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, and more preferably an integer of 0 or 1.
Examples of the acid stable monomer (a2-1) include monomers described in JP 2010-204646A. Among these, the monomers are preferably monomers represented by the formula (a2-1-1) to the formula (a2-1-6), more preferably monomers represented by the formula (a2-1-1) to the formula (a2-1-4), and still more preferably monomers represented by the formula (a2-1-1) and the formula (a2-1-3) below.







When the resin (A2) contains the acid stable structural unit derived from the monomer represented by the formula (a2-1), the proportion thereof is generally 3 to 45 mol %, preferably 5 to 40 mol %, more preferably 5 to 35 mol %, and still more preferably 5 to 30 mol %, with respect to the total structural units (100 mol %) constituting the resin (A2).
<Acid Stable Monomer (a3)>
The lactone ring included in the acid stable monomer (a3) may be a monocyclic compound such as β-propiolactone ring, γ-butyrolactone, δ-valerolactone, or a condensed ring with monocyclic lactone ring and other ring. Among these, γ-butyrolactone and condensed ring with γ-butyrolactone and other ring are preferable.
Examples of the acid stable monomer (a3) having the lactone ring include monomers represented by the formula (a3-1), the formula (a3-2) and the formula (a3-3). These monomers may be used as a single monomer or as a combination of two or more monomers.




wherein La4 to La6 independently represent —O— or *-O—(CH2)k3—CO—O—;
k3 represents an integer of 1 to 7, * represents a bind to —CO—;
Ra18 to Ra20 independently represent a hydrogen atom or a methyl group;
Ra21 in each occurrence represents a C1 to C4 alkyl group;
p1 represents an integer of 0 to 5;
Ra22 to Ra23 in each occurrence independently represent a carboxyl group, cyano group, and a C1 to C4 alkyl group;
q1 and r1 independently represent an integer of 0 to 3.
In the formulae (a3-1) to (a3-3), La4 to La6 include the same group as described in La3 above, and are independently preferably —O—, *-O—(CH2)k3—CO—O—, here k3′ represents an integer of 1 to 4 (preferably 1), and more preferably —O—;
Ra18 to Ra21 are independently preferably a methyl group.
Ra22 and Ra23 are independently preferably a carboxyl group, cyano group or methyl group;
p1 to r1 are independently preferably an integer of 0 to 2, and more preferably an integer of 0 or 1.
Examples of the monomer (a3) include monomers described in JP 2010-204646A. Among these, the monomers are preferably monomers represented by the formula (a3-1-1) to the formula (a3-1-4), the formula (a3-2-1) to the formula (a3-2-4), the formula (a3-3-1) to the formula (a3-3-4), more preferably monomers represented by the formula (a3-1-1) to the formula (a3-1-2), the formula (a3-2-3) to the formula (a3-2-4), and still more preferably monomers represented by the formula (a3-1-1) and the formula (a3-2-3) below.










When the resin (A2) contains the structural units derived from the acid stable monomer (a3) having the lactone ring, the total proportion thereof is preferably 5 to 70 mol %, more preferably 10 to 65 mol %, still more preferably 15 to 60 mol %, with respect to the total structural units (100 mol %) constituting the resin (A2).
When the resin (A2) is the copolymer of the acid labile monomer (a1) and the acid stable monomer, the proportion of the structural unit derived from the acid labile monomer (a1) is preferably 10 to 80 mol %, and more preferably 20 to 60 mol %, with respect to the total structural units (100 mol %) constituting the resin (A2).
The resin (A2) preferably contains 15 mol % or more of the structural unit derived from the monomer having an adamantyl group (in particular, the monomer having the acid labile group (a1-1)) with respect to the structural units derived from the acid labile monomer (a1). As the mole ratio of the structural unit derived from the monomer having an adamantyl group increases within this range, the dry etching resistance of the resulting resist improves.
The resin (A2) preferably is a copolymer of the acid labile monomer (a1) and the acid stable monomer. In this copolymer, the acid labile monomer (a1) is preferably at least one of the acid labile monomer (a1-1) having an adamantyl group and the acid labile monomer (a1-2) having a cyclohexyl group, and more preferably is the acid labile monomer (a1-1).
The acid stable monomer is preferably the acid stable monomer (a2) having a hydroxy group and/or the acid stable monomer (a3) having a lactone ring. The acid stable monomer (a2) is preferably the monomer having the hydroxyadamantyl group (a2-1). The acid stable monomer (a3) is preferably at least one of the monomer having the γ-butyrolactone ring (a3-1) and the monomer having the condensed ring of the γ-butyrolactone ring and the norbornene ring (a3-2).
The resin (A2) can be produced by a known polymerization method, for example, radical polymerization method, using at least one of the acid labile monomer (a1) and/or at least one of the acid stable monomer (a2) having a hydroxy group and/or at least one of the acid stable monomer (a3) having a lactone ring and/or at least one of a known compound.
The weight average molecular weight of the resin (A2) is preferably 2,500 or more (more preferably 3,000 or more, and still more preferably 4,000 or more), and 50,000 or less (more preferably 30,000 or less, and still more preferably 10,000 or less).
In the present resist composition, the weight ratio of the resins (A1)/(A2) is preferably, for example, 0.01/10 to 5/10, more preferably 0.05/10 to 3/10, still more preferably 0.1/10 to 2/10, in particular, preferably 0.2/10 to 1/10.
<Resin Other than Resin (A1) and Resin (A2)>
The resist composition of the present invention may include a resin other than the resin (A1) and the resin (A2) described above. Such resin is a resin having at least one of the structural unit derived from the acid labile monomer (a1), at least one of the structural unit derived from the acid stable monomer, as described above, and/or at least one of the structural unit derived from a known monomer in this field.
The proportion of the resin (A) can be adjusted with respect to the total solid proportion of the resist composition. For example, the resist composition of the present invention preferably contains 80 weight % or more and 99 weight % or less of the resin (A), with respect to the total solid proportion of the resist composition.
In the specification, the term “solid proportion of the resist composition” means the entire proportion of all ingredients other than the solvent (E).
The proportion of the resin (A) and the solid proportion of the resist composition can be measured with a known analytical method such as, for example, liquid chromatography and gas chromatography.
<Acid Generator (B)>
An acid generator (B) is classified into non-ionic-based or ionic-based acid generator.
Examples of the non-ionic-based acid generator include organic halogenated compounds; sulfonate esters such as 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyl oxyimide, sulfonyl oxyketone and diazo naphthoquinone 4-sulfonate; sulfones such as disulfone, ketosulfone and sulfonyl diazomethane.
Examples of the ionic acid generator includes onium salts containing onium cation (such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts).
Examples of anion of onium salts include sulfonate anion, sulfonylimide anion and sulfonylmethyde anion.
For the acid generator (B), compounds which generate an acid by radiation described in JP S63-26653-A, JP S55-164824-A, JP S62-69263-A, JP S63-146038-A, JP S63-163452-A, JP S62-153853-A, JP S63-146029-A, U.S. Pat. No. 3,779,778-B, U.S. Pat. No. 3,849,137-B, DE3,914,407-B and EP-126,712-A can be used. Also, the acid generator formed according to conventional methods can be used.
A fluorine-containing acid generator is preferable for the acid generator (B), and a sulfonic acid salt represented by the formula (B1) is more preferable.




wherein Q1 and Q2 independently represent a fluorine atom or a C1 to C6 perfluoroalkyl group;
Lb1 represents a single bond or an C1 to C17 divalent saturated hydrocarbon group, and one or more —CH2— contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—;
Y represents an optionally substituted C1 to C18 alkyl group or an optionally substituted C3 to C18 alicyclic hydrocarbon group, and one or more —CH2— contained in the alkyl group and alicyclic hydrocarbon group may be replaced by —O—, —CO— or —SO2—; and
Z+ represents an organic cation.
In the formula (B1), a moiety having a negative charge in which an organic cation, Z+, having a positive charge is removed sometimes refers to as a sulfonate anion.
Examples of the perfluoroalkyl group of Q1 and Q2 include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoro-isopropyl, perfluorobutyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoropentyl and perfluorohexyl groups.
Among these, Q1 and Q2 independently are preferably trifluoromethyl or fluorine atom, and more preferably a fluorine atom.
Examples of the a divalent saturated hydrocarbon group of Lb1 include any of;
a chain alkanediyl group such as methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, ethane-1,1-diyl, propan-1,1-diyl and propan-2,2-diyl groups;
a branched chain alkanediyl group such as a group in which a chain alkanediyl group is bonded a side chain of a C1 to C4 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl, for example, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl and 2-methylbutane-1,4-diyl groups;
a mono-alicyclic saturated hydrocarbon group such as a cycloalkanediyl group (e.g., cyclobutan-1,3-diyl, cyclopentan-1,3-diyl, cyclohexane-1,4-diyl and cyclooctan-1,5-diyl groups);
a poly-alicyclic saturated hydrocarbon group such as norbornane-2,3-diyl, norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl and adamantane-2,6-diyl groups; and
a combination of two or more groups.
Examples of the saturated hydrocarbon group of Lb1 in which one or more —CH2— contained in the saturated hydrocarbon group is replaced by —O— or —CO— include groups represented by the formula (b1-1) to the formula (b1-6) below. In the formula (b1-1) to the formula (b1-6), the group is represented so as to correspond with two sides of the formula (B1), that is, the left side of the group bonds to the carbon atom of C(Q1)(Q2)- and the right side of the group bonds to —Y (examples of the formula (b1-1) to the formula (b1-6) are the same as above). * represents a bond.




wherein Lb2 represents a single bond or a C1 to C15 divalent saturated hydrocarbon group;
Lb3 represents a single bond or a C1 to C12 divalent saturated hydrocarbon group;
Lb4 represents a C1 to C13 divalent saturated hydrocarbon group, the total number of the carbon atoms in Lb3 and Lb4 is at most 13;
Lb5 represents a C1 to C15 divalent saturated hydrocarbon group;
Lb6 and Lb7 independently represent a C1 to C15 divalent saturated hydrocarbon group, the total number of the carbon atoms in Lb6 and Lb7 is at most 16;
Lb8 represents a C1 to C14 divalent saturated hydrocarbon group;
Lb9 and Lb10 independently represent a C1 to C11 divalent saturated hydrocarbon group, the total number of the carbon atoms in Lb9 and Lb10 is at most 12.
The saturated hydrocarbon group of Lb2 to Lb9 is preferably an alkanediyl group, the saturated hydrocarbon group of Lb10 is preferably an alkanediyl group and a C3 to C10 alicyclic hydrocarbon group, and more preferably an alkanediyl, cycloalkyl and adamantyl groups.
Lb1 is preferably the groups represented by the formula (b1-1) to the formula (b1-4), more preferably the group represented by the formula (b1-1) or the formula (b1-2), and still more preferably the group represented by the formula (b1-1). In particular, the divalent group represented by the formula (b1-1) in which Lb2 represents a single bond or —CH2— is preferable.
Specific examples of the divalent group represented by the formula (b1-1) include groups below. In the formula below, * represent a bond.




Specific examples of the divalent group represented by the formula (b1-2) include groups below.




Specific examples of the divalent group represented by the formula (b1-3) include groups below.




Specific examples of the divalent group represented by the formula (b1-4) include a group below.




Specific examples of the divalent group represented by the formula (b1-5) include groups below.




Specific examples of the divalent group represented by the formula (b1-6) include groups below.




Examples of the alkyl group of Y include methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, 2,2-dimethylethyl, propyl, 1-methylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-propylbutyl, pentyl, 1-methylpentyl, hexyl, 1,4-dimethylhexyl, heptyl, 1-methylheptyl, octyl, methyloctyl, methylnonyl, 2-ethylhexyl, nonyl, decyl, undecyl and dodecyl groups.
The alkyl group of Y is preferably a C1 to C6 alkyl group.
Examples of the alicyclic hydrocarbon group of Y include groups represented by the formula (Y1) to the formula (Y11).
Examples of the alicyclic hydrocarbon group of Y in which one or more —CH2— contained in the alicyclic hydrocarbon group is replaced by —O—, —CO— or —SO2— include groups represented by the formula (Y12) to the formula (Y26).







