SULFONIUM SALT, RESIST COMPOSITION AND PATTERN FORMING PROCESS

Abstract

A sulfonium salt consisting of a carboxylate anion having a hydroxy group and fluorine or trifluoromethyl at ?- or ?-position and a phenyldibenzothiophenium cation having a hydrocarbylcarbonyl or hydrocarbyloxycarbonyl group has a high decomposition efficiency and a high acid diffusion controlling ability upon exposure. A resist composition comprising the sulfonium salt offers a high sensitivity, reduced LWR and improved CDU independent of whether it is of positive or negative tone.

Claims

1. A sulfonium salt having the formula (1): ##STR00333## wherein p, q and r are each independently an integer of 0 to 3, s is 1 or 2, R.sup.1 and R.sup.2 are each independently halogen, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro, cyano, C(?O)R.sup.4, OC(?O)R.sup.5 or OR.sup.5, R.sup.3 is halogen, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro, cyano, OC(?O)R.sup.5 or OR.sup.5, R.sup.4 is a C.sub.1-C.sub.10 hydrocarbyl group, C.sub.1-C.sub.10 hydrocarbyloxy group, or OR.sup.4A, the hydrocarbyl group and hydrocarbyloxy group may be substituted with fluorine or hydroxy, R.sup.4A is an acid labile group, R.sup.5 is a C.sub.1-C.sub.10 hydrocarbyl group, X.sup.1 is a single bond, ether bond, carbonyl group, N(R), sulfide bond or sulfonyl group, R is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group, Xq.sup.? is a carboxylate anion having a hydroxy group attached to a carbon atom other than aromatic ring-constituting carbon atoms and fluorine or trifluoromethyl at ?- or ?-position.

2. The sulfonium salt of claim 1 wherein the carboxylate anion has the formula (2): ##STR00334## wherein n is 0 or 1, R.sup.6 to R.sup.9 are each independently hydrogen, fluorine, or trifluoromethyl, at least one of R.sup.6 and R.sup.7 is fluorine or trifluoromethyl in case of n=0, at least one of R.sup.6 to R.sup.9 is fluorine or trifluoromethyl in case of n=1, and R.sup.10 is a single bond or a C.sub.1-C.sub.20 hydrocarbylene group which may contain a heteroatom, with the proviso that the carbon atom in R.sup.10 to which OH is bonded is not an aromatic ring-constituting carbon atom.

3. The sulfonium salt of claim 2 wherein n=0, R.sup.10 is a single bond, R.sup.6 and R.sup.7 are trifluoromethyl.

4. A resist composition comprising a quencher containing the sulfonium salt of claim 1.

5. The resist composition of claim 4, further comprising a base polymer.

6. The resist composition of claim 5 wherein the base polymer comprises repeat units having the formula (a1) or repeat units having the formula (a2): ##STR00335## wherein R.sup.A is each independently hydrogen or methyl, Y.sup.1 is a single bond, phenylene, naphthylene, or a C.sub.1-C.sub.12 linking group containing an ester bond and/or lactone ring, Y.sup.2 is a single bond or ester bond, Y.sup.3 is a single bond, ether bond or ester bond, R.sup.11 and R.sup.12 are each independently an acid labile group, R.sup.13 is fluorine, trifluoromethyl, cyano or a C.sub.1-C.sub.6 saturated hydrocarbyl group, R.sup.14 is a single bond or a C.sub.1-C.sub.6 alkanediyl group in which some carbon may be replaced by an ether bond or ester bond, a is 1 or 2, b is an integer of 0 to 4, and a+b is from 1 to 5.

7. The resist composition of claim 6 which is a chemically amplified positive resist composition.

8. The resist composition of claim 5 wherein the base polymer is free of an acid labile group.

9. The resist composition of claim 8 which is a chemically amplified negative resist composition.

10. The resist composition of claim 5 wherein the base polymer comprises repeat units of at least one type selected from repeat units having the formulae (f1) to (f3): ##STR00336## wherein R.sup.A is each independently hydrogen or methyl, Z.sup.1 is a single bond, a C.sub.1-C.sub.6 aliphatic hydrocarbylene group, phenylene group, naphthylene group, or C.sub.7-C.sub.18 group obtained by combining the foregoing, or OZ.sup.11, C(?O)OZ.sup.11 or C(?O)NHZ.sup.11, Z.sup.11 is a C.sub.1-C.sub.6 aliphatic hydrocarbylene group, phenylene group, naphthylene group, or C.sub.7-C.sub.18 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety, Z.sup.2 is a single bond or ester bond, Z.sup.3 is a single bond, Z.sup.31C(?O)O, Z.sup.31O or Z.sup.31OC(?O), Z.sup.31 is a C.sub.1-C.sub.12 aliphatic hydrocarbylene group, phenylene group, or C.sub.7-C.sub.18 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond, urethane bond, nitro, cyano, fluorine, iodine or bromine, Z.sup.4 is methylene, 2,2,2-trifluoro-1,1-ethanediyl or carbonyl, Z.sup.5 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene group, OZ.sup.51, C(?O)OZ.sup.51, or C(?O)NHZ.sup.51, Z.sup.51 is a C.sub.1-C.sub.6 aliphatic hydrocarbylene group, phenylene group, fluorinated phenylene group, or trifluoromethyl-substituted phenylene group, which may contain a carbonyl moiety, ester bond, ether bond, halogen or hydroxy moiety, R.sup.21 to R.sup.28 are each independently halogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom, a pair of R.sup.23 and R.sup.24 or R.sup.26 and R.sup.27 may bond together to form a ring with the sulfur atom to which they are attached, and M.sup.? is a non-nucleophilic counter ion.

11. The resist composition of claim 4, further comprising an acid generator capable of generating a strong acid.

12. The resist composition of claim 11 wherein the acid generator generates a sulfonic acid, imide acid or methide acid.

13. The resist composition of claim 4, further comprising an organic solvent.

14. The resist composition of claim 4, further comprising a surfactant.

15. A pattern forming process comprising the steps of applying the resist composition of claim 4 onto a substrate to form a resist film thereon, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.

16. The process of claim 15 wherein the high-energy radiation is KrF excimer laser, ArF excimer laser, EB or EUV of wavelength 3 to 15 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0061] As used herein, the singular forms a, an and the include plural referents unless the context clearly dictates otherwise. Optional or optionally means that the subsequently described event or circumstances may or may not occur, and that description includes instances where the event or circumstance occurs and instances where it does not. The notation (Cn-Cm) means a group containing from n to m carbon atoms per group. In chemical formulae, the broken line designates a valence bond. As used herein, the term fluorinated refers to a fluorine-substituted or fluorine-containing compound or group. The terms group and moiety are interchangeable.

[0062] The abbreviations and acronyms have the following meaning. [0063] EB: electron beam [0064] EUV: extreme ultraviolet [0065] Mw: weight average molecular weight [0066] Mn: number average molecular weight [0067] Mw/Mn: molecular weight distribution or dispersity [0068] GPC: gel permeation chromatography [0069] PEB: post-exposure bake [0070] PAG: photoacid generator [0071] LWR: line width roughness [0072] CDU: critical dimension uniformity

Sulfonium Salt

[0073] One embodiment of the invention is a sulfonium salt of specific structure, which is referred to as Sulfonium Salt A, hereinafter. Sulfonium Salt A has the formula (1).

##STR00005##

[0074] In formula (1), p, q and r are each independently an integer of 0 to 3, s is 1 or 2, and r+s is from 1 to 3.

[0075] In formula (1), R.sup.1 and R.sup.2 are each independently halogen, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro, cyano, C(?O)R.sup.4, OC(?O)R.sup.5 or OR.sup.5.

[0076] In formula (1), R.sup.3 is halogen, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, nitro, cyano, OC(?O)R.sup.5 or OR.sup.5.

[0077] In formula (1), R.sup.4 is a C.sub.1-C.sub.10 hydrocarbyl group, C.sub.1-C.sub.10 hydrocarbyloxy group, or OR.sup.4A. The hydrocarbyl group and hydrocarbyloxy group may be substituted with fluorine or hydroxy. R.sup.4A is an acid labile group.

[0078] R.sup.5 is a C.sub.1-C.sub.10 hydrocarbyl group.