Among these, the alicyclic hydrocarbon group is preferably any one of groups represented by the formula (Y1) to the formula (Y19), more preferably any one of groups represented by the formula (Y11), (Y14), (Y15) or (Y19), and still more preferably group represented by the formula (Y11) or (Y14).
Y may have a substituent.
Examples of the substituent of Y include a halogen atom, a hydroxy group, a C1 to C12 alkyl group, a hydroxy group-containing C1 to C12 alkyl group, a C3 to C16 alicyclic hydrocarbon group, a C1 to C12 alkoxy group, a C6 to C18 aromatic hydrocarbon group, a C7 to C21 aralkyl group, a C2 to C4 acyl group, a glycidyloxy group or a —(CH2)j2—O—CO—Rb1 group, wherein Rb1 represents a C1 to C16 alkyl group, a C3 to C16 alicyclic hydrocarbon group or a C6 to C18 aromatic hydrocarbon group, j2 represents an integer of 0 to 4. The alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and the aralkyl group of the substituent may further have a substituent such as a C1 to C6 alkyl group, a halogen atom and a hydroxy group.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the hydroxy group-containing alkyl group include hydroxymethyl and hydroxyethyl groups
Examples of the alkoxyl group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy groups.
Examples of the aromatic hydrocarbon group include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.
Examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, naphthylmethyl and naphthylethyl groups.
Examples of the acyl group include acetyl, propionyl and butyryl groups.
Examples of the alkyl and the alicyclic hydrocarbon groups are the same examples as described above.
Examples of Y include the groups below.




When Y represents an alkyl group and Lb1 represents a C1 to C17 divalent saturated hydrocarbon group, the —CH2— contained in the divalent saturated hydrocarbon group bonding Y is preferably replaced by an oxygen atom or carbonyl group. In this case, the —CH2— contained in the alkyl group constituting Y is not replaced by an oxygen atom or carbonyl group. The same shall be applied when the alkyl group of Y and divalent saturated hydrocarbon group of Lb1 has a substituent.
Y is preferably an alicyclic hydrocarbon group which may optionally have a substituent, more preferably an adamantyl group which may optionally have a substituent, for example, an oxo group and a hydroxy group, and still more preferably an adamantyl group, a hydroxyadamantyl group and an oxoadamantyl group.
The sulfonate anion is preferably an anions represented by the formula (b1-1-1) to the formula (b1-1-9) below. In the formula (b1-1-1) to the formula (b 1-1-9), Q1, Q2 and Lb2 represents the same meaning as defined above. Rb2 and Rb3 independently represent a C1 to C4 alkyl group (preferably methyl group).




Specific examples of the sulfonate anion include sulfonate anions described in JP2010-204646A.
Examples of the cation of the acid generator (B) include an organic onium cation, for example, organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation and organic phosphonium cation. Among these, organic sulfonium cation and organic iodonium cation are preferable, and aryl sulfonium cation is more preferable.
Z+ of the formula (B1) is preferably represented by any of the formula (b2-1) to the formula (b2-4).




wherein Rb4, Rb5 and Rb6 independently represent a C1 to C30 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a C6 to C36 aromatic hydrocarbon group, or Rb4 and Rb5 may be bonded together to form a sulfur-containing ring, one or more hydrogen atoms contained in the alkyl group may be replaced by a hydroxy group, a C3 to C18 alicyclic hydrocarbon group, a C1 to C12 alkoxy group or a C6 to C18 aromatic hydrocarbon group, one or more hydrogen atoms contained in the alicyclic hydrocarbon group may be replaced by a halogen atom, a C1 to C18 alkyl group, a C2 to C4 acyl group and a glycidyloxy group, one or more hydrogen atoms contained in the aromatic hydrocarbon group may be replaced by a halogen atom, a hydroxy group or a C1 to C12 alkoxy group;
Rb7 and Rb8 in each occurrence independently represent a hydroxy group, a C1 to C12 alkyl group or a C1 to C12 alkoxyl group;
m2 and n2 independently represent an integer of 0 to 5;
Rb9 and Rb10 independently represent a C1 to C18 alkyl group or a C3 to C18 alicyclic hydrocarbon group, or Rb9 and Rb10 may be bonded together with a sulfur atom bonded thereto to form a sulfur-containing 3- to 12-membered (preferably 3- to 7-membered) ring, and one or more —CH2— contained in the ring may be replaced by —O—, —CO— or —S—;
Rb11 represents a hydrogen atom, a C1 to C18 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a C6 to C18 aromatic hydrocarbon group;
Rb12 represents a C1 to C12 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a C6 to C18 aromatic hydrocarbon group, one or more hydrogen atoms contained in the alkyl group may be replaced by a C6 to C18 aromatic hydrocarbon group, one or more hydrogen atoms contained in the aromatic hydrocarbon group may be replaced by a C1 to 012 alkoxy group or a C1 to C12 alkyl carbonyloxy group;
Rb11 and Rb12 may be bonded together with —CH—CO— bonded thereto to form a 3- to 12-membered (preferably a 3- to 7-membered) ring, and one or more —CH2— contained in the ring may be replaced by —O—, —CO— or —S—;
Rb13, Rb14, Rb15, Rb16, Rb17 and Rb18 in each occurrence independently represent a hydroxy group, a C1 to C12 alkyl group or a C1 to C12 alkoxy group;
Lb11 represents —S— or —O—;
o2, p2, s2 and t2 independently represent an integer of 0 to 5;
q2 or r2 independently represent an integer of 0 to 4;
u2 represents an integer of 0 or 1.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2-ethylhexyl groups. In particular, the alkyl group of Rb9 to Rb12 is preferably a C1 to C12 alkyl group.
Examples of the alkyl group in which one or more hydrogen atoms are replaced by an alicyclic hydrocarbon group include 1-(1-adamatane-1-yl)-alkane-1-yl group.
Examples of the alicyclic hydrocarbon group include a monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl; a polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl and norbornyl groups as well as groups below.




In particular, the alicyclic hydrocarbon group of Rb9 to Rb12 is preferably a C3 to C18 alicyclic hydrocarbon group, and more preferably a C4 to C12 alicyclic hydrocarbon group.
Examples of the alicyclic hydrocarbon group in which one or more hydrogen atoms are replaced by an alkyl group include methyl cyclohexyl, dimethyl cyclohexyl, 2-alkyl-2-adamantyl, methyl norbornyl and isobornyl groups.
Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.
When the aromatic hydrocarbon include an alkyl group or an alicyclic hydrocarbon group, a C1 to C18 alkyl group or a C3 to C18 alicyclic hydrocarbon group is preferable.
Examples of the alkyl group in which one or more hydrogen atoms are replaced by an aromatic hydrocarbon group, i.e., aralkyl group include benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl and naphthylethyl groups.
Examples of the alkoxyl group include methoxy, ethoxy, propoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the acyl group include acetyl, propionyl and butyryl groups.
Examples of the alkyl carbonyloxy group include methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, pentyl carbonyloxy, hexyl carbonyloxy, octylcarbonyloxy and 2-ethylhexylcarbonyloxy groups.
The sulfur-containing ring formed by Rb4 and Rb5 may be either of monocyclic or polycyclic, aromatic or non-aromatic, or saturated or unsaturated ring, and may further have at least one of sulfur atom and/or at least one of oxygen atom as long as the ring has one sulfur atom. The ring is preferably a ring having 3 to 18 carbon atoms, and more preferably a ring having 4 to 12 carbon atoms.
Examples of the ring having a sulfur atom and formed by Rb9 and Rb10 bonded together include thiolane-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring and 1,4-oxathian-4-ium ring.
Examples of the ring having —CH—CO— and formed by Rb11 and Rb12 bonded together include oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring and oxoadamantane ring.
Among the cations represented by the formula (b2-1) to the formula (b2-4), the cation represented by the formula (b2-1-1) is preferable, and triphenyl sulfonium cation (v2=w2=x2=0 in the formula (b2-1-1)), diphenyl sulfonium cation (v2=w2=0, x2=1, and Rb21 is a methyl group in the formula (b2-1-1)), and tritolyl sulfonium cation (v2=w2=X2=1, Rb19, Rb20 and Rb21 are a methyl group in the formula (b2-1-1)) are more preferable.




wherein Rb19, Rb20 and Rb21 in each occurrence independently represent a halogen atom, a hydroxy group, a C1 to C18 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a C1 to C12 alkoxy group, or two of Rb19, Rb20 and Rb21 may be bonded together to form a sulfur-containing ring;
v2 to x2 independently represent an integer of 0 to 5.
In the formula (b2-1-1), the sulfur-containing ring formed by two of Rb19, Rb20 and Rb21 may be either of monocyclic or polycyclic, aromatic or non-aromatic, or saturated or unsaturated ring, and may further have at least one of sulfur atom and/or at least one of oxygen atom as long as the ring has one sulfur atom.
In particular, the alkyl group of Rb19 to Rb21 is preferably a C1 to C12 alkyl group, the alicyclic hydrocarbon group of Rb19 to Rb21 is preferably a C4 to C18 alicyclic hydrocarbon group,
Rb19 to Rb21 independently preferably represent a halogen atom (and more preferably fluorine atom), a hydroxy group, a C1 to C12 alkyl group or a C1 to C12 alkoxy group; or two of Rb19, Rb20 and Rb21 preferably are bonded together to form a sulfur-containing ring, and
v2 to x2 independently represent preferably 0 or 1.
Specific examples of the organic cations represented by the formula (b2-1) to the formula (b2-4) and the formula (b2-1-1) include, for example, compounds described in JP2010-204646A.
The acid generator (B1) is a compound combined the above sulfonate anion with an organic cation.
The above sulfonate anion and the organic cation may optionally be combined, a combination of any of the anion represented by the formula (b1-1-1) to the formula (b1-1-9) and the cation represented by the formula (b2-1-1), as well as a combination of any of the anion represented by the formula (b1-1-3) to the formula (b1-1-5) and the cation represented by the formula (b2-3) are preferable.
Preferred acid generators (B1) are represented by the formula (B1-1) to the formula (B1-20). Among these, the formulae (B1-1), (B1-2), (B1-6), (B1-11), (B1-12), (B1-13) and (B1-14) which contain triphenyl sulfonium cation, and the formulae (B1-3) and (B1-7) which contain tritolyl sulfonium cation are preferable.
















In the resist composition of the present invention, the proportion of the acid generator (B) is preferably not less than 1 weight % (and more preferably not less than 3 weight %), and not more than 40 weight % (and more preferably not more than 35 weight %, and still more preferably not more than 30 weight %), with respect to 100 weight % of the resin (A2).
In the resist composition of the present invention, the acid generator (B) may be used as a single salt or as a combination of two or more salts.
<Salt Having Anion (IA)>
The salt having the anion (IA) is represented by the formula (IA)




wherein R1A and R2A independently represent a hydrogen atom, a C1 to C12 aliphatic hydrocarbon group, a C3 to C20 alicyclic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group or a C7 to C21 aralkyl group, one or more hydrogen atoms contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group and the aralkyl group may be replaced by a hydroxy group, a cyano group, a fluorine atom, trifluoromethyl group or a nitro group, one or more —CH2— contained in the aliphatic hydrocarbon group may be replaced by —O— or —CO—; or R1A and R2A may be bonded to form at least one nitrogen atom-containing C4 to C20 ring.
Examples of the aliphatic hydrocarbon group of R1A and R2A in the formula (IA) include methyl (IR-1), ethyl (IR-2), n-propyl (IR-3), iso-propyl (IR-4) n-butyl (IR-5), sec-butyl (IR-6), tert-butyl (IR-7), n-pentyl (IR-8), n-hexyl (IR-9), heptyl (IR-10), octyl (IR-11), 2-ethylhexyl (IR-12), nonyl (IR-13), decyl (IR-14), undecyl (IR-15) and dodecyl (IR-16) groups.
The alicyclic hydrocarbon group may be either monocyclic or polycyclic hydrocarbon group. Examples of the alicyclic hydrocarbon group include cyclopropyl (IR-21), cyclobutyl (IR-22), cyclopentyl (IR-23), cyclohexyl (IR-24), cycloheptyl (IR-25), cyclooctyl (IR-26), cyclononyl (IR-27), cyclodecyl (IR-28), 1-norbornyl (IR-29), 1-adamantyl (IR-30), 2-adamantyl (IR-31), 2-isobonyl (IR-32), 2-norbornyl (IR-39) and groups described below.




Examples of the aromatic hydrocarbon group include phenyl (IR-51), 1-naphthyl (IR-52), 1-anthryl (IR-53), p-methylphenyl (IR-54), p-tert-butylphenyl (IR-55), p-adamantylphenyl (IR-56), 2-naphthyl (IR-57), 2-anthryl (IR-58) and 9-anthryl (IR-59) groups.
Examples of the aliphatic hydrocarbon group which is substituted with hydroxy group include groups described below.




Examples of the aliphatic hydrocarbon group which is substituted with cyano group include groups described below.




Examples of the aliphatic hydrocarbon group which is substituted with a fluorine atom include groups described below.




Examples of the aliphatic hydrocarbon group which is substituted with a nitro group include groups described below.




Examples of the alicyclic hydrocarbon group which is substituted with a hydroxy group include groups described below.




Examples of the alicyclic hydrocarbon group which is substituted with cyano group include groups described below.




Examples of the alicyclic hydrocarbon group which is substituted with fluorine atom or fluoromethyl group include groups described below.




Examples of the alicyclic hydrocarbon group which is substituted with a nitro group include groups described below.




Examples of the aromatic hydrocarbon group which is substituted with a hydroxy group include groups described below.




Examples of the aromatic hydrocarbon group which is substituted with a cyano group include groups described below.




Examples of the aromatic hydrocarbon group which is substituted with a fluorine atom or fluoromethyl group include groups described below.







Examples of the aromatic hydrocarbon group which is substituted with a nitro group include groups described below.




Examples of the aralkyl hydrocarbon group which is substituted with a hydroxy group include groups described below.




Examples of the aralkyl hydrocarbon group which is substituted with a cyano group include groups described below.




Examples of the aralkyl hydrocarbon group which is substituted with a fluorine atom or trifluomethyl group include groups described below.




Examples of the aralkyl hydrocarbon group which is substituted with a nitro group include groups described below.




Examples of one or more —CH2— contained in the aliphatic hydrocarbon group replaced by —O— include groups described below.




Examples of one or more —CH2— contained in the aliphatic hydrocarbon group replaced by —CO— include groups described below.




Examples of two —CH2— contained in the aliphatic hydrocarbon group replaced by —O— and —CO— include groups described below.







When R1A and R2A are bonded together with a nitrogen atom bonded thereto to form a ring, examples —NR1AR2A include groups described below. * represents a bond to SO3—.










In the formula (IA), an anion in which one of R1A and R2A is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or an anion represented by the formula (IE) below is preferable.




wherein ring W1 represents an optionally substituted heterocyclic ring.
Examples of the optionally substituted heterocyclic ring include groups represented by the formula (IR-301) to the formula (IR-329) described above. Among these, a group in which one of R1A and R2A is cyclohexyl group or adamantyl group, a group represented by the formula (IR-316), or a group represented by the formula (IR-326) is preferable.
The salt having an anion (IA) generally contains a cation.
Examples of the cation include an onium cation such as diazonium cation, organic phosphonium cation, organic sulfonium cation, organic iodonium cation, among these, organic sulfonium cation and organic iodonium cation are preferable.
Examples of the cation include cations represented by the formulae (b2-1) to (b2-4) and the formula (b2-1-1) described above, the formula (IB), the formula (IC) and the formula (ID), among these, the cations represented by the formula (IB), the formula (IC) and the formula (ID) are preferable, and the cations represented by the formula (IB) is more preferable.




wherein R3, R4 and R5 in each occurrence independently represent a hydroxy group, a halogen atom, a C1 to C12 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a C1 to C12 alkoxy group, or two of R3, R4 and R5 may be bonded together to form a sulfur-containing ring, one or more hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group and the alkoxy group may be replaced by a halogen atom, a hydroxy group, a C1 to C12 alkoxy group, a C6 to C18 aromatic hydrocarbon group, a C2 to C4 acyl group or a glycidyloxy group,
mx, my and m/z independently represent an integer of 0 to 5.
In particular, the sulfur-containing ring which is formed by two of R3, R4 and R5 may be any of a monocyclic, polycyclic, aromatic or non-aromatic ring, and may further include at least one sulfur atm and/or at least one oxygen atom in addition to one sulfur atom.




wherein R6 and R7 independently represent a C1 to C36 aliphatic hydrocarbon group or a C3 to C36 alicyclic hydrocarbon group, or R6 and R7 may be bonded together with a sulfur atom bonded thereto to form a sulfur-containing 3- to 12-membered ring, and one or more —CH2— contained in the ring may be replaced by —O—, —S— or —CO—;
R8 represents a hydrogen atom, a C1 to C36 aliphatic hydrocarbon group, a C3 to C36 alicyclic hydrocarbon group or a C6 to C18 aromatic hydrocarbon group;
R9 represents a C1 to C12 aliphatic hydrocarbon group, a C3 to C18 alicyclic hydrocarbon group and a C6 to C18 aromatic hydrocarbon group, the aromatic hydrocarbon group may be substituted with a C1 to C12 aliphatic hydrocarbon group, a C1 to C12 alkoxy group, a C3 to C18 alicyclic hydrocarbon group or a C1 to C12 alkyl carbonyloxy group;
R8 and R9 may be bonded together with —CH—CO— bonded thereto to form a 3- to 12-membered ring, and one or more —CH2-contained in the ring may be replaced by —O—, —S— or —CO—.
In particular, the aliphatic hydrocarbon group of R6 to R8 is preferably a C1 to C12 aliphatic hydrocarbon group, the alicyclic hydrocarbon group of R6 to R8 is preferably a C3 to C36 alicyclic hydrocarbon group, and more preferably a C4 to C12 alicyclic hydrocarbon group.




wherein R3d and R4d in each occurrence independently represent a C1 to 030 aliphatic hydrocarbon group, a C3 to C36 alicyclic hydrocarbon group or a C6 to C18 aromatic hydrocarbon group, one or more hydrogen atom contained in the aliphatic hydrocarbon group may be replaced by a hydroxy group, a C1 to C12 alkoxy group or a C6 to C18 aromatic hydrocarbon group, one or more hydrogen atom contained in the alicyclic hydrocarbon group may be replaced by a halogen atom, a C2 to C4 acyl group or a glycidyloxy group and one or more hydrogen atom contained in the aromatic hydrocarbon group may be replaced by a halogen atom, a hydroxy group, a C1 to C36 aliphatic hydrocarbon group, a C3 to C36 alicyclic hydrocarbon group or a C1 to 012 alkoxy group;
md and md′ independently represent an integer of 0 to 5.
Specific examples of the cation represented by the formula (IB) include cations below.
















Specific examples of the cation represented by the formula (IC) include cations below.













Specific examples of the cation represented by the formula (ID) include cations below.










Examples of the sulfonium salts having an anion represented by the formula (IA) include sulfonium salts described in the Tables below. In the Table, “IR-1”, for example, means the group represented by the formula (IR-1) described above, and “I-1” hereinafter may be expressed “salt represented by the formula (I-1)”.