[0079] The hydrocarbyl group represented by R.sup.4 and R.sup.5 and the hydrocarbyl moiety in the hydrocarbyloxy group represented by R.sup.4 may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include C.sub.1-C.sub.10 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, 3-pentyl, tert-pentyl, neopentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl; C.sub.3-C.sub.10 cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, methylcyclopropyl, methylcyclobutyl, methylcyclopentyl, methylcyclohexyl, ethylcyclopropyl, ethylcyclobutyl, ethylcyclopentyl, and ethylcyclohexyl; C.sub.2-C.sub.10 alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, and decenyl; C.sub.2-C.sub.10 alkynyl groups such as ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, and decynyl; C.sub.3-C.sub.10 cyclic unsaturated aliphatic hydrocarbyl groups such as cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, ethylcyclopentenyl, ethylcyclohexenyl, and norbornenyl; C.sub.6-C.sub.10 aryl groups such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, and naphthyl; C.sub.7-C.sub.10 aralkyl groups such as benzyl, phenethyl, phenylpropyl, and phenylbutyl, and combinations thereof.

[0080] The acid labile group R.sup.4A may be any of well-known acid labile groups commonly used in resist materials. Typical of the acid labile group R.sup.4A are acid labile groups having formula (AL-1) to (AL-3) to be described later.

[0081] In formula (1), X.sup.1 is a single bond, ether bond, carbonyl group, N(R), sulfide bond or sulfonyl group. R is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group.

[0082] Examples of the cation in Sulfonium Salt A are shown below, but not limited thereto.

##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030##

##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045##

[0083] The preferred sulfonium cations are dibenzothiophenium cations, that is, cations in formula (1) wherein X.sup.1 is a single bond. These cations are preferred in the EUV lithography because of high photo-decomposition efficiency. More preferred are the cations whose substituent is an ester bond, that is, cations in formula (1) wherein R.sup.4 is an alkoxy group. Since the ester site is hydrolyzed during alkaline development, the dissolution of resist film in exposed region is improved and residue defects are minimized.

[0084] In formula (1), Xq.sup.? is a carboxylate anion having a hydroxy group attached to a carbon atom other than aromatic ring-constituting carbon atoms and fluorine or trifluoromethyl at ?- or ?-position. An anion having the formula (2) is preferred.

##STR00046##

[0085] In formula (2), n is 0 or 1.

[0086] In formula (2), R.sup.6 to R.sup.9 are each independently hydrogen, fluorine, or trifluoromethyl. At least one of R.sup.6 and R.sup.7 is fluorine or trifluoromethyl in case of n=0, and at least one of R.sup.6 to R.sup.9 is fluorine or trifluoromethyl in case of n=1.

[0087] In formula (2), R.sup.10 is a single bond or a C.sub.1-C.sub.20 hydrocarbylene group which may contain a heteroatom. The hydrocarbylene group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include C.sub.1-C.sub.20 alkanediyl groups such as methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-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, and dodecane-1,12-diyl; C.sub.3-C.sub.20 cyclic saturated hydrocarbylene groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl and adamantanediyl; C.sub.4-C.sub.20 divalent groups obtained by combining an alkanediyl group with a cyclic saturated hydrocarbylene group; C.sub.6-C.sub.20 arylene groups such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene and tert-butylnaphthylene; and C.sub.7-C.sub.20 divalent groups obtained by combining an arylene group with an alkanediyl and/or cyclic saturated hydrocarbylene group. In the hydrocarbylene group, some or all of the hydrogen atoms may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some constituent CH.sub.2 may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (C(?O)OC(?O)) or haloalkyl moiety. It is noted that the carbon atom in R.sup.10 to which OH is bonded is not an aromatic ring-constituting carbon atom.

[0088] Also preferably, R.sup.10 is a group having the formula (2)-1.

##STR00047##

[0089] Herein, * designates a point of attachment to the carbon atom to which R.sup.6 and R.sup.7 are bonded in case of n=0 or a point of attachment to the carbon atom to which R.sup.8 and R.sup.9 are bonded in case of n=1, and ** designates a point of attachment to OH.

[0090] In formula (2)-1, R.sup.10A and R.sup.10B are each independently hydrogen or a C.sub.1-C.sub.10 hydrocarbyl group which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof are as exemplified above for the hydrocarbyl group represented by R.sup.4 and R.sup.5 in formula (1). In the hydrocarbyl group, some or all of the hydrogen atoms may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some constituent CH.sub.2 may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (C(?O)OC(?O)) or haloalkyl moiety.

[0091] Also, R.sup.10A and R.sup.10B may bond together to form a ring with the carbon atom to which they are attached. Typical rings include cyclopropane, cyclopentane, cyclohexane, norbornane, and adamantane rings.

[0092] In formula (2)-1, R.sup.10C is a single bond or C.sub.1-C.sub.10 hydrocarbylene group which may contain a heteroatom. The hydrocarbylene group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof are as exemplified above for the hydrocarbylene group represented by R.sup.10, but of 1 to 10 carbon atoms. In the hydrocarbylene group, some or all of the hydrogen atoms may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some constituent CH.sub.2 may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (C(?O)OC(?O)) or haloalkyl moiety. It is noted that the carbon atom in R.sup.10 to which OH is bonded is not an aromatic ring-constituting carbon atom.

[0093] Of the carboxylate anions having formula (2), those of formula (2) wherein n=0, R.sup.10 is a single bond, R.sup.6 and R.sup.7 are trifluoromethyl are preferred.

[0094] It is noted that the number of carbon atoms in the group having formula (2)-1 is 20 or less.

[0095] Examples of the anion having formula (2) are shown below, but not limited thereto.

##STR00048## ##STR00049##

[0096] Sulfonium Salt A may be synthesized, for example, by ion exchange between a sulfonium salt having a sulfonium cation as mentioned above and an ammonium salt having an anion as mentioned above or protic acid having an anion as mentioned above. The sulfonium cation can be obtained from reaction of a dibenzothiophene compound having a carbonyl or alkoxycarbonyl group with a diphenyl iodonium salt.

Resist Composition

[0097] Another embodiment of the invention is a resist composition comprising a quencher containing Sulfonium Salt A.

[0098] In the resist composition, Sulfonium Salt A is preferably used in an amount of 0.001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight per 100 parts by weight of a base polymer to be described below. Sulfonium Salt A may be used alone or in admixture of two or more.

Base Polymer

[0099] In one embodiment, the resist composition contains a base polymer. In the case of positive resist compositions, the base polymer comprises repeat units containing an acid labile group. The preferred repeat units containing an acid labile group are repeat units having the formula (a1) or repeat units having the formula (a2), which are also referred to as repeat units (a1) or (a2).

##STR00050##

[0100] In formulae (a1) and (a2), R.sup.A is each independently hydrogen or methyl. Y.sup.1 is a single bond, phenylene group, naphthylene group, or a C.sub.1-C.sub.12 linking group containing an ester bond and/or lactone ring. Y.sup.2 is a single bond or ester bond. Y.sup.3 is a single bond, ether bond or ester bond. R.sup.1 and R.sup.12 are each independently an acid labile group. It is noted that when the base polymer contains both repeat units (a1) and (a2), R.sup.11 and R.sup.12 may be identical or different. R.sup.13 is fluorine, trifluoromethyl, cyano or a C.sub.1-C.sub.6 saturated hydrocarbyl group. R.sup.14 is a single bond or a C.sub.1-C.sub.6 alkanediyl group in which some carbon may be replaced by an ether bond or ester bond. The subscript a is 1 or 2, b is an integer of 0 to 4, and the sum of a+b is from 1 to 5.

[0101] Examples of the monomer from which repeat units (a1) are derived are shown below, but not limited thereto. Herein R.sup.A and R.sup.11 are as defined above.

##STR00051## ##STR00052##

[0102] Examples of the monomer from which repeat units (a2) are derived are shown below, but not limited thereto. Herein R.sup.A and R.sup.12 are as defined above.

##STR00053## ##STR00054##

[0103] The acid labile groups represented by R.sup.4A, R.sup.11 and R.sup.12 in formulae (1), (a1) and (a2) may be selected from a variety of such groups, for example, those groups described in JP-A 2013-080033 (U.S. Pat. No. 8,574,817) and JP-A 2013-083821 (U.S. Pat. No. 8,846,303).

[0104] Typical of the acid labile group are groups of the following formulae (AL-1) to (AL-3).

##STR00055##

[0105] In formulae (AL-1) and (AL-2), R.sup.L1 and R.sup.L2 are each independently a C.sub.1-C.sub.40 hydrocarbyl group which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Inter alia, C.sub.1-C.sub.40 saturated hydrocarbyl groups are preferred, and C.sub.1-C.sub.20 saturated hydrocarbyl groups are more preferred.