TABLE 1









Salt
R1A
R2A
Cation







I-1
H
IR-1
IB-1



I-2
H
IR-2
IB-1



I-3
H
IR-3
IB-1



I-4
H
IR-4
IB-1



I-5
H
IR-5
IB-1



I-6
H
IR-6
IB-1



I-7
H
IR-7
IB-1



I-8
H
IR-8
IB-1



I-9
H
IR-9
IB-1



I-10
H
IR-10
IB-1



I-11
H
IR-11
IB-1



I-12
H
IR-12
IB-1



I-13
H
IR-13
IB-1



I-14
H
IR-14
IB-1



I-15
H
IR-15
IB-1



I-16
H
IR-16
IB-1



I-17
H
IR-21
IB-1



I-18
H
IR-22
IB-1



I-19
H
IR-23
IB-1



I-20
H
IR-24
IB-1



I-21
H
IR-25
IB-1



I-22
H
IR-26
IB-1



I-23
H
IR-27
IB-1



I-24
H
IR-28
IB-1



I-25
H
IR-29
IB-1



I-26
H
IR-30
IB-1



I-27
H
IR-31
IB-1



I-28
H
IR-32
IB-1



I-29
H
IR-33
IB-1



I-30
H
IR-34
IB-1



I-31
H
IR-35
IB-1



I-32
H
IR-36
IB-1



I-33
H
IR-37
IB-1



I-34
H
IR-38
IB-1



I-35
H
IR-51
IB-1



I-36
H
IR-52
IB-1



I-37
H
IR-53
IB-1



I-38
H
IR-54
IB-1



I-39
H
IR-55
IB-1



I-40
H
IR-56
IB-1



I-41
H
IR-61
IB-1



I-42
H
IR-91
IB-1



I-43
H
IR-92
IB-1



I-44
H
IR-93
IB-1



I-45
H
IR-94
IB-1



I-46
H
IR-95
IB-1



I-47
H
IR-96
IB-1



I-48
H
IR-101
IB-1



I-49
H
IR-102
IB-1



I-50
H
IR-103
IB-1



I-51
H
IR-104
IB-1



I-52
H
IR-105
IB-1



I-53
H
IR-106
IB-1



I-54
H
IR-111
IB-1



I-55
H
IR-112
IB-1



I-56
H
IR-113
IB-1



I-57
H
IR-114
IB-1



I-58
H
IR-115
IB-1



I-59
H
IR-116
IB-1



I-60
H
IR-117
IB-1



I-61
H
IR-118
IB-1



I-61-1
H
IR-119
IB-1



I-62
H
IR-121
IB-1



I-63
H
IR-122
IB-1



I-64
H
IR-123
IB-1



I-65
H
IR-124
IB-1



I-66
H
IR-125
IB-1



I-67
H
IR-126
IB-1



I-68
H
IR-131
IB-1



I-69
H
IR-132
IB-1



I-70
H
IR-133
IB-1



I-71
H
IR-134
IB-1



I-72
H
IR-135
IB-1



I-73
H
IR-141
IB-1



I-74
H
IR-142
IB-1



I-75
H
IR-143
IB-1



I-76
H
IR-144
IB-1



I-77
H
IR-145
IB-1



I-78
H
IR-151
IB-1



I-79
H
IR-152
IB-1



I-80
H
IR-153
IB-1



I-81
H
IR-154
IB-1



I-82
H
IR-155
IB-1



I-82-1
H
IR-156
IB-1



I-82-2
H
IR-157
IB-1



I-82-3
H
IR-158
IB-1



I-82-4
H
IR-159
IB-1



I-83
H
IR-161
IB-1



I-84
H
IR-162
IB-1



I-85
H
IR-163
IB-1



I-86
H
IR-164
IB-1



I-87
H
IR-165
IB-1



I-88
H
IR-171
IB-1



I-89
H
IR-172
IB-1



I-90
H
IR-173
IB-1



I-91
H
IR-174
IB-1



I-92
H
IR-181
IB-1



I-93
H
IR-182
IB-1



I-94
H
IR-183
IB-1



I-95
H
IR-184
IB-1



I-96
H
IR-191
IB-1



I-97
H
IR-192
IB-1



I-98
H
IR-193
IB-1



I-99
H
IR-194
IB-1



I-100
H
IR-195
IB-1



I-101
H
IR-196
IB-1



I-102
H
IR-197
IB-1



I-103
H
IR-198
IB-1



I-104
H
IR-199
IB-1



I-105
H
IR-200
IB-1



I-106
H
IR-211
IB-1



I-107
H
IR-212
IB-1



I-108
H
IR-213
IB-1



I-109
H
IR-214
IB-1



I-110
H
IR-221
IB-1



I-111
H
IR-231
IB-1



I-112
H
IR-241
IB-1



I-112-1
H
IR-245
IB-1



I-113
H
IR-251
IB-1



I-114
H
IR-261
IB-1



I-115
H
IR-262
IB-1



I-116
H
IR-263
IB-1



I-117
H
IR-264
IB-1



I-118
H
IR-265
IB-1



I-119
H
IR-266
IB-1



I-120
H
IR-271
IB-1



I-121
H
IR-272
IB-1



I-122
H
IR-273
IB-1



I-123
H
IR-274
IB-1



I-124
H
IR-275
IB-1



I-125
H
IR-276
IB-1



I-126
H
IR-281
IB-1



I-127
H
IR-282
IB-1



I-128
H
IR-283
IB-1



I-129
H
IR-284
IB-1



I-130
H
IR-285
IB-1



I-131
H
IR-286
IB-1



I-132
IR-1
IR-1
IB-1



I-133
IR-2
IR-2
IB-1



I-134
IR-3
IR-3
IB-1



I-135
IR-4
IR-4
IB-1



I-136
IR-5
IR-5
IB-1



I-137
IR-6
IR-6
IB-1



I-138
IR-7
IR-7
IB-1



I-139
IR-8
IR-8
IB-1



I-140
IR-9
IR-9
IB-1



I-141
IR-10
IR-10
IB-1



I-142
IR-11
IR-11
IB-1



I-143
IR-12
IR-12
IB-1



I-144
IR-13
IR-13
IB-1



I-145
IR-14
IR-14
IB-1



I-146
IR-15
IR-15
IB-1



I-147
IR-16
IR-16
IB-1



I-148
IR-21
IR-21
IB-1



I-149
IR-22
IR-22
IB-1



I-150
IR-23
IR-23
IB-1



I-151
IR-24
IR-24
IB-1



I-152
IR-25
IR-25
IB-1



I-153
IR-26
IR-26
IB-1



I-154
IR-27
IR-27
IB-1



I-155
IR-28
IR-28
IB-1



I-156
IR-29
IR-29
IB-1



I-157
IR-30
IR-30
IB-1



I-158
IR-31
IR-31
IB-1



I-159
IR-32
IR-32
IB-1



I-160
IR-33
IR-33
IB-1



I-161
IR-34
IR-34
IB-1



I-162
IR-35
IR-35
IB-1



I-163
IR-36
IR-36
IB-1



I-164
IR-37
IR-37
IB-1



I-165
IR-38
IR-38
IB-1



I-166
H
IR-287
IB-1



I-167
H
IR-288
IB-1



I-168
H
IR-289
IB-1



I-169
H
IR-290
IB-1



I-170
IR-271
IR-23
IB-1



I-171
IR-271
IR-24
IB-1



I-172
IR-271
IR-30
IB-1













Salt
Ring formed with R1A, R2A and N
Cation





I-201
IR-301
IB-1


I-202
IR-302
IB-1


I-203
IR-303
IB-1


I-204
IR-304
IB-1


I-205
IR-305
IB-1


I-206
IR-306
IB-1


I-207
IR-307
IB-1


I-208
IR-308
IB-1


I-209
IR-309
IB-1


I-210
IR-310
IB-1


I-211
IR-311
IB-1


I-212
IR-312
IB-1


I-213
IR-313
IB-1


I-214
IR-314
IB-1


I-215
IR-315
IB-1


I-216
IR-316
IB-1


I-217
IR-317
IB-1


I-218
IR-318
IB-1


I-219
IR-319
IB-1


I-220
IR-320
IB-1


I-221
IR-321
IB-1


I-222
IR-322
IB-1


I-223
IR-323
IB-1


I-224
IR-324
IB-1


I-225
IR-325
IB-1


I-226
IR-326
IB-1


I-227
IR-327
IB-1


I-228
IR-328
IB-1


I-229
IR-329
IB-1















Salt
R1A
R2A
Cation







I-301
H
IR-6
IB-10



I-302
H
IR-6
IB-12



I-303
H
IR-6
IB-21



I-304
H
IR-6
IC-49



I-305
H
IR-23
IB-10



I-306
H
IR-23
IB-12



I-307
H
IR-23
IB-21



I-308
H
IR-23
IC-49



I-309
H
IR-24
IB-10



I-310
H
IR-24
IB-12



I-311
H
IR-24
IB-21



I-312
H
IR-24
IC-49



I-313
H
IR-30
IB-10



I-314
H
IR-30
IB-12



I-315
H
IR-30
IB-21



I-316
H
IR-30
IC-49



I-317
H
IR-33
IB-10



I-318
H
IR-33
IB-12



I-319
H
IR-33
IB-21



I-320
H
IR-33
IC-49



I-321
H
IR-35
IB-10



I-322
H
IR-35
IB-12



I-323
H
IR-35
IB-21



I-324
H
IR-35
IC-49



I-325
H
IR-113
IB-10



I-326
H
IR-113
IB-12



I-327
H
IR-113
IB-21



I-328
H
IR-113
IC-49



I-329
H
IR-131
IB-10



I-330
H
IR-131
IB-12



I-331
H
IR-131
IB-21



I-332
H
IR-131
IC-49



I-333
H
IR-151
IB-10



I-334
H
IR-151
IB-12



I-335
H
IR-151
IB-21



I-336
H
IR-151
IC-49



I-337
H
IR-172
IB-10



I-338
H
IR-172
IB-12



I-339
H
IR-172
IB-21



I-340
H
IR-172
IC-49



I-341
H
IR-194
IB-10



I-342
H
IR-194
IB-12



I-343
H
IR-194
IB-21



I-344
H
IR-194
IC-49



I-345
IR-23
IR-23
IB-10



I-346
IR-23
IR-23
IB-12



I-347
IR-23
IR-23
IB-21



I-348
IR-23
IR-23
IC-49



I-349
IR-24
IR-24
IB-10



I-350
IR-24
IR-24
IB-12



I-351
IR-24
IR-24
IB-21



I-352
IR-24
IR-24
IC-49



I-353
H
IR-287
IB-6



I-354
H
IR-287
IB-10



I-355
H
IR-287
IC-49



I-356
H
IR-288
IB-6



I-357
H
IR-288
IB-10



I-358
H
IR-288
IC-49



I-359
H
IR-289
IB-6



I-360
H
IR-289
IB-10



I-361
H
IR-289
IC-49



I-362
H
IR-290
IB-6



I-363
H
IR-290
IB-10



I-364
H
IR-290
IC-49



I-365
H
IR-193
IB-6



I-366
H
IR-193
IB-10



I-367
H
IR-193
IC-49



I-368
IR-271
IR-23
IB-10



I-369
IR-271
IR-24
IB-10



I-370
IR-271
IR-30
IB-10















Salt
Ring formed with R1A, R2A and N
Cation







I-401
IR-306
IB-10



I-402
IR-306
IB-12



I-403
IR-306
IB-21



I-404
IR-306
IC-49



I-405
IR-314
IB-10



I-406
IR-314
IB-12



I-407
IR-314
IB-21



I-408
IR-314
IC-49



I-409
IR-316
IB-10



I-410
IR-316
IB-12



I-411
IR-316
IB-21



I-412
IR-316
IC-49



I-413
IR-305
IB-6



I-414
IR-305
IB-10



I-415
IR-305
IC-49



I-416
IR-326
IB-6



I-417
IR-326
IB-10



I-418
IR-326
IC-49



I-419
IR-327
IB-6



I-420
IR-327
IB-10



I-421
IR-327
IC-49



I-422
IR-328
IB-6



I-423
IR-328
IB-10



I-424
IR-328
IC-49



I-425
IR-329
IB-6



I-426
IR-329
IB-10



I-427
IR-329
IC-49
















Salt
R1A
R2A
Cation







I′-1
H
IR-30
ID-11



I′-2
IR-1
IR-30
ID-11



I′-3
IR-2
IR-30
ID-11



I′-4
IR-3
IR-30
ID-11



I′-5
IR-4
IR-30
ID-11



I′-6
IR-5
IR-30
ID-11



I′-7
IR-6
IR-30
ID-11



I′-8
IR-7
IR-30
ID-11



I′-9
IR-8
IR-30
ID-11



I′-10
IR-9
IR-30
ID-11



I′-11
IR-10
IR-30
ID-11



I′-12
IR-11
IR-30
ID-11



I′-13
IR-12
IR-30
ID-11



I′-14
IR-13
IR-30
ID-11



I′-15
IR-14
IR-30
ID-11



I′-16
IR-15
IR-30
ID-11



I′-17
IR-21
IR-30
ID-11



I′-18
IR-22
IR-30
ID-11



I′-19
IR-23
IR-30
ID-11



I′-20
IR-24
IR-30
ID-11



I′-21
IR-25
IR-30
ID-11



I′-22
IR-26
IR-30
ID-11



I′-23
IR-27
IR-30
ID-11



I′-24
IR-28
IR-30
ID-11



I′-25
IR-29
IR-30
ID-11



I′-26
IR-30
IR-30
ID-11



I′-27
IR-31
IR-30
ID-11



I′-28
IR-32
IR-30
ID-11



I′-29
IR-33
IR-30
ID-11



I′-30
IR-34
IR-30
ID-11



I′-31
IR-35
IR-30
ID-11



I′-32
IR-36
IR-30
ID-11



I′-33
IR-37
IR-30
ID-11



I′-34
IR-38
IR-30
ID-11



I′-35
IR-51
IR-30
ID-11



I′-36
IR-52
IR-30
ID-11



I′-37
IR-53
IR-30
ID-11



I′-38
IR-54
IR-30
ID-11



I′-39
IR-55
IR-30
ID-11



I′-40
IR-56
IR-30
ID-11



I′-41
IR-61
IR-30
ID-11



I′-42
IR-91
IR-30
ID-11



I′-43
IR-92
IR-30
ID-11



I′-44
IR-93
IR-30
ID-11



I′-45
IR-94
IR-30
ID-11



I′-46
IR-95
IR-30
ID-11



I′-47
IR-96
IR-30
ID-11



I′-48
IR-101
IR-30
ID-11



I′-49
IR-102
IR-30
ID-11



I′-50
IR-103
IR-30
ID-11



I′-51
IR-104
IR-30
ID-11



I′-52
IR-105
IR-30
ID-11



I′-53
IR-106
IR-30
ID-11



I′-54
IR-111
IR-30
ID-11



I′-55
IR-112
IR-30
ID-11



I′-56
IR-113
IR-30
ID-11



I′-57
IR-114
IR-30
ID-11



I′-58
IR-115
IR-30
ID-11



I′-59
IR-116
IR-30
ID-11



I′-60
IR-117
IR-30
ID-11



I′-61
IR-118
IR-30
ID-11



I′-61-1
IR-119
IR-30
ID-11



I′-62
IR-121
IR-30
ID-11



I′-63
IR-122
IR-30
ID-11



I′-64
IR-123
IR-30
ID-11



I′-65
IR-124
IR-30
ID-11



I′-66
IR-125
IR-30
ID-11



I′-67
IR-126
IR-30
ID-11



I′-68
IR-131
IR-30
ID-11



I′-69
IR-132
IR-30
ID-11



I′-70
IR-133
IR-30
ID-11



I′-71
IR-134
IR-30
ID-11



I′-72
IR-135
IR-30
ID-11



I′-73
IR-141
IR-30
ID-11



I′-74
IR-142
IR-30
ID-11



I′-75
IR-143
IR-30
ID-11



I′-76
IR-144
IR-30
ID-11



I′-77
IR-145
IR-30
ID-11



I′-78
IR-151
IR-30
ID-11



I′-79
IR-152
IR-30
ID-11