[0106] In formula (AL-1), c is an integer of 0 to 10, preferably 1 to 5.

[0107] In formula (AL-2), R.sup.L3 and R.sup.L4 are each independently hydrogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Inter alia, C.sub.1-C.sub.20 saturated hydrocarbyl groups are preferred. Any two of R.sup.L2, R.sup.L3 and RN may bond together to form a C.sub.3-C.sub.20 ring with the carbon atom or carbon and oxygen atoms to which they are attached. The ring preferably contains 4 to 16 carbon atoms and is typically alicyclic.

[0108] In formula (AL-3), R.sup.L5, R.sup.L6 and R.sup.L7 are each independently a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Inter alia, C.sub.1-C.sub.20 saturated hydrocarbyl groups are preferred. Any two of R.sup.L5, R.sup.L6 and R.sup.L7 may bond together to form a C.sub.3-C.sub.20 ring with the carbon atom to which they are attached. The ring preferably contains 4 to 16 carbon atoms and is typically alicyclic.

[0109] The base polymer may further comprise repeat units (b) having a phenolic hydroxy group as an adhesive group. Examples of suitable monomers from which repeat units (b) are derived are given below, but not limited thereto. Herein R.sup.A is as defined above.

##STR00056## ##STR00057##

[0110] The base polymer may further comprise repeat units (c) having another adhesive group selected from hydroxy group (other than the foregoing phenolic hydroxy), lactone ring, sultone ring, ether bond, ester bond, sulfonic ester bond, carbonyl group, sulfonyl group, cyano group, and carboxy group. Examples of suitable monomers from which repeat units (c) are derived are given below, but not limited thereto. Herein RA is as defined above.

##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068##

##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077##

[0111] In another preferred embodiment, the base polymer may further comprise repeat units (d) derived from indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, and norbornadiene, or derivatives thereof. Suitable monomers are exemplified below.

##STR00078##

[0112] Furthermore, the base polymer may comprise repeat units (e) derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindene, vinylpyridine, vinylcarbazole, or derivatives thereof.

[0113] In a further embodiment, the base polymer may comprise repeat units (f) derived from an onium salt having a polymerizable unsaturated bond. Specifically, the base polymer may comprise repeat units of at least one type selected from repeat units having formula (f1), repeat units having formula (f2), and repeat units having formula (f3), all shown below. These units are simply referred to as repeat units (f1), (f2) and (f3), which may be used alone or in combination of two or more types.

##STR00079##

[0114] In formulae (f1) to (f3), R.sup.A is each independently hydrogen or methyl. Z.sup.1 is a single bond, C.sub.1-C.sub.6 aliphatic hydrocarbylene group, phenylene group, naphthylene group, or C.sub.7-Cis group obtained by combining the foregoing, OZ.sup.11, C(?O)OZ.sup.11, or C(?O)NHZ.sup.11. Z.sup.11 is a C.sub.1-C.sub.6 aliphatic hydrocarbylene group, phenylene group, naphthylene group, or C.sub.7-C.sub.18 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety. Z.sup.2 is a single bond or ester bond. Z.sup.3 is a single bond, Z.sup.31C(?O)O, Z.sup.31O or Z.sup.31OC(?O). Z.sup.31 is a C.sub.1-C.sub.12 aliphatic hydrocarbylene group, phenylene group, or C.sub.7-C.sub.18 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond, urethane bond, nitro bond, cyano moiety, fluorine, iodine or bromine. Z.sup.4 is methylene, 2,2,2-trifluoro-1,1-ethanediyl or carbonyl group. Z.sup.5 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, OZ.sup.51, C(?O)OZ.sup.51, or C(?O)NHZ.sup.51. Z.sup.51 is a C.sub.1-C.sub.6 aliphatic hydrocarbylene group, phenylene group, fluorinated phenylene group, or trifluoromethyl-substituted phenylene group, which may contain a carbonyl moiety, ester bond, ether bond, halogen or hydroxy moiety.

[0115] In formulae (f1) to (f3), R.sup.21 to R.sup.11 are each independently halogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Examples of the halogen and hydrocarbyl group are as will be exemplified later for R.sup.101 to R.sup.105 in formulae (3-1) and (3-2). In these hydrocarbyl groups, some or all of the hydrogen atoms may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen and some constituent CH.sub.2 may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxy moiety, fluorine, chlorine, bromine, iodine, cyano moiety, nitro moiety, carbonyl moiety, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (C(?O)OC(?O)), or haloalkyl moiety. A pair of R.sup.23 and R.sup.24, or R.sup.26 and R.sup.27 may bond together to form a ring with the sulfur atom to which they are attached. Examples of the ring are as will be exemplified later for the ring that R.sup.101 and R.sup.102 in formulae (3-1) and (3-2), taken together, form with the sulfur atom to which they are attached.

[0116] In formula (f1), M.sup.? is a non-nucleophilic counter ion. Examples of the non-nucleophilic counter ion include halide ions such as chloride and bromide ions; fluoroalkylsulfonate ions such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; arylsulfonate ions such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkylsulfonate ions such as mesylate and butanesulfonate; imide ions such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide; methide ions such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide.

[0117] Also included are sulfonate ions having fluorine substituted at ?-position as represented by the formula (f1-1) and sulfonate ions having fluorine substituted at ?-position and trifluoromethyl at ?-position as represented by the formula (f1-2).

##STR00080##

[0118] In formula (f1-1), R.sup.31 is hydrogen, or a C.sub.1-C.sub.20 hydrocarbyl group which may contain an ether bond, ester bond, carbonyl moiety, lactone ring, or fluorine atom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Examples of the hydrocarbyl group are as will be exemplified later for R.sup.fa1 in formula (3A).

[0119] In formula (f1-2), R.sup.32 is hydrogen, or a C.sub.1-C.sub.30 hydrocarbyl group or C.sub.2-C.sub.30 hydrocarbylcarbonyl group, which may contain an ether bond, ester bond, carbonyl moiety or lactone ring. The hydrocarbyl group and hydrocarbyl moiety in the hydrocarbylcarbonyl group may be saturated or unsaturated and straight, branched or cyclic. Examples of the hydrocarbyl group are as will be exemplified later for R.sup.fa1 in formula (3A).

[0120] Examples of the cation in the monomer from which repeat unit (f1) is derived are shown below, but not limited thereto. R.sup.A is as defined above.

##STR00081## ##STR00082## ##STR00083##

[0121] Examples of the cation in the monomer from which repeat unit (f2) or (f3) is derived are as exemplified above for the cation in the sulfonium salt having formula (1) or as will be exemplified later for the cation in the sulfonium salt having formula (3-1).

[0122] Examples of the anion in the monomer from which repeat unit (f2) is derived are shown below, but not limited thereto. R.sup.A is as defined above.

##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097##

##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111##

##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131##

##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148##

##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167##

##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191##

##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204##

[0123] Examples of the anion in the monomer from which repeat unit (0) is derived are shown below, but not limited thereto. R.sup.A is as defined above.

##STR00205## ##STR00206##

[0124] Repeat units (f1) to (f3) have an acid generator function. The attachment of an acid generator to the polymer main chain is effective in restraining acid diffusion, thereby preventing a reduction of resolution due to blur by acid diffusion. Also, LWR or CDU is improved since the acid generator is uniformly distributed. Where a base polymer containing repeat units (f), i.e., polymer-bound acid generator is used, the blending of an acid generator of addition type (to be described later) may be omitted.

[0125] In the base polymer, a fraction of units (a1), (a2), (b), (c), (d), (e), (f1), (f2) and (f3) is: preferably 0?a1?0.9, 0?a?0.9, 0?a1+a2?0.9, 0?b?0.9, 0?c?0.9, 0?d?0.5, 0?e?0.5, 0?f1?0.5, 0?f2?0.5, 0?f3?0.5, and 0?f1+f2+f3?0.5; more preferably 0?a1?0.8, 0?a2?0.8, 0?a1+a2?0.8, 0?b?0.8, 0?c?0.8, 0?d?0.4, 0?e?0.4, 0?f1?0.4, 0?f2?0.4, 0?f3?0.4, and 0?f1+f2+f3?0.4; and even more preferably 0?a1?0.7, 0?a2?0.7, 0?a1+a2?0.7, 0?b?0.7, 0?c?0.7, 0?d?0.3, 0?e?0.3, 0?f1?0.3, 0?f2?0.3, 0?f?0.3, and 0?f1+f2+f3?0.3. Notably, a1+a2+b+c+d+e+f1+f2+f3=1.0.