I′-80
IR-153
IR-30
ID-11



I′-81
IR-154
IR-30
ID-11



I′-82
IR-155
IR-30
ID-11



I′-82-1
IR-156
IR-30
ID-11



I′-82-2
IR-157
IR-30
ID-11



I′-82-3
IR-158
IR-30
ID-11



I′-82-4
IR-159
IR-30
ID-11



I′-83
IR-161
IR-30
ID-11



I′-84
IR-162
IR-30
ID-11



I′-85
IR-163
IR-30
ID-11



I′-86
IR-164
IR-30
ID-11



I′-87
IR-165
IR-30
ID-11



I′-88
IR-171
IR-30
ID-11



I′-89
IR-172
IR-30
ID-11



I′-90
IR-173
IR-30
ID-11



I′-91
IR-174
IR-30
ID-11



I′-92
IR-181
IR-30
ID-11



I′-93
IR-182
IR-30
ID-11



I′-94
IR-183
IR-30
ID-11



I′-95
IR-184
IR-30
ID-11



I′-96
IR-191
IR-30
ID-11



I′-97
IR-192
IR-30
ID-11



I′-98
IR-193
IR-30
ID-11



I′-99
IR-194
IR-30
ID-11



I′-100
IR-195
IR-30
ID-11



I′-101
IR-196
IR-30
ID-11



I′-102
IR-197
IR-30
ID-11



I′-103
IR-198
IR-30
ID-11



I′-104
IR-199
IR-30
ID-11



I′-105
IR-200
IR-30
ID-11



I′-106
IR-211
IR-30
ID-11



I′-107
IR-212
IR-30
ID-11



I′-108
IR-213
IR-30
ID-11



I′-109
IR-214
IR-30
ID-11



I′-110
IR-221
IR-30
ID-11



I′-111
IR-231
IR-30
ID-11



I′-112
IR-241
IR-30
ID-11



I′-112-1
IR-245
IR-30
ID-11



I′-113
IR-251
IR-30
ID-11



I′-114
IR-261
IR-30
ID-11



I′-115
IR-262
IR-30
ID-11



I′-116
IR-263
IR-30
ID-11



I′-117
IR-264
IR-30
ID-11



I′-118
IR-265
IR-30
ID-11



I′-119
IR-266
IR-30
ID-11



I′-120
IR-271
IR-30
ID-11



I′-121
IR-272
IR-30
ID-11



I′-122
IR-273
IR-30
ID-11



I′-123
IR-274
IR-30
ID-11



I′-124
IR-275
IR-30
ID-11



I′-125
IR-276
IR-30
ID-11



I′-126
IR-281
IR-30
ID-11



I′-127
IR-282
IR-30
ID-11



I′-128
IR-283
IR-30
ID-11



I′-129
IR-284
IR-30
ID-11



I′-130
IR-285
IR-30
ID-11



I′-131
IR-286
IR-30
ID-11



I′-132
IR-287
IR-30
ID-11



I′-133
IR-288
IR-30
ID-11



I′-134
IR-289
IR-30
ID-11



I′-135
IR-290
IR-30
ID-11



I′-136
IR-10
IR-10
ID-11



I′-137
IR-11
IR-11
ID-11



I′-138
IR-12
IR-12
ID-11



I′-139
IR-13
IR-13
ID-11



I′-140
IR-14
IR-14
ID-11



I′-141
IR-15
IR-15
ID-11



I′-142
IR-16
IR-16
ID-11



I′-143
IR-21
IR-21
ID-11



I′-144
IR-22
IR-22
ID-11



I′-145
IR-23
IR-23
ID-11



I′-146
IR-24
IR-24
ID-11



I′-147
IR-25
IR-25
ID-11



I′-148
IR-26
IR-26
ID-11



I′-149
IR-27
IR-27
ID-11



I′-150
IR-28
IR-28
ID-11



I′-151
IR-29
IR-29
ID-11



I′-152
IR-30
IR-30
ID-11



I′-153
IR-31
IR-31
ID-11



I′-154
IR-32
IR-32
ID-11



I′-155
IR-33
IR-33
ID-11



I′-156
IR-34
IR-34
ID-11



I′-157
IR-35
IR-35
ID-11



I′-158
IR-36
IR-36
ID-11



I′-159
IR-37
IR-37
ID-11



I′-160
IR-38
IR-38
ID-11













Salt
Ring formed with R1A, R2A and N
Cation





I′-201
IR-301
ID-11


I′-202
IR-302
ID-11


I′-203
IR-303
ID-11


I′-204
IR-304
ID-11


I′-205
IR-305
ID-11


I′-206
IR-306
ID-11


I′-207
IR-307
ID-11


I′-208
IR-308
ID-11


I′-209
IR-309
ID-11


I′-210
IR-310
ID-11


I′-211
IR-311
ID-11


I′-212
IR-312
ID-11


I′-213
IR-313
ID-11


I′-214
IR-314
ID-11


I′-215
IR-315
ID-11


I′-216
IR-316
ID-11


I′-217
IR-317
ID-11


I′-218
IR-318
ID-11


I′-219
IR-319
ID-11


I′-220
IR-320
ID-11


I′-221
IR-321
ID-11


I′-222
IR-322
ID-11


I′-223
IR-323
ID-11


I′-224
IR-324
ID-11


I′-225
IR-325
ID-11


I′-226
IR-326
ID-11


I′-227
IR-327
ID-11


I′-228
IR-328
ID-11


I′-229
IR-329
ID-11















Salt
R1A
R2A
Cation







I′-301
IR-30
H
ID-1



I′-302
IR-30
H
ID-2



I′-303
IR-30
H
ID-3



I′-304
IR-30
H
ID-4



I′-305
IR-30
H
ID-5



I′-306
IR-30
H
ID-6



I′-307
IR-30
H
ID-7



I′-308
IR-30
H
ID-8



I′-309
IR-30
H
ID-9



I′-310
IR-30
H
ID-10



I′-311
IR-30
H
ID-12



I′-312
IR-30
H
ID-13



I′-313
IR-30
H
ID-14



I′-314
IR-30
IR-1
ID-1



I′-315
IR-30
IR-1
ID-9



I′-316
IR-30
IR-1
ID-10



I′-317
IR-30
IR-2
ID-1



I′-318
IR-30
IR-2
ID-9



I′-319
IR-30
IR-2
ID-10



I′-320
IR-30
IR-3
ID-1



I′-321
IR-30
IR-3
ID-9



I′-322
IR-30
IR-3
ID-10



I′-323
IR-30
IR-4
ID-1



I′-324
IR-30
IR-4
ID-9



I′-325
IR-30
IR-4
ID-10



I′-326
IR-30
IR-5
ID-1



I′-327
IR-30
IR-5
ID-9



I′-328
IR-30
IR-5
ID-10



I′-329
IR-30
IR-6
ID-1



I′-330
IR-30
IR-6
ID-9



I′-331
IR-30
IR-6
ID-10



I′-332
IR-30
IR-7
ID-1



I′-333
IR-30
IR-7
ID-9



I′-334
IR-30
IR-7
ID-10















Salt
Ring formed with R1A, R2A and N
Cation







I′-401
IR-305
ID-1



I′-402
IR-305
ID-9



I′-403
IR-306
ID-1



I′-404
IR-306
ID-9



I′-405
IR-314
ID-1



I′-406
IR-314
ID-9



I′-407
IR-315
ID-1



I′-408
IR-315
ID-9



I′-409
IR-316
ID-1



I′-410
IR-316
ID-2



I′-411
IR-316
ID-3



I′-412
IR-316
ID-4



I′-413
IR-316
ID-5



I′-414
IR-316
ID-6



I′-415
IR-316
ID-7



I′-416
IR-316
ID-8



I′-417
IR-316
ID-9



I′-418
IR-316
ID-10



I′-419
IR-316
ID-12



I′-420
IR-316
ID-13



I′-421
IR-316
ID-14



I′-422
IR-326
ID-1



I′-423
IR-326
ID-9



I′-424
IR-327
ID-1



I′-425
IR-327
ID-9



I′-426
IR-328
ID-1



I′-427
IR-328
IB-9










Among these, the salts represented by the formulae (I-19), (I-29), (I-78), (I-150), (I-151), (I-205), (I-206), (I-214), (I-216), (I-301), (I-305), (I-313), (I-317), (I-321), (I-325), (I-329), (I-333), (I-337), (I-341), (I-345), (I-349), (I-401), (I-405), (I-409), (I-410) are preferable, and the salts represented by the formulae (I-151), (I-216), (I-309), (I-313), (I-366), (I-349), (I-401), (I-409), (I-414), (I-417), (I-420) are more preferable. Also, the salts represented by the formulae (I′-1), (I′-2), (I′-216), (I′-228), (I′-301), (I′-305), (I′-409) are preferable, and the salts represented by the formulae (I′-1) and (I′-216) are more preferable.
(1) The sulfonium salt having the anion (IA) and the cation represented by the formula (IB) can be produced by the method described below.
A salt represented by the formula (IA-R2) can be produced by reacting an amine represented by the formula (IA-R1) with a sulfur-containing compound selected from chlorosulfuric acid, sulfuric ion or sulfur trioxide in a solvent under basic condition.
The sulfonium salt having the anion (IA) and the sulfonium salt having sulfonium cation represented by the formula (IB) can be produced by reacting the obtained salt represented by the formula (IA-R2) with a salt represented by the formula (IB-R1) in a solvent. Preferred examples of the solvent include organic solvent such as chloroform, dichloroethane, dichloromethane, acetonitrile, dimethyl formamide and tetrahydrofuran. Preferred examples of the base include triethylamine, DBU, dimethylamino pyridine and pyridine.




wherein XA1+ represents an ammonium cation;
XB1+ represents halogen anion selected from Cl, Br, I, or an alkyl sulfate ion, a sulfate ion, a carboxylate anion, an alkoxy anion, or a hydroxide ion.
(2) A sulfonium salt having an anion (IA) and a cation represented by the formula (ID) can be produced by the method described below.
A salt represented by the formula (IA-R2) can be produced by reacting an amine represented by the formula (IA-R1) with a sulfur-containing compound selected from chlorosulfuric acid, sulfuric ion or sulfur trioxide in a solvent under basic condition.
The sulfonium salt having an anion (IA) and a cation represented by the formula (ID) can be produced by stirring the obtained salt represented by the formula (IA-R2) and a salt represented by the formula (ID-R1) in a solvent. Preferred examples of the solvent include organic solvent such as chloroform, dichloroethane, dichloromethane, acetonitrile, dimethyl formamide and tetrahydrofuran. Preferred examples of the base include triethylamine, DBU, dimethylamino pyridine and pyridine




wherein XA1+ and XB1+ represent the same meaning as described above.
The salt having the anion (IA) may be used as a single salt or as a combination of two or more salts.
The salt having the anion (IA) contains preferably 0.01 to 1.5 parts by weight, and more preferably 0.02 to 0.5 parts by weight, with respect to 10 parts by weight of the resin (A) in the resist composition.
<Solvent (E)>
The resist composition of the present invention may include a solvent (E) in the amount of 90 weight % or more, preferably 92 weight % or more, and more preferably 94 weight % or more, and 99.9 weight % or less, preferably 99 weight % or less in the composition.
The content of the solvent (E) can be measured with a known analytical method such as, for example, liquid chromatography and gas chromatography.
Examples of the solvent (E) include glycol ether esters such as ethylcellosolve acetate, methylcellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethers such as diethylene glycol dimethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; and cyclic esters such as γ-butyrolactone. These solvents may be used as a single solvent or as a mixture of two or more solvents.
<Basic Compound (C)>
The resist composition of the present invention may contain a basic compound (C). The basic compound (C) is a compound having a property to quench an acid, in particular, generated from the acid generator (B), and called “quencher”.
As the basic compounds (C), nitrogen-containing basic compounds (for example, amine and basic ammonium salt) are preferable. The amine may be an aliphatic amine or an aromatic amine. The aliphatic amine includes any of a primary amine, secondary amine and tertiary amine. Preferred basic compounds (C) include compounds presented by the formula (C1) to the formula (C8) and the formula (C1-1) as described below. Among these, the basic compound presented by the formula (C1-1) is more preferable.