[0126] The base polymer may be synthesized by any desired methods, for example, by dissolving one or more monomers selected from the monomers corresponding to the foregoing repeat units in an organic solvent, adding a radical polymerization initiator thereto, and heating for polymerization. Examples of the organic solvent which can be used for polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, and dioxane. Examples of the polymerization initiator used herein include 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Preferably, the reaction temperature is 50 to 80? C. and the reaction time is 2 to 100 hours, more preferably 5 to 20 hours.

[0127] Where a monomer having a hydroxy group is copolymerized, the hydroxy group may be replaced by an acetal group susceptible to deprotection with acid, typically ethoxyethoxy, prior to polymerization, and the polymerization be followed by deprotection with weak acid and water. Alternatively, the hydroxy group may be replaced by an acetyl, formyl, pivaloyl or similar group prior to polymerization, and the polymerization be followed by alkaline hydrolysis.

[0128] When hydroxystyrene or hydroxyvinylnaphthalene is copolymerized, an alternative method is possible. Specifically, acetoxystyrene or acetoxyvinylnaphthalene is used instead of hydroxystyrene or hydroxyvinylnaphthalene, and after polymerization, the acetoxy group is deprotected by alkaline hydrolysis, for thereby converting the polymer product to hydroxystyrene or hydroxyvinylnaphthalene. For alkaline hydrolysis, a base such as aqueous ammonia or triethylamine may be used. Preferably the reaction temperature is ?20? C. to 100? C., more preferably 0? C. to 60? C., and the reaction time is 0.2 to 100 hours, more preferably 0.5 to 20 hours.

[0129] The base polymer should preferably have a weight average molecular weight (Mw) in the range of 1,000 to 500,000, and more preferably 2,000 to 30,000, as measured by GPC versus polystyrene standards using tetrahydrofuran (THF) solvent. A Mw in the range ensures that the resist film is fully heat resistant and dissolvable in alkaline developer.

[0130] If a base polymer has a wide molecular weight distribution or dispersity (Mw/Mn), which indicates the presence of lower and higher molecular weight polymer fractions, there is a possibility that foreign matter is left on the pattern or the pattern profile is degraded. The influences of Mw and Mw/Mn become stronger as the pattern rule becomes finer. Therefore, the base polymer should preferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide a resist composition suitable for micropatterning to a small feature size.

[0131] It is understood that a blend of two or more polymers which differ in compositional ratio, Mw or Mw/Mn is acceptable.

Acid Generator

[0132] The resist composition may comprise an acid generator capable of generating a strong acid (referred to as acid generator of addition type, hereinafter). As used herein, the term strong acid refers to a compound having a sufficient acidity to induce deprotection reaction of an acid labile group on the base polymer in the case of a chemically amplified positive resist composition, or a compound having a sufficient acidity to induce acid-catalyzed polarity switch reaction or crosslinking reaction in the case of a chemically amplified negative resist composition. The inclusion of such an acid generator ensures that Sulfonium Salt A functions as a quencher and the inventive resist composition functions as a chemically amplified positive or negative resist composition.

[0133] The acid generator is typically a compound (PAG) capable of generating an acid in response to actinic ray or radiation. Although the PAG used herein may be any compound capable of generating an acid upon exposure to high-energy radiation, those compounds capable of generating sulfonic acid, imide acid (imidic acid) or methide acid are preferred. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators. Exemplary PAGs are described in JP-A 2008-111103, paragraphs [0122]-[0142] (U.S. Pat. No. 7,537,880).

[0134] As the PAG used herein, sulfonium salts having the formula (3-1) and iodonium salts having the formula (3-2) are also preferred.

##STR00207##

[0135] In formulae (3-1) and (3-2), R.sup.101 to R.sup.105 are each independently halogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom.

[0136] Of the groups represented by R.sup.101 to R.sup.105, suitable halogen atoms include fluorine, chlorine, bromine and iodine.

[0137] The C.sub.1-C.sub.20 hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include C.sub.1-C.sub.20 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl and icosyl; C.sub.3-C.sub.20 cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; C.sub.2-C.sub.20 alkenyl groups such as vinyl, propenyl, butenyl, and hexenyl; C.sub.2-C.sub.20 alkynyl groups such as ethynyl, propynyl, and butynyl; C.sub.3-C.sub.20 cyclic unsaturated aliphatic hydrocarbyl groups such as cyclohexenyl and norbornenyl; C.sub.6-C.sub.20 aryl groups such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, and tert-butylnaphthyl; C.sub.7-C.sub.20 aralkyl groups such as benzyl and phenethyl, and combinations thereof. In the foregoing hydrocarbyl groups, some or all hydrogen may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, and some constituent CH.sub.2 may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, nitro, mercapto, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate, lactone ring, sultone ring, carboxylic anhydride (C(?O)OC(?O)), or haloalkyl moiety.

[0138] R.sup.101 and R.sup.102 may bond together to form a ring with the sulfur atom to which they are attached. Preferred rings are of the structures shown below.

##STR00208##

[0139] Herein the broken line designates a point of attachment to R.sup.103.

[0140] Examples of the cation in the sulfonium salt having formula (3-1) are shown below, but not limited thereto.

##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226##

##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248##

##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260##

[0141] The cations in the sulfonium salt having formula (1) are also useful as the cation in the sulfonium salt having formula (3-1).

[0142] Examples of the cation in the iodonium salt having formula (3-2) are shown below, but not limited thereto.

##STR00261## ##STR00262## ##STR00263##

[0143] In formulae (3-1) and (3-2), Xa.sup.? is an anion of the following formula (3A), (3B), (3C) or (3D).

##STR00264##

[0144] In formula (3A), R.sup.fa is fluorine or a C.sub.1-C.sub.40 hydrocarbyl group which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof are as will be exemplified later for hydrocarbyl group R.sup.fa1 in formula (3A).

[0145] Of the anions of formula (3A), a structure having formula (3A) is preferred.

##STR00265##

[0146] In formula (3A), R.sup.HF is hydrogen or trifluoromethyl, preferably trifluoromethyl.

[0147] R.sup.fa1 is a C.sub.1-C.sub.38 hydrocarbyl group which may contain a heteroatom. Suitable heteroatoms include oxygen, nitrogen, sulfur and halogen, with oxygen being preferred. Of the hydrocarbyl groups, those of 6 to 30 carbon atoms are preferred because a high resolution is available in fine pattern formation. The hydrocarbyl group R.sup.fa1 may be saturated or unsaturated and straight, branched or cyclic. Suitable hydrocarbyl groups include C.sub.1-C.sub.38 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, icosyl; C.sub.3-C.sub.38 cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl; C.sub.2-C.sub.38 unsaturated aliphatic hydrocarbyl groups such as allyl and 3-cyclohexenyl; C.sub.6-C.sub.38 aryl groups such as phenyl, 1-naphthyl and 2-naphthyl; C.sub.7-C.sub.38 aralkyl groups such as benzyl and diphenylmethyl; and combinations thereof.

[0148] In the hydrocarbyl group, some or all of the hydrogen atoms may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some constituent CH.sub.2 may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (C(?O)OC(?O)) or haloalkyl moiety. Examples of the heteroatom-containing hydrocarbyl group include tetrahydrofuryl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl.

[0149] With respect to the synthesis of the sulfonium salt having an anion of formula (3A), reference is made to JP-A 2007-145797, JP-A 2008-106045, JP-A 2009-007327, and JP-A 2009-258695. Also useful are the sulfonium salts described in JP-A 2010-215608, JP-A 2012-041320, JP-A 2012-106986, and JP-A 2012-153644.

[0150] Examples of the anion having formula (3A) are as exemplified for the anion having formula (1A) in US 20180335696 (JP-A 2018-197853).

[0151] In formula (3B), R.sup.fb1 and R.sup.fb2 are each independently fluorine or a C.sub.1-C.sub.40 hydrocarbyl group which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Suitable hydrocarbyl groups are as exemplified above for R.sup.fa1 in formula (3A). Preferably R.sup.fb1 and R.sup.fb2 each are fluorine or a straight C.sub.1-C.sub.4 fluorinated alkyl group. A pair of R.sup.fb1 and R.sup.fb2 may bond together to form a ring with the linkage (CF.sub.2SO.sub.2NSO.sub.2CF.sub.2) to which they are attached, and the ring-forming pair R.sup.fb1-R.sup.fb2 is preferably a fluorinated ethylene or fluorinated propylene group.