wherein Rc1, Rc2 and Rc3 independently represent a hydrogen atom, a C1 to C6 alkyl group, C5 to C10 alicyclic hydrocarbon group or a C6 to C10 aromatic hydrocarbon group, one or more hydrogen atom contained in the alkyl group and alicyclic hydrocarbon group may be replaced by a hydroxy group, an amino group or a C1 to C6 alkoxyl group, one or more hydrogen atom contained in the aromatic hydrocarbon group may be replaced by a C1 to C6 alkyl group, a C1 to C6 alkoxyl group, a C5 to C10 alicyclic hydrocarbon group or a C6 to C10 aromatic hydrocarbon group.




wherein Rc2 and Rc3 have the same definition of the above;
Rc4 in each occurrence represents a C1 to C6 alkyl group, a C1 to C6 alkoxyl group, a C5 to C10 alicyclic hydrocarbon group or a C6 to C10 aromatic hydrocarbon group;
m3 represents an integer 0 to 3.




wherein Rc5, Rc6, Rc7 and Rc8 independently represent the any of the group as described in Rc1 of the above;
Rc9 in each occurrence independently represents a C1 to C6 alkyl group, a C3 to C6 alicyclic hydrocarbon group or a C2 to C6 alkanoyl group;
n3 represents an integer of 0 to 8.




wherein Rc10, Rc11, Rc12, Rc13 and Rc16 independently represent the any of the groups as described in Rc1;
Rc14, Rc15 and Rc17 in each occurrence independently represent the any of the groups as described in Rc4;
o3 and p3 represent an integer of 0 to 3;
Lc1 represents a divalent C1 to C6 alkanediyl group, —CO—, —C(═NH)—, —S— or a combination thereof.




wherein Rc18, Rc19 and Rc20 in each occurrence independently represent the any of the groups as described in Rc4;
q3, r3 and s3 represent an integer of 0 to 3;
Lc2 represents a single bond, a C1 to C6 alkanediyl group, —CO—, —C(═NH)—, —S— or a combination thereof.
In the formula (C1) to the formula (C8) and the formula (C1-1), the alkyl, alicyclic hydrocarbon, aromatic, alkoxy and alkanediyl groups include the same examples as the above.
Examples of the alkanoyl group include acetyl, 2-methyl acetyl, 2,2-dimethyl acetyl, propionyl, butyryl, isobutyryl, pentanoyl and 2,2-dimethyl propionyl groups.
Specific examples of the amine represented by the formula (C1) include 1-naphtylamine, 2-naphtylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylene diamine, tetramethylene diamine, hexamethylene diamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane and 4,4′-diamino-3,3′-diethyldiphenylmethane.
Among these, diisopropylaniline is preferable, particularly 2,6-diisopropylaniline is more preferable as the basic compounds (C) contained in the present resist composition.
Specific examples of the compound represented by the formula (C2) include, for example, piperazine.
Specific examples of the compound represented by the formula (C3) include, for example, morpholine.
Specific examples of the compound represented by the formula (C4) include, for example, piperidine, a hindered amine compound having piperidine skeleton described in JP H11-52575-A.
Specific examples of the compound represented by the formula (C5) include, for example, 2,2′-methylenebisaniline.
Specific examples of the compound represented by the formula (C6) include, for example, imidazole and 4-methylimidazole.
Specific examples of the compound represented by the formula (C7) include, for example, pyridine and 4-methylpyridine.
Specific examples of the compound represented by the formula (C8) include, for example, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4′-dipyridyl sulfide, 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipicolylamine and bipyridine.
Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethyl ammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butyl ammonium salicylate and choline.
The proportion of the basic compound (C) is preferably 0.01 to 5 weight %, more preferably 0.01 to 3 weight %, and still more preferably 0.01 to 1 weight % with respect to the total solid proportion of the resist composition.
<Other Ingredient (Hereinafter is Sometimes Referred to as “Other Ingredient (F)”>
The resist composition can also include small amounts of various known additives such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes, as needed.
<Preparing the Resist Composition>
The present resist composition can be prepared by mixing the resin (A1), the resin (A2), the acid generator (B) and the salt having the anion (IA), and the basic compound (C), the solvent (E) and the other ingredient (F) as needed. There is no particular limitation on the order of mixing. The mixing may be performed in an arbitrary order. The temperature of mixing may be adjusted to an appropriate temperature within the range of 10 to 40° C., depending on the kinds of the resin and solubility in the solvent (E) of the resin. The time of mixing may be adjusted to an appropriate time within the range of 0.5 to 24 hours, depending on the mixing temperature. There is no particular limitation to the tool for mixing. An agitation mixing may be adopted.
After mixing the above ingredients, the present resist compositions can be prepared by filtering the mixture through a filter having about 0.003 to 0.2 μm pore diameter.
<Method for Producing a Resist Pattern>
The method for producing a resist pattern of the present invention includes the steps of:
(1) applying the resist composition of the present invention onto a substrate;
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) heating the exposed composition layer, and
(5) developing the heated composition layer.
Applying the resist composition onto the substrate can generally be carried out through the use of a resist application device, such as a spin coater known in the field of semiconductor microfabrication technique.
Drying the applied composition layer, for example, can be carried out using a heating device such as a hotplate (so-called “prebake”), a decompression device, or a combination thereof. Thus, the solvent evaporates from the resist composition and a composition layer with the solvent removed is formed. The condition of the heating device or the decompression device can be adjusted depending on the kinds of the solvent used. The temperature in this case is generally within the range of 50 to 200° C. Moreover, the pressure is generally within the range of 1 to 1.0×105 Pa.
The composition layer thus obtained is generally exposed using an exposure apparatus or a liquid immersion exposure apparatus. The exposure is generally carried out through a mask that corresponds to the desired pattern. Various types of exposure light source can be used, such as irradiation with ultraviolet lasers such as KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F2 excimer laser (wavelength: 157 nm), or irradiation with far-ultraviolet wavelength-converted laser light from a solid-state laser source (YAG or semiconductor laser or the like), or vacuum ultraviolet harmonic laser light or the like. Also, the exposure device may be one which irradiates electron beam or extreme-ultraviolet light (EUV).
After exposure, the composition layer is subjected to a heat treatment (so-called “post-exposure bake”) to promote the deprotection reaction. The heat treatment can be carried out using a heating device such as a hotplate. The heating temperature is generally in the range of 50 to 200° C., preferably in the range of 70 to 150° C.
The composition layer is developed after the heat treatment, generally with an alkaline developing solution and using a developing apparatus. The development here means to bring the composition layer after the heat treatment into contact with an alkaline solution. Thus, the exposed portion of the composition layer is dissolved by the alkaline solution and removed, and the unexposed portion of the composition layer remains on the substrate, whereby producing a resist pattern. Here, as the alkaline developing solution, various types of aqueous alkaline solutions used in this field can be used. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (common name: choline).
After the development, it is preferable to rinse the substrate and the pattern with ultrapure water and to remove any residual water thereon.
<Application>
The resist composition of the present invention is useful as the resist composition for excimer laser lithography such as with ArF, KrF or the like, and the resist composition for electron beam (EB) exposure lithography and extreme-ultraviolet (EUV) exposure lithography, as well as liquid immersion exposure lithography.
The resist composition of the present invention can be used in semiconductor microfabrication and in manufacture of liquid crystals, thermal print heads for circuit boards and the like, and furthermore in other photofabrication processes, which can be suitably used in a wide range of applications.
EXAMPLES
The present invention will be described more specifically by way of examples, which are not construed to limit the scope of the present invention.
All percentages and parts expressing the content or amounts used in the Examples and Comparative Examples are based on weight, unless otherwise specified.
The structure of a compound is measured by MASS (LC: manufactured by Agilent, 1100 type, MASS: manufactured by Agilent, LC/MSD type or LC/MSD TOF type).
The weight average molecular weight is a value determined by gel permeation chromatography.
Apparatus: HLC-8120GPC type (Tosoh Co. Ltd.)
Column: TSK gel Multipore HXL-M×3+guardcolumn (Tosoh Co. Ltd.)
Eluant: tetrahydrofuran
Flow rate: 1.0 mL/min
Detecting device: R1 detector
Column temperature: 40° C.
Injection amount: 100 μl,
Standard material for calculating molecular weight: standard polystylene (Toso Co. ltd.)
Synthesis Example 1
Synthesis of Compound Represented by the Formula (A)




9.60 parts of a compound (A-2), 38.40 parts of tetrahydrofuran and 5.99 parts of pyridine were mixed, and stirred for 30 minutes at 23° C. The obtained mixture was cooled to 0° C. To this mixture, 14.00 parts of a compound (A-1) was added over 1 hour while maintaining at the same temperature. The temperature of the mixture was then elevated to about 10° C., and the mixture was stirred for 1 hour at the same temperature. To the obtained reactant including a compound (A-3), 14.51 parts of a compound of (A-4), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, and 8.20 parts of a compound of (A-5) were added, and stirred for 3 hours at 23° C. 271.95 parts of ethyl acetate and 16.57 parts of 5% of hydrochloric acid solution were added to the obtained mixture, the mixture was stirred for 30 minutes at 23° C. The obtained solution was allowed to stand, and then separated to recover an organic layer. To the recovered organic layer, 63.64 parts of a saturated sodium hydrogen carbonate was added, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer. These washing operations were repeated for 2 times. To the washed organic layer, 67.99 parts of ion-exchanged water was added, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer with water. These washing operations were repeated for 5 times. The obtained organic layer was concentrated, to the obtained concentrate, 107.71 parts of ethyl acetate was added, stirred to dissolve the concentrate completely, and 64.26 parts of n-heptane was added in the form of drops to this. After addition, the obtained mixture was stirred for 30 minutes at 23° C., and filtrated, resulting in 15.11 parts of the compound (A).
MS (mass spectroscopy): 486.2 (molecular ion peak)
Synthesis Example 2
Synthesis of Compound Represented by the Formula (B)




6.32 parts of a compound (B-2), 30.00 parts of tetrahydrofuran and 5.99 parts of pyridine were mixed, and stirred for 30 minutes at 23° C. The obtained mixture was cooled to 0° C. To this mixture, 14.00 parts of a compound (B-1) was added over 1 hour while maintaining at the same temperature. The temperature of the mixture was then elevated to about 10° C., and the mixture was stirred for 1 hour at the same temperature. To the obtained reactant including a compound (B-3), 14.51 parts of a compound of (B-4), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, and 8.20 parts of a compound of (B-5) were added, and stirred for 3 hours at 23° C. 270.00 parts of ethyl acetate and 16.57 parts of 5% of hydrochloric acid solution were added to the obtained mixture, the mixture was stirred for 30 minutes at 23° C. The obtained solution was allowed to stand, and then separated to recover an organic layer. To the recovered organic layer, 65.00 parts of a saturated sodium hydrogen carbonate was added, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer. These washing operations were repeated for 2 times. To the washed organic layer was added 65.00 parts of ion-exchanged water, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer with water. These washing operations were repeated for 5 times. The obtained organic layer was concentrated, to the obtained concentrate, and separated by a column (condition; stationary phase: silica gel 60-200 mesh manufactured by Merk, developing solvent: n-heptane/ethyl acetate), resulting in 9.90 parts of the compound (B).
MS (mass spectroscopy): 434.1 (molecular ion peak)
Synthesis Example 3
Synthesis of Compound Represented by the Formula (C)




7.08 parts of a compound (C-2), 30.00 parts of tetrahydrofuran and 5.99 parts of pyridine were mixed, and stirred for 30 minutes at 23° C. The obtained mixture was cooled to 0° C. To this mixture, 14.00 parts of a compound (C-1) was added over 1 hour while maintaining at the same temperature. The temperature of the mixture was then elevated to about 10° C., and the mixture was stirred for 1 hour at the same temperature. To the obtained reactant including a compound (C-3), 14.51 parts of a compound of (C-4), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, and 8.20 parts of a compound of (C-5) were added, and stirred for 3 hours at 23° C. 270.00 parts of ethyl acetate and 16.57 parts of 5% of hydrochloric acid solution were added to the obtained mixture, the mixture was stirred for 30 minutes at 23° C. The obtained solution was allowed to stand, and then separated to recover an organic layer. To the recovered organic layer, 65.00 parts of a saturated sodium hydrogen carbonate was added, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer. These washing operations were repeated for 2 times. To the washed organic layer was added 65.00 parts of ion-exchanged water, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer with water. These washing operations were repeated for 5 times. The obtained organic layer was concentrated, to the obtained concentrate, and separated by a column (condition; stationary phase: silica gel 60-200 mesh manufactured by Merk, developing solvent: n-heptane/ethyl acetate), resulting in 10.24 parts of the compound (C).
MS (mass spectroscopy): 446.1 (molecular ion peak)
Synthesis Example 4
Synthesis of Compound Represented by the Formula (E)




25 parts of a compound (E-1) and 25 parts of tetrahydrofuran were mixed, and stirred for 30 minutes at 23° C. The obtained mixture was cooled to 0° C. To this mixture, 10.2 parts of a compound (E-2), 11.2 parts of pyridine and 30 parts of tetrahydrofuran were added over 1 hour while maintaining at the same temperature. The temperature of the mixture was then elevated to about 25° C., and the mixture was stirred for 1 hour at the same temperature. To the obtained reactant, 200 parts of ethyl acetate and 50 parts of ion-exchanged-water were added, stirred, and then separated to recover an organic layer. The obtained organic layer was concentrated, to this concentrate, 500 parts of n-heptane was added to obtain a solution, and the solution was stirred and filtrated, resulting in 40.18 parts of a compound (E-3). 35.21 parts of the compound (E-3), 160 parts of tetrahydrofuran, 22.8 parts of the compound (E-5) and 8.3 parts of pyridine were charged, and stirred for 30 minutes at 23° C. The obtained mixture was cooled to 0° C. To the obtained mixture, 33.6 parts of a compound of (E-4), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, and 140 parts of chloroform were added, and stirred for 18 hours at 23° C. To this reactant solution, 850 parts of n-heptane and 77 parts of 5% of hydrochloric acid solution were added, the mixture was stirred for 30 minutes at 23° C. The obtained solution was allowed to stand, and then separated to recover an organic layer. To the recovered organic layer, 61 parts of 10% potassium carbonate was added, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer. These washing operations were repeated for 2 times. To the washed organic layer, 230 parts of ion-exchanged water was added, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer with water. These washing operations were repeated for 5 times. The obtained organic layer was concentrated, resulting in 31.5 parts of the compound (E).
MS (mass spectroscopy): 420.1 (molecular ion peak)
Synthesis Example 5
Synthesis of Compound Represented by the Formula (F)




25.00 parts of a compound (F-1) and 25.00 parts of tetrahydro tetrahydrofuran were mixed, and stirred for 30 minutes at 23° C. The obtained mixture was cooled to 0° C. To this mixture, a mixture of 8.50 parts of a compound (F-2), 25.00 parts of tetrahydrofuran and 11.2 parts of pyridine was added, over 1 hour while maintaining at the same temperature. The temperature of the mixture was then elevated to about 25° C., and the mixture was stirred for 1 hour at the same temperature. To the obtained reactant, 190 parts of ethyl acetate and 50 parts of ion-exchanged water were added, and then separated to recover an organic layer. The obtained organic layer was concentrated. To the obtained concentrate, 150.0 parts of n-heptane was added, and the obtained mixture was stirred, and the supernatant was removed. The obtained mixture was concentrated, resulting in 28.7 parts of the compound (F-3).
19.80 parts of a compound (F-3), 90.0 parts of tetrahydrofuran, 10.3 parts of a compound (F-5) and 5.0 parts of pyridine were mixed, and stirred for 30 minutes at 23° C. The obtained mixture was cooled to 0° C. To this mixture, 15.2 parts of a compound (F-4), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, was added, and stirred for 18 hours at 23° C. 450.0 parts of n-heptane and 47.0 parts of 5% of hydrochloric acid solution were added to the obtained mixture, the mixture was stirred for 30 minutes at 23° C. The obtained solution was allowed to stand, and then separated to recover an organic layer. To the recovered organic layer, 37.0 parts of 10% potassium carbonate was added, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer. These washing operations were repeated for 2 times. To the washed organic layer, 120.0 parts of ion-exchanged water was added, and the obtained solution was stirred for 30 minutes at 23° C., allowed to stand, and then separated to wash the organic layer with water. These washing operations were repeated for 5 times. The obtained organic layer was concentrated to the obtained concentrate, resulting in 20.1 parts of the compound (F).
MS (mass spectroscopy): 406.1 (molecular ion peak)
Synthesis Example 6
Synthesis of a Salt (I-409)




To a solution of 1.7 parts of a compound represented by the formula (I-409-b) (obtained from Tokyo Chemical Industry Co., LTD) and 50.00 parts of chloroform, 2.8 parts of trimethyl amine was added, cooled to −10° C., and 1.6 parts of a compound represented by the formula (I-409-c) was added thereto. After that, the obtained mixture was stirred for 1 hour at room temperature. To the reacted mixture, a salt represented by the formula (I-409-d) was added, and stirred over one night. 20 parts of ion-exchanged water was added to the obtained mixture, and the obtained mixture was extracted by chloroform. The chloroform solution was vacuum-concentrated, a mixture solution of acetonitrile and 2-methoxy-2-methylpropane was added thereto, and removed a supernatant by decantation. The obtained residue was dried, whereby giving 5.4 parts of a salt represented by the formula (I-409).
MS (ESI(+) Spectrum): M+ 305.1
MS (ESI(−) Spectrum): M− 218.1
Synthetic Example of the Resin
The monomers used the synthesis of the resin are shown below.













These monomers are referred to as “monomer (a1-1-1)” to “monomer (F)”.
Synthetic Example 7
Synthesis of Resin A1-1
Monomer (a4-1-7) and monomer (A) were mixed together with a mole ratio of Monomer (a4-1-7):monomer (A)=90:10, and dioxane was added thereto in an amount equal to 1.5 times by weight of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator to obtain a solution in an amount of 0.7 mol % and 2.1 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. After that, the obtained reacted mixture was poured into a large amount of methanol/water mixed solvent to precipitate a resin. The obtained resin was filtrated. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a mixture of methanol/water mixed solvent to precipitate a resin. The obtained resin was filtrated. These operations were repeated for two times, resulting in a 82% yield of copolymer having a weight average molecular weight of about 17000. This copolymer, which had the structural units of the following formula, was referred to Resin A1-1.




Synthetic Example 8
Synthesis of Resin A1-2
Monomer (B) was used, and dioxane was added thereto in an amount equal to 1.5 times by weight of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator to obtain a solution in an amount of 0.7 mol % and 2.1 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. After that, the obtained reacted mixture was poured into a large amount of methanol/water mixed solvent to precipitate a resin. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a mixture of methanol/water mixed solvent to precipitate a resin. The obtained resin was filtrated. These operations were repeated for two times, resulting in a 85% yield of polymer having a weight average molecular weight of about 20000. This polymer, which had the structural units of the following formula, was referred to Resin A1-2.




Synthetic Example 9
Synthesis of Resin A1-3
Monomer (C) was used, and dioxane was added thereto in an amount equal to 1.5 times by weight of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator to obtain a solution in an amount of 0.7 mol % and 2.1 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. After that, the obtained reacted mixture was poured into a large amount of methanol/water mixed solvent to precipitate a resin. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a mixture of methanol/water mixed solvent to precipitate a resin. The obtained resin was filtrated. These operations were repeated for two times, resulting in a 83% yield of polymer having a weight average molecular weight of about 19000. This polymer, which had the structural units of the following formula, was referred to Resin A1-3.




Synthetic Example 10
Synthesis of Resin A1-4
Monomer (E) was used, and dioxane was added thereto in an amount equal to 1.2 times by weight of the total amount of monomers to obtain a solution. Azobis(2,4-dimethylvaleronitrile) was added as an initiator to obtain a solution in an amount of 4.5 mol % with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 60° C. After that, the obtained reacted mixture was poured into a large amount of n-heptane to precipitate a resin. The obtained resin was filtrated, resulting in a 89% yield of polymer having a weight average molecular weight of about 26000. This polymer, which had the structural units of the following formula, was referred to Resin A1-4.




Synthetic Example 11
Synthesis of Resin A1-5
Monomer (F) was used, and dioxane was added thereto in an amount equal to 1.2 times by weight of the total amount of monomers to obtain a solution. Azobis(2,4-dimethylvaleronitrile) was added as an initiator to obtain a solution in an amount of 4.5 mol % with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 60° C. After that, the obtained reacted mixture was poured into a large amount of n-heptane to precipitate a resin. The obtained resin was filtrated, resulting in a 90% yield of polymer having a weight average molecular weight of about 39000. This polymer, which had the structural units of the following formula, was referred to Resin A1-5.




Synthetic Example 12
Synthesis of Resin A2-1
Monomer (a1-1-3), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1) and monomer (a3-2-3) were charged with molar ratio 30:14:6:20:30, and dioxane was added thereto in an amount equal to 1.5 weight times of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator thereto in an amount of 1 mol % and 3 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 73° C. After that, the reaction solution was poured into a mixture of methanol and ion-exchanged water (4:1) in large amounts to precipitate a resin. The obtained resin was filtrated. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a large amount of a mixture of methanol and water to precipitate a resin. The obtained resin was filtrated. These operations were repeated two times for purification, resulting in 65% yield of copolymer having a weight average molecular weight of about 8100. This copolymer, which had the structural units derived from the monomers of the following formula, was designated Resin A2-1.




Synthetic Example 13
Synthesis of Resin A2-2
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1) and monomer (a3-2-3) were charged with molar ratio 30:14:6:20:30, and dioxane was added thereto in an amount equal to 1.5 weight times of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator thereto in an amount of 1 mol % and 3 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 73° C. After that, the reaction solution was poured into a mixture of methanol and ion-exchanged water (4:1) in large amounts to precipitate a resin. The obtained resin was filtrated. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a large amount of a mixture of methanol and water to precipitate a resin. The obtained resin was filtrated. These operations were repeated two times for purification, resulting in 68% yield of copolymer having a weight average molecular weight of about 7800. This copolymer, which had the structural units derived from the monomers of the following formula, was designated Resin A2-2.