[0152] In formula (3C), R.sup.fc1, R.sup.fc2 and R.sup.fc3 are each independently fluorine or a C.sub.1-C.sub.40 hydrocarbyl group which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Suitable hydrocarbyl groups are as exemplified above for R.sup.fa1 in formula (3A). Preferably R.sup.fc1, R.sup.fc2 and R.sup.fc3 each are fluorine or a straight C.sub.1-C.sub.4 fluorinated alkyl group. A pair of R.sup.fc1 and R.sup.fc2 may bond together to form a ring with the linkage (CF.sub.2SO.sub.2CSO.sub.2CF.sub.2) to which they are attached, and the ring-forming pair R.sup.fc1-R.sup.fc2 is preferably a fluorinated ethylene or fluorinated propylene group.

[0153] In formula (3D), R.sup.fd is a C.sub.1-C.sub.40 hydrocarbyl group which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Suitable hydrocarbyl groups are as exemplified above for R.sup.fa1 in formula (3A).

[0154] With respect to the synthesis of the sulfonium salt having an anion of formula (3D), reference is made to JP-A 2010-215608 and JP-A 2014-133723.

[0155] Examples of the anion having formula (3D) are as exemplified for the anion having formula (1D) in US 20180335696 (JP-A 2018-197853).

[0156] The compound having the anion of formula (3D) has a sufficient acid strength to cleave acid labile groups in the base polymer because it is free of fluorine at ?-position of sulfo group, but has two trifluoromethyl groups at ?-position. Thus the compound is a useful PAG.

[0157] Also compounds having the formula (4) are useful as the PAG.

##STR00266##

[0158] In formula (4), R.sup.201 and R.sup.202 are each independently halogen or a C.sub.1-C.sub.30 hydrocarbyl group which may contain a heteroatom. R.sup.203 is a C.sub.1-C.sub.30 hydrocarbylene group which may contain a heteroatom. Any two of R.sup.201, R.sup.202 and R.sup.203 may bond together to form a ring with the sulfur atom to which they are attached. Exemplary rings are as described above for the ring that R.sup.101 and R.sup.102 in formula (3-1), taken together, form with the sulfur atom to which they are attached.

[0159] The hydrocarbyl groups R.sup.201 and R.sup.202 may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include C.sub.1-C.sub.30 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; C.sub.3-C.sub.30 cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, tricyclo[5.2.1.0.sup.2,6]decyl, and adamantyl; C.sub.6-C.sub.30 aryl groups such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl, and anthracenyl; and combinations thereof. In the hydrocarbyl group, some or all of the hydrogen atoms may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some constituent CH.sub.2 may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (C(?O)OC(?O)) or haloalkyl moiety.

[0160] The hydrocarbylene group R.sup.203 may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include C.sub.1-C.sub.30 alkanediyl groups such as methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-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, and heptadecane-1,17-diyl; C.sub.3-C.sub.30 cyclic saturated hydrocarbylene groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl and adamantanediyl; C.sub.6-C.sub.30 arylene groups such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene and tert-butylnaphthylene; and combinations thereof. In the hydrocarbylene group, some or all of the hydrogen atoms may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some constituent CH.sub.2 may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (C(?O)OC(?O)) or haloalkyl moiety. Of the heteroatoms, oxygen is preferred.

[0161] In formula (4), L.sup.A is a single bond, ether bond or a C.sub.1-C.sub.20 hydrocarbylene group which may contain a heteroatom. The hydrocarbylene group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof are as exemplified above for R.sup.203.

[0162] In formula (4), X.sup.A, X.sup.B, X.sup.C and X.sup.D are each independently hydrogen, fluorine or trifluoromethyl, with the proviso that at least one of X.sup.A, X.sup.B, X.sup.C and X.sup.D is fluorine or trifluoromethyl.

[0163] In formula (4), d is an integer of 0 to 3.

[0164] Of the PAGs having formula (4), those having the formula (4) are preferred.

##STR00267##

[0165] In formula (4), L.sup.A is as defined above. R.sup.HF is hydrogen or trifluoromethyl, preferably trifluoromethyl. R.sup.301, R.sup.302 and R.sup.303 are each independently hydrogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof are as exemplified above for R.sup.fa1 in formula (3A). The subscripts x and y are each independently an integer of 0 to 5, and z is an integer of 0 to 4.

[0166] Examples of the PAG having formula (4) are as exemplified for the PAG having formula (2) in JP-A 2017-026980.

[0167] Of the foregoing PAGs, those having an anion of formula (3A) or (3D) are especially preferred because of reduced acid diffusion and high solubility in the solvent. Also those having formula (4) are especially preferred because of extremely reduced acid diffusion.

[0168] Also a sulfonium or iodonium salt having an anion containing an iodized or brominated aromatic ring may be used as the PAG. Suitable are sulfonium and iodonium salts having the formulae (5-1) and (5-2).

##STR00268##

[0169] In formulae (5-1) and (5-2), p is an integer of 1 to 3, q is an integer of 1 to 5, and r is an integer of 0 to 3, and 1?q+r?5. Preferably, q is 1, 2 or 3, more preferably 2 or 3, and r is 0, 1 or 2.

[0170] In formulae (5-1) and (5-2), X.sup.BI is iodine or bromine, and may be the same or different when p and/or q is 2 or more.

[0171] L.sup.1 is a single bond, ether bond, ester bond, or a C.sub.1-C.sub.6 saturated hydrocarbylene group which may contain an ether bond or ester bond. The saturated hydrocarbylene group may be straight, branched or cyclic.

[0172] L.sup.2 is a single bond or a C.sub.1-C.sub.20 divalent linking group when p is 1, and a C.sub.1-C.sub.20 (p+1)-valent linking group which may contain oxygen, sulfur or nitrogen when p is 2 or 3.

[0173] R.sup.401 is a hydroxy group, carboxy group, fluorine, chlorine, bromine, amino group, or a C.sub.1-C.sub.20 hydrocarbyl, C.sub.1-C.sub.20 hydrocarbyloxy, C.sub.2-C.sub.20 hydrocarbylcarbonyl, C.sub.2-C.sub.20 hydrocarbyloxycarbonyl, C.sub.2-C.sub.20 hydrocarbylcarbonyloxy or C.sub.1-C.sub.20 hydrocarbylsulfonyloxy group, which may contain fluorine, chlorine, bromine, hydroxy, amino or ether bond, or N(R.sup.401A)(R.sup.401B), N(R.sup.401C)C(?O)R.sup.401D or N(R.sup.401C)C(?O)OR.sup.401D. R.sup.401A and R.sup.401B are each independently hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group. R.sup.401C is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group which may contain halogen, hydroxy, C.sub.1-C.sub.6 saturated hydrocarbyloxy, C.sub.2-C.sub.6 saturated hydrocarbylcarbonyl or C.sub.2-C.sub.6 saturated hydrocarbylcarbonyloxy moiety. R.sup.401D is a C.sub.1-C.sub.16 aliphatic hydrocarbyl group, C.sub.6-C.sub.14 aryl group or C.sub.7-C.sub.15 aralkyl group, which may contain halogen, hydroxy, C.sub.1-C.sub.6 saturated hydrocarbyloxy, C.sub.2-C.sub.6 saturated hydrocarbylcarbonyl or C.sub.2-C.sub.6 saturated hydrocarbylcarbonyloxy moiety. The aliphatic hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. The hydrocarbyl, hydrocarbyloxy, hydrocarbylcarbonyl, hydrocarbyloxycarbonyl, and hydrocarbylcarbonyloxy groups may be straight, branched or cyclic. Groups R.sup.401 may be the same or different when p and/or r is 2 or more. Of these, R.sup.401 is preferably hydroxy, N(R.sup.401C)C(?O)R.sup.401D, N(R.sup.401C)C(?O)OR.sup.401D, fluorine, chlorine, bromine, methyl or methoxy.

[0174] In formulae (5-1) and (5-2), Rf.sup.1 to Rf.sup.4 are each independently hydrogen, fluorine or trifluoromethyl, at least one of Rf.sup.1 to Rf.sup.4 is fluorine or trifluoromethyl. Rf.sup.1 and Rf.sup.2, taken together, may form a carbonyl group. Preferably, both Rf.sup.3 and Rf.sup.4 are fluorine.