Synthetic Example 14
Synthesis of Resin A2-3
Monomer (a1-1-2), monomer (a2-1-1) and monomer (a3-1-1) were mixed with molar ratio 50:25:25, and dioxane was added thereto in an amount equal to 1.5 weight times of the total amount of monomers. Azobisisobutyronitrile and azobis(2,4-dimethyl valeronitrile) was added as an initiator thereto in an amount of 1 mol % and 3 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 8 hours at 80° C. After that, the reaction solution was poured into a mixture of methanol and ion-exchanged water (4:1) in large amounts to precipitate a resin. The obtained resin was filtrated. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a large amount of a mixture of methanol and water to precipitate a resin. The obtained resin was filtrated. These operations were repeated three times for purification, resulting in 60% yield of copolymer having a weight average molecular weight of about 9200. This copolymer, which had the structural units derived from the monomers of the following formulae, was designated Resin A2-3.




Synthetic Example 15
Synthesis of Resin A2-4
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-2-3) and monomer (a3-1-1) were charged with molar ratio 30:14:6:20:30, and dioxane was added thereto in an amount equal to 1.5 weight times of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator thereto in an amount of 1 mol % and 3 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. After that, the reaction solution was poured into a mixture of methanol and ion-exchanged water (4:1) in large amounts to precipitate a resin. The obtained resin was filtrated. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a large amount of a mixture of methanol and water to precipitate a resin. The obtained resin was filtrated. These operations were repeated two times for purification, resulting in 78% yield of copolymer having a weight average molecular weight of about 7200. This copolymer, which had the structural units derived from the monomers of the following formula, was designated Resin A2-4.




Synthetic Example 16
Synthesis of Resin A2-5
Monomer (a1-1-2), monomer (a1-5-1), monomer (a2-1-1), monomer (a3-2-3) and monomer (a3-1-1) were charged with molar ratio 30:14:6:20:30, and dioxane was added thereto in an amount equal to 1.5 weight times of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator thereto in an amount of 1 mol % and 3 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. After that, the reaction solution was poured into a mixture of methanol and ion-exchanged water in large amounts to precipitate a resin. The obtained resin was filtrated. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a large amount of a mixture of methanol and water to precipitate a resin. The obtained resin was filtrated. These operations were repeated two times for purification, resulting in 78% yield of copolymer having a weight average molecular weight of about 7200. This copolymer, which had the structural units derived from the monomers of the following formula, was designated Resin A2-5.




Synthetic Example 17
Synthesis of Resin X1
Monomer (a1-1-1), monomer (a3-1-1) and monomer (a2-1-1) were mixed with molar ratio 35:45:20, and dioxane was added thereto in an amount equal to 1.5 times by weight of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator to obtain a solution in an amount of 1.0 mol % and 3.0 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. After that, the obtained reacted mixture was poured into a mixture of a large amount of methanol and water to precipitate a resin. The obtained resin was filtrated. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a mixture of methanol and water to precipitate a resin. The obtained resin was filtrated. These operations were repeated 2 times for purification, resulting in a 75% yield of copolymer having a weight average molecular weight of about 7000. This copolymer, which had the structural units of the following formula, was referred to Resin X1.




Synthetic Example 18
Synthesis of Resin X2
Monomer (F) and monomer (a1-1-1) were mixed with molar ratio=80:20, and dioxane was added thereto in an amount equal to 1.5 times by weight of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator to obtain a solution in an amount of 0.5 mol % and 1.5 mol % respectively with respect to the entire amount of monomers, and the resultant mixture was heated for about 5 hours at 70° C. After that, the obtained reacted mixture was poured into a mixture of a large amount of methanol and water to precipitate a resin. The obtained resin was filtrated. Thus obtained resin was dissolved in another dioxane to obtain a solution, and the solution was poured into a mixture of methanol and ion-exchanged water to precipitate a resin. The obtained resin was filtrated. These operations were repeated 2 times, resulting in a 70% yield of copolymer having a weight average molecular weight of about 28000. This copolymer, which had the structural units of the following formula, was referred to Resin X2.




(Preparing Resist Composition)

Resist compositions were prepared by mixing and dissolving each of the components shown in Table 2, and then filtrating through a fluororesin filter having 0.2 μm pore diameter.







TABLE 2







(Unit: parts)















Basic
Salt having
PB/PEB



Resin
Acid Generator
Comp.
Anion (IA)
° C./° C.
















Ex.







 1
A1-1/A2-2 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
110/105


 2
A1-2/A2-1 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
95/85


 3
A1-2/A2-2 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
110/105


 4
A1-2/A2-3 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
110/105


 5
A1-2/A2-1 = 0.7/10
B1 = 1.0
C1 = 0.02
I-409 = 0.04
95/85


 6
A1-2/A2-2 = 0.7/10
B1 = 1.0
C1 = 0.02
I-409 = 0.04
110/105


 7
A1-2/A2-3 = 0.7/10
B1 = 1.0
C1 = 0.02
I-409 = 0.04
110/105


 8
A1-3/A2-2 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
110/105


 9
A1-2/X1 = 0.3/10
B1 = 1.0
C1 = 0.02
I-409 = 0.04
110/105


10
A1-2/X1 = 0.3/10
B2/B3 = 1.0/0.1
C1 = 0.02
I-409 = 0.04
110/105


11
A1-2/A2-4 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
110/105


12
A1-2/A2-5 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
110/105


13
A1-4/A2-5 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
110/105


14
A1-5/A2-5 = 0.7/10
B1 = 1.0
—
I-409 = 0.04
110/105


Comparative


Ex.


 1
X2/X1 = 0.3/10
B2/B3 = 1.0/0.1
C1 = 0.02
—
110/105









<Resin>

Resins A1-1 to A1-4, A2-1 to A2-4, X1 and X2 prepared by the Synthetic Examples
<Acid Generator>
B1: this was prepared by a method according to the method described in the Examples of JP2010-152341A




B2: this was prepared by a method according to the method described in the Examples of WO2008/99869 and JP2010-26478A




B3: this was prepared by a method according to the method described in the Examples of JP2005-221721A




<Basic Compound: Qencher>

C1: 2,6-diisopropylaniline (obtained from Tokyo Chemical Industry Co., LTD)<
<Salt Having Anion (IA)>
D1: compound represented by the formula (I-409)




<Solvent of Resist Composition>

















Propylene glycol monomethyl ether acetate
265 parts 



Propylene glycol monomethyl ether
20 parts



2-Heptanone
20 parts



γ-butyrolactone
3.5 parts 










(Producing Resist Pattern)

A composition for an organic antireflective film (“ARC-29”, by Nissan Chemical Co. Ltd.) was applied onto 12-inch silicon wafers and baked for 60 seconds at 205° C. to form a 78 nm thick organic antireflective film.
The above resist compositions were then applied thereon by spin coating so that the thickness of the resulting film became 85 nm after drying.
The obtained wafers were then pre-baked for 60 sec on a direct hot plate at the temperatures given in the “PB” column in Table 2 to obtain a composition layer.
Line and space patterns were then exposed through stepwise changes in exposure quantity using an ArF excimer stepper for immersion lithography (“XT: 1900Gi” by ASML Ltd.: NA=1.35, 3/4 Annular, X-Y deflection), on the wafers on which the composition layer thus been formed. The ultrapure water was used for medium of immersion.
After the exposure, post-exposure baking was carried out by 60 seconds at the temperatures given in the “PEB” column in Table 2.
Then, puddle development was carried out with 2.38 wt % tetramethylammonium hydroxide aqueous solution for 60 seconds to obtain a resist pattern.
Effective sensitivity was represented as the exposure amount at which a 50 nm line and space pattern resolved to 1:1 with the each resist film.
(Focus Margin (DOF) Evaluation)
The index (DOF) is measured as the focus range in which the line width of the resist patterns was kept within 50 nm±5% (47.5 to 52.5 nm), where the resist patterns were formed based on the effective sensitivity while the focus was adjusted stepwise.
A “∘∘” was given when the DOF value was 0.17 μm or more,
a “∘” was given when the DOF value was 0.12 μm or more, and less than 0.17, and
an “x” was given when the DOF value was less than 0.12 μm.
Table 3 illustrates the results thereof. The parenthetical number means DOF values.
(Evaluation of Defects)
The above resist compositions were applied on each of the 12-inch-silicon wafers by spin coating so that the thickness of the resulting film became 150 nm after drying.
The obtained wafers were then pre-baked for 60 seconds on a direct hot plate at the temperatures given in the “PB” column in Table 2 to obtain a composition layer.
The thus obtained wafers with the produced composition layers were rinsed with water for 60 seconds using a developing apparatus (ACT-12, Tokyo electron Co. Ltd.).
Thereafter, the number of defects was counted using a defect inspection apparatus (KLA-2360, KLA-Tencor Co. Ltd.)
Table 3 illustrates the results thereof.









TABLE 3





Ex.
DOF
Defects

















1
∘∘(0.18)
70


2
∘∘(0.21)
90


3
∘∘(0.24)
110


4
∘∘(0.21)
190


5
∘∘(0.21)
110


6
∘∘(0.24)
120


7
∘∘(0.21)
220


8
∘∘(0.21)
100


9
∘(0.18)
240


10
∘(0.15)
340


11
∘∘(0.24)
100


12
∘∘(0.24)
90


13
∘∘(0.24)
140


14
∘∘(0.24)
180


Com. Ex. 1
x(0.09)
730









According to the resist composition of the present invention, it is possible to achieve satisfactory wide focus margin (DOF) and defect-free. Therefore, the present resist composition can be used for semiconductor microfabrication.

## Claims

1. A resist composition comprising
a resin having a structural unit represented by the formula (I),
a resin being insoluble or poorly soluble in alkali aqueous solution, but becoming soluble in an alkali aqueous solution by the action of an acid and not including the structural unit represented by the formula (I),
an acid generator, and
a salt having an anion represented by the formula (IA).




wherein R1 represents a hydrogen atom or a methyl group;
A1 represents a C1 to C6 alkanediyl group;
A13 represents a C1 to C18 divalent aliphatic hydrocarbon group that optionally has one or more halogen atoms;
X12 represents *-CO—O— or *-O—CO—;
* represents a bond to A13;
A14 represents a C1 to C17 aliphatic hydrocarbon group that optionally has one or more halogen atoms;




wherein R1A and R2A independently represent a hydrogen atom, a C1 to C12 aliphatic hydrocarbon group, a C3 to C20 alicyclic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group or a C7 to C21 aralkyl group, one or more hydrogen atoms contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group and the aralkyl group may be replaced by a hydroxy group, a cyano group, a fluorine atom, trifluoromethyl group or a nitro group, one or more —CH2— contained in the aliphatic hydrocarbon group may be replaced by —O— or —CO—; or R1A and R2A may be bonded to form at least one nitrogen atom-containing C4 to C20 ring.

2. The resist composition according to claim 1, wherein A1 in the formula (I) is an ethylene group.

3. The resist composition according to claim 1, wherein A13 in the formula (I) is a C1 to C6 perfluoro alkanediyl group.

4. The resist composition according to claim 1, wherein X12 in the formula (I) is *-CO—O—, * represents a bond to A13.

5. The resist composition according to claim 1, wherein A14 in the formula (I) is a cyclopropylmethyl, cyclopentyl, cyclohexyl, norbornyl or adamantyl group.

6. The resist composition according to claim 1, wherein the a salt having an anion represented by the formula (IA) contains a cation represented by the formula (IB);



wherein R3, R4 and R5 in each occurrence independently represent a hydroxy group, a halogen atom, a C1 to C12 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a C1 to C12 alkoxy group, or two of R3, R4 and R5 may be bonded together to form a sulfur-containing ring, one or more hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group and the alkoxy group may be replaced by a halogen atom, a hydroxy group, a C1 to C12 alkoxy group, a C6 to C18 aromatic hydrocarbon group, a C2 to C4 acyl group or a glycidyloxy group,
mx, my and m/z independently represent an integer of 0 to 5.

7. The resist composition according to claim 1, which further comprises a solvent.

8. A method for producing a resist pattern comprising steps of;
(1) applying the resist composition of claim 1 onto a substrate;
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) heating the exposed composition layer, and
(5) developing the heated composition layer.