[0175] R.sup.402 to R.sup.406 are each independently halogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof are as exemplified above for the hydrocarbyl groups R.sup.101 to R.sup.105 in formulae (3-1) and (3-2). In the hydrocarbyl group, some or all of the hydrogen atoms may be substituted by hydroxy, carboxy, halogen, cyano, nitro, mercapto, sultone ring, sulfo, or sulfonium salt-containing moiety, and some constituent CH.sub.2 may be replaced by an ether bond, ester bond, carbonyl moiety, amide bond, carbonate bond or sulfonic ester bond. R.sup.402 and R.sup.403 may bond together to form a ring with the sulfur atom to which they are attached. Exemplary rings are as described above for the ring that R.sup.101 and R.sup.102 in formula (3-1), taken together, form with the sulfur atom to which they are attached.

[0176] Examples of the cation in the sulfonium salt having formula (5-1) include those exemplified above as the cation in the sulfonium salt having formula (3-1). Examples of the cation in the iodonium salt having formula (5-2) include those exemplified above as the cation in the iodonium salt having formula (3-2).

[0177] Examples of the anion in the onium salts having formulae (5-1) and (5-2) are shown below, but not limited thereto. Herein X.sup.BI is as defined above.

##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275## ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282##

##STR00283## ##STR00284## ##STR00285## ##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294##

##STR00295## ##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300## ##STR00301## ##STR00302## ##STR00303## ##STR00304## ##STR00305## ##STR00306## ##STR00307## ##STR00308## ##STR00309##

##STR00310## ##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316## ##STR00317## ##STR00318## ##STR00319##

[0178] When used, the acid generator of addition type is preferably added in an amount of 0.1 to 50 parts, and more preferably 1 to 40 parts by weight per 100 parts by weight of the base polymer. The resist composition functions as a chemically amplified resist composition when the base polymer includes repeat units (f) and/or the acid generator of addition type is contained.

Organic Solvent

[0179] An organic solvent may be added to the resist composition. The organic solvent used herein is not particularly limited as long as the foregoing and other components are soluble therein. Examples of the organic solvent are described in JP-A 2008-111103, paragraphs [0144]-[0145] (U.S. Pat. No. 7,537,880). Exemplary solvents include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone and 2-heptanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol (DAA); ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; and lactones such as ?-butyrolactone.

[0180] The organic solvent is preferably added in an amount of 100 to 10,000 parts, and more preferably 200 to 8,000 parts by weight per 100 parts by weight of the base polymer. The organic solvent may be used alone or in admixture.

Other Components

[0181] In addition to the foregoing components, the resist composition may further comprise other components such as a surfactant, dissolution inhibitor, crosslinker, quencher other than Sulfonium Salt A, water repellency improver, and acetylene alcohol. Each of additional components may be used alone or in admixture of two or more.

[0182] Exemplary surfactants are described in JP-A 2008-111103, paragraphs [0165]-[0166]. Inclusion of a surfactant may improve or control the coating characteristics of the resist composition. When used, the surfactant is preferably added in an amount of 0.0001 to 10 parts by weight per 100 parts by weight of the base polymer.

[0183] When the resist composition is of positive tone, the inclusion of a dissolution inhibitor may lead to an increased difference in dissolution rate between exposed and unexposed areas and a further improvement in resolution. The dissolution inhibitor which can be used herein is a compound having at least two phenolic hydroxy groups on the molecule, in which an average of from 0 to 100 mol % of all the hydrogen atoms on the phenolic hydroxy groups are replaced by acid labile groups or a compound having at least one carboxy group on the molecule, in which an average of 50 to 100 mol % of all the hydrogen atoms on the carboxy groups are replaced by acid labile groups, both the compounds having a molecular weight of 100 to 1,000, and preferably 150 to 800. Typical are bisphenol A, trisphenol, phenolphthalein, cresol novolac, naphthalenecarboxylic acid, adamantanecarboxylic acid, and cholic acid derivatives in which the hydrogen atom on the hydroxy or carboxy group is replaced by an acid labile group, as described in U.S. Pat. No. 7,771,914 (JP-A 2008-122932, paragraphs [0155]-[0178]).

[0184] When the resist composition is of positive tone and contains a dissolution inhibitor, the dissolution inhibitor is preferably added in an amount of 0 to 50 parts, more preferably 5 to 40 parts by weight per 100 parts by weight of the base polymer.

[0185] When the resist composition is of negative tone, a negative pattern may be formed by adding a crosslinker to reduce the dissolution rate of a resist film in exposed area. Suitable crosslinkers include epoxy compounds, melamine compounds, guanamine compounds, glycoluril compounds and urea compounds having substituted thereon at least one group selected from among methylol, alkoxymethyl and acyloxymethyl groups, isocyanate compounds, azide compounds, and compounds having a double bond such as an alkenyloxy group. These compounds may be used as an additive or introduced into a polymer side chain as a pendant. Hydroxy-containing compounds may also be used as the crosslinker.

[0186] Examples of the epoxy compound include tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether. Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine compounds having 1 to 6 methylol groups methoxymethylated and mixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol melamine compounds having 1 to 6 methylol groups acyloxymethylated and mixtures thereof. Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethylol guanamine compounds having 1 to 4 methylol groups methoxymethylated and mixtures thereof, tetramethoxyethyl guanamine, tetraacyloxyguanamine, tetramethylol guanamine compounds having 1 to 4 methylol groups acyloxymethylated and mixtures thereof. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds having 1 to 4 methylol groups methoxymethylated and mixtures thereof, tetramethylol glycoluril compounds having 1 to 4 methylol groups acyloxymethylated and mixtures thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds having 1 to 4 methylol groups methoxymethylated and mixtures thereof, and tetramethoxyethyl urea.

[0187] Suitable isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and cyclohexane diisocyanate. Suitable azide compounds include 1,1-biphenyl-4,4-bisazide, 4,4-methylidenebisazide, and 4,4-oxybisazide. Examples of the alkenyloxy group-containing compound include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylol propane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylol propane trivinyl ether.

[0188] When the resist composition is of negative tone and contains a crosslinker, the crosslinker is preferably added in an amount of 0.1 to 50 parts, more preferably 1 to 40 parts by weight per 100 parts by weight of the base polymer.

[0189] The other quencher is typically selected from conventional basic compounds. Conventional basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxy group, nitrogen-containing compounds with sulfonyl group, nitrogen-containing compounds with hydroxy group, nitrogen-containing compounds with hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and carbamate derivatives. Also included are primary, secondary, and tertiary amine compounds, specifically amine compounds having a hydroxy group, ether bond, ester bond, lactone ring, cyano group, or sulfonic ester bond as described in JP-A 2008-111103, paragraphs [0146]-[0164], and compounds having a carbamate group as described in JP 3790649. Addition of a basic compound may be effective for further suppressing the diffusion rate of acid in the resist film or correcting the pattern profile.

[0190] Onium salts such as sulfonium, iodonium and ammonium salts of sulfonic acids which are not fluorinated at ?-position as described in U.S. Pat. No. 8,795,942 (JP-A 2008-158339) and similar onium salts of carboxylic acid may also be used as the quencher. While an ?-fluorinated sulfonic acid, imide acid, and methide acid are necessary to deprotect the acid labile group of carboxylic acid ester, an ?-non-fluorinated sulfonic acid and a carboxylic acid are released by salt exchange with an ?-non-fluorinated onium salt. An ?-non-fluorinated sulfonic acid and a carboxylic acid function as a quencher because they do not induce deprotection reaction.

[0191] Also useful are quenchers of polymer type as described in U.S. Pat. No. 7,598,016 (JP-A 2008-239918). The polymeric quencher segregates at the resist surface and thus enhances the rectangularity of resist pattern. When a protective film is applied as is often the case in the immersion lithography, the polymeric quencher is also effective for preventing a film thickness loss of resist pattern or rounding of pattern top.

[0192] When used, the other quencher is preferably added in an amount of 0 to 5 parts, more preferably 0 to 4 parts by weight per 100 parts by weight of the base polymer.

[0193] To the resist composition, a water repellency improver may also be added for improving the water repellency on surface of a resist film. The water repellency improver may be used in the topcoatless immersion lithography. Suitable water repellency improvers include polymers having a fluoroalkyl group and polymers of specific structure having a 1,1,1,3,3,3-hexafluoro-2-propanol residue and are described in JP-A 2007-297590 and JP-A 2008-111103, for example. The water repellency improver should be soluble in the alkaline developer and organic solvent developer. The water repellency improver of specific structure having a 1,1,1,3,3,3-hexafluoro-2-propanol residue is well soluble in the developer. A polymer comprising repeat units having an amino group or amine salt may serve as the water repellent additive and is effective for preventing evaporation of acid during PEB, thus preventing any hole pattern opening failure after development. An appropriate amount of the water repellency improver is 0 to 20 parts, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the base polymer.

[0194] Also, an acetylene alcohol may be blended in the resist composition. Suitable acetylene alcohols are described in JP-A 2008-122932, paragraphs [0179]-[0182]. An appropriate amount of the acetylene alcohol blended is 0 to 5 parts by weight per 100 parts by weight of the base polymer.

Process

[0195] The resist composition is used in the fabrication of various integrated circuits. Pattern formation using the resist composition may be performed by well-known lithography processes. The process generally involves the steps of applying the resist composition onto a substrate to form a resist film thereon, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer. If necessary, any additional steps may be added.

[0196] Specifically, the resist composition is first applied onto a substrate on which an integrated circuit is to be formed (e.g., Si, SiO.sub.2, SiN, SiON, TiN, WSi, BPSG, SOG, or organic antireflective coating) or a substrate on which a mask circuit is to be formed (e.g., Cr, CrO, CrON, MoSi.sub.2, or SiO.sub.2) by a suitable coating technique such as spin coating, roll coating, flow coating, dipping, spraying or doctor coating. The coating is prebaked on a hotplate preferably at a temperature of 60 to 150? C. for 10 seconds to 30 minutes, more preferably at 80 to 120? C. for 30 seconds to 20 minutes. The resulting resist film is generally 0.01 to 2 ?m thick.

[0197] The resist film is then exposed to a desired pattern of high-energy radiation such as UV, deep-UV, EB, EUV of wavelength 3 to 15 nm, x-ray, soft x-ray, excimer laser light, ?-ray or synchrotron radiation. When UV, deep-UV, EUV, x-ray, soft x-ray, excimer laser light, ?-ray or synchrotron radiation is used as the high-energy radiation, the resist film is exposed thereto directly or through a mask having a desired pattern in a dose of preferably about 1 to 200 mJ/cm.sup.2, more preferably about 10 to 100 mJ/cm.sup.2. When EB is used as the high-energy radiation, the resist film is exposed thereto directly or through a mask having a desired pattern in a dose of preferably about 0.1 to 300 ?C/cm.sup.2, more preferably about 0.5 to 200 ?C/cm.sup.2. It is appreciated that the inventive resist composition is suited in micropatterning using KrF excimer laser, ArF excimer laser, EB, EUV, x-ray, soft x-ray, ?-ray or synchrotron radiation, especially in micropatterning using EB or EUV.

[0198] After the exposure, the resist film may be baked (PEB) on a hotplate or in an oven preferably at 30 to 150? C. for 10 seconds to 30 minutes, more preferably at 50 to 130? C. for 30 seconds to 20 minutes.

[0199] After the exposure or PEB, the resist film is developed in a developer in the form of an aqueous base solution for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes by conventional techniques such as dip, puddle and spray techniques. A typical developer is a 0.1 to 10 wt %, preferably 2 to 5 wt % aqueous solution of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), or tetrabutylammonium hydroxide (TBAH). In the case of positive tone, the resist film in the exposed area is dissolved in the developer whereas the resist film in the unexposed area is not dissolved. In this way, the desired positive pattern is formed on the substrate. In the case of negative tone, inversely the resist film in the exposed area is insolubilized whereas the resist film in the unexposed area is dissolved away.

[0200] In an alternative embodiment, a negative pattern can be obtained from the positive resist composition comprising a base polymer containing acid labile groups by effecting organic solvent development. The developer used herein is preferably selected from among 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate, and mixtures thereof.

[0201] At the end of development, the resist film is rinsed. As the rinsing liquid, a solvent which is miscible with the developer and does not dissolve the resist film is preferred. Suitable solvents include alcohols of 3 to 10 carbon atoms, ether compounds of 8 to 12 carbon atoms, alkanes, alkenes, and alkynes of 6 to 12 carbon atoms, and aromatic solvents. Specifically, suitable alcohols of 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol. Suitable ether compounds of 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-s-butyl ether, di-n-pentyl ether, diisopentyl ether, di-s-pentyl ether, di-t-pentyl ether, and di-n-hexyl ether. Suitable alkanes of 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Suitable alkynes of 6 to 12 carbon atoms include hexyne, heptyne, and octyne. Suitable aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, t-butylbenzene and mesitylene.

[0202] Rinsing is effective for minimizing the risks of resist pattern collapse and defect formation. However, rinsing is not essential. If rinsing is omitted, the amount of solvent used is reduced.

[0203] A hole or trench pattern after development may be shrunk by the thermal flow, RELACS? or DSA process. A hole pattern is shrunk by coating a shrink agent thereto, and baking such that the shrink agent may undergo crosslinking at the resist film surface as a result of the acid catalyst diffusing from the resist film during bake, and the shrink agent may attach to the sidewall of the hole pattern. The bake is preferably at a temperature of 70 to 180? C., more preferably 80 to 170? C., for a time of 10 to 300 seconds. The extra shrink agent is stripped and the hole pattern is shrunk.

EXAMPLES

[0204] Examples of the invention are given below by way of illustration and not by way of limitation. All parts are by weight (pbw).

Example 1-1 Synthesis of Quencher Q-1

(1) Synthesis of Intermediate In-1

[0205] ##STR00320##

[0206] In nitrogen atmosphere, a 20-mL portion of a dilution of 50 g of 2-bromobenzothiophene with 320 mL of THF was added to 4.85 g of magnesium, whereupon the temperature of the solution rose to 60? C. After the reaction solution was cooled at 40? C., the remainder of the dilution was added thereto while keeping the temperature of 40-50? C. The solution was stirred for 18 hours, yielding a Grignard reagent. The Grignard reagent was added to 300 mL of a solution of dry ice in THF, followed by 7 hours of stirring. In this step, the amount of dry ice was adjusted as needed such that an excess of dry ice was always available. Thereafter, 200 g of 20 wt % hydrochloric acid was added to the reaction solution to quench the reaction. 400 g of ethyl acetate was added to extract the end compound, and the end compound was washed 4 times with 100 g of deionized water. The organic layer was taken out and the solvent was distilled off whereupon crystals precipitated out. 300 mL of toluene was added for recrystallization. The crystals were collected and dried in vacuum, obtaining 19.8 g of Intermediate In-1 as white solid (yield 46%).

(2) Synthesis of Intermediate In-2

[0207] ##STR00321##

[0208] After 58.5 g of Intermediate In-1 was dissolved in 350 g of methanol, 6.3 g of sulfuric acid was added. The solution was heated under reflux at 80? C. for 24 hours while monitoring the process by NMR spectroscopy. After the completion of reaction, the solution was returned to room temperature. While cooling in an ice bath, the solution was adjusted with triethylamine to neutral (pH 7). The solvent was then distilled off. After 800 g of a 2:1 solvent mixture of toluene and ethyl acetate was added, separatory operation was carried out 2 times with 100 g of deionized water, once with 100 g of saturated sodium hydrogencarbonate aqueous solution, and 5 times with 100 g of deionized water. After confirmation of neutrality, the organic layer was taken out. The extraction solvent was distilled off under reduced pressure, followed by recrystallization with 300 g of cool hexane and vacuum drying. There was obtained 48.8 g of Intermediate In-2 as white crystals (yield 79%).

(3) Synthesis of Intermediate In-3

[0209] ##STR00322##

[0210] After 10 g of Intermediate In-2, 0.26 g of copper sulfate, 19.6 g of reactant M-1, and 50 g of anisole were mixed, the reaction system was heated at 95? C. and stirred for 2 hours. At the end of reaction, 150 g of diisopropyl ether was added to the reaction system whereupon white crystals precipitated. The solution was stirred for a further 1 hour. White solids were collected by filtration and dissolved in dichloromethane. Activated carbon was added to the solution, followed by 2 hours of stirring. After the activated carbon was removed by filtration, the solvent was distilled off under reduced pressure. This was followed by recrystallization from 50 g of methyl isobutyl ketone and vacuum drying, obtaining 15.5 g of Intermediate In-3 as white crystals (yield 80%).

(4) Synthesis of Intermediate In-4

[0211] ##STR00323##

[0212] A mixture of 13 g of Intermediate In-3, 40 g of an ion exchange resin (Amberlite?) and 100 g of methanol was stirred at room temperature for 3 hours. At the end of reaction, Amberlite was removed by filtration and the solvent was distilled off. Using hexane, decantation was performed several times. This was followed by recrystallization and vacuum drying, obtaining 8.9 g of Intermediate In-4 as white solids (yield 90%).

(5) Synthesis of Quencher Q-1

[0213] ##STR00324##

[0214] A mixture of 16.1 g of Intermediate In-4, 12.5 g of reactant M-2, 165 g of dichloromethane, and 50 g of deionized water was stirred at room temperature for 1 hour. At the end of reaction, the organic layer was taken out and washed 4 times with 50 g of deionized water until its pH was confirmed to be neutral. The solvent was distilled off under reduced pressure. This was followed by recrystallization from 60 g of diisopropyl ether, filtration and vacuum drying. There was obtained 21.7 g of the target quencher Q-1 as white crystals (yield 92%).

Examples 1-2 to 1-22 Synthesis of Quenchers Q-2 to Q-22

[0215] Quenchers Q-2 to Q-22 were synthesized by the same procedure as in Example 1-1. The structure of Quenchers Q-1 to Q-22 is shown below.

##STR00325## ##STR00326## ##STR00327## ##STR00328##

Synthesis Example Synthesis of Base Polymers P-1 to P-5

[0216] Base polymers P-1 to P-5 were synthesized by combining monomers, performing copolymerization reaction in THF solvent, pouring the reaction solution to methanol for precipitation, washing the solid precipitate with hexane, isolation and drying. The polymer was analyzed for composition by .sup.1H-NMR spectroscopy and for Mw and Mw/Mn by GPC versus polystyrene standards using THF solvent.

##STR00329##

Examples 2-1 to 2-26 and Comparative Examples 1-1 to 1-3

(1) Preparation of Resist Compositions

[0217] Resist compositions in solution form were prepared by dissolving selected components in a solvent in accordance with the formulation shown in Tables 1 and 2, and filtering through a filter with a pore size of 0.2 ?m. The resist compositions of Examples 1 to 25 and Comparative Examples 1 and 2 were of positive tone whereas the resist compositions of Example 26 and Comparative Example 3 were of negative tone.

[0218] The components in Tables 1 and 2 are identified below.

Organic Solvents:

[0219] PGMEA (propylene glycol monomethyl ether acetate) [0220] DAA (diacetone alcohol) [0221] EL (ethyl acetate)

Acid Generators PAG-1 to PAG-4

[0222] ##STR00330##

Blend Quenchers bQ-1 and bQ-2

##STR00331##

Comparative Quenchers cQ-1 and cQ-2

##STR00332##

(2) EUV Lithography Test

[0223] Each of the resist compositions in Tables 1 and 2 was spin coated on a silicon substrate having a 20-nm coating of silicon-containing spin-on hard mask SHB-A940 (Shin-Etsu Chemical Co., Ltd., silicon content 43 wt %) and prebaked on a hotplate at 100? C. for 60 seconds to form a resist film of 60 nm thick. Using an EUV scanner NXE3400 (ASML, NA 0.33, ?0.9/0.6, quadrupole illumination), the resist film was exposed to EUV through a mask bearing a hole pattern having a pitch of 44 nm+20% bias (on-wafer size). The resist film was baked (PEB) on a hotplate at the temperature shown in Tables 1 and 2 for 60 seconds and developed in a 2.38 wt % TMAH aqueous solution for 30 seconds. Hole patterns with a size of 22 nm were obtained in Examples 1 to 25 and Comparative Examples 1 and 2 whereas dot patterns with a size of 22 nm were obtained in Example 26 and Comparative Example 3.

[0224] The hole or dot pattern was observed under CD-SEM (CG6300, Hitachi High-Technologies Corp.). The exposure dose that provides a hole or dot pattern having a size of 22 nm was determined and reported as sensitivity. The size of 50 holes or dots at that dose was measured, from which a 3-fold value (36) of the standard deviation (6) was computed and reported as CDU. The results are also shown in Tables 1 and 2.

TABLE-US-00001 TABLE 1 Acid Organic PEB Polymer generator Quencher solvent temp. Sensitivity CDU (pbw) (pbw) (pbw) (pbw) (? C.) (mJ/cm.sup.2) (nm) Example 1 P-1 PAG-1 Q-1 PGMEA (3000) 90 26 2.6 (100) (30.2) (5.24) DAA (500) 2 P-1 PAG-2 Q-2 PGMEA (3000) 90 25 2.7 (100) (24.8) (5.08) DAA (500) 3 P-1 PAG-2 Q-3 PGMEA (3000) 90 24 2.4 (100) (24.8) (8.18) DAA (500) 4 P-1 PAG-2 Q-4 (3.84) PGMEA (3000) 90 27 2.4 (100) (24.8) bQ-1 (3.80) DAA (500) 5 P-1 PAG-2 Q-5 PGMEA (3000) 90 24 2.6 (100) (24.8) (7.07) DAA (500) 6 P-1 PAG-2 Q-6 PGMEA (3000) 90 26 2.7 (100) (24.8) (5.40) DAA (500) 7 P-1 PAG-2 Q-7 PGMEA (3000) 90 23 2.8 (100) (24.8) (5.12) DAA (500) 8 P-1 PAG-2 Q-8 PGMEA (3000) 90 25 2.6 (100) (24.8) (5.28) DAA (500) 9 P-1 PAG-3 Q-9 (2.64) PGMEA (3000) 90 27 2.5 (100) (25.7) bQ-2 (3.27) DAA (500) 10 P-1 PAG-3 Q-10 PGMEA (3000) 90 24 2.6 (100) (25.7) (5.24) DAA (500) 11 P-1 PAG-3 Q-11 PGMEA (3000) 90 24 2.5 (100) (25.7) (5.40) DAA (500) 12 P-1 PAG-3 Q-12 EL (3000) 90 28 2.4 (100) (25.7) (5.69) DAA (500) 13 P-1 PAG-3 Q-13 EL (3500) 90 26 2.3 (100) (25.7) (5.58) 14 P-1 PAG-3 Q-14 PGMEA (3000) 90 23 2.4 (100) (25.7) (5.50) DAA (500) 15 P-1 PAG-3 Q-15 PGMEA (3000) 90 26 2.5 (100) (25.7) (6.92) DAA (500) 16 P-1 PAG-3 Q-16 PGMEA (3000) 90 26 2.6 (100) (25.7) (6.06) DAA (500) 17 P-1 PAG-3 Q-17 PGMEA (3000) 90 27 2.4 (100) (25.7) (6.34) DAA (500) 18 P-1 PAG-3 Q-18 PGMEA (3000) 90 28 2.3 (100) (25.7) (6.89) DAA (500) 19 P-1 PAG-3 Q-19 PGMEA (3000) 90 24 2.3 (100) (25.7) (6.14) DAA (500) 20 P-1 PAG-3 Q-20 PGMEA (3000) 90 24 2.4 (100) (25.7) (6.50) DAA (500) 21 P-1 PAG-3 Q-21 PGMEA (3000) 90 26 2.4 (100) (25.7) (5.76) DAA (500) 22 P-1 PAG-3 Q-22 PGMEA (3000) 90 27 2.4 (100) (25.7) (6.76) DAA (500) 23 P-2 PAG-2 Q-8 PGMEA (3000) 90 28 2.2 (100) (24.8) (5.28) DAA (500) 24 P-3 Q-8 PGMEA (3000) 90 27 2.3 (100) (5.28) DAA (500) 25 P-4 Q-8 PGMEA (3000) 90 23 2.3 (100) (5.28) DAA (500) 26 P-5 PAG-1 Q-8 PGMEA (3000) 110 32 3.2 (100) (24.1) (5.28) DAA (500)

TABLE-US-00002 TABLE 2 Acid Organic PEB Polymer generator Quencher solvent temp. Sensitivity CDU (pbw) (pbw) (pbw) (pbw) (? C.) (mJ/cm.sup.2) (nm) Comparative 1 P-1 PAG-2 cQ-1 PGMEA (3000) 90 31 3.3 Example (100) (24.8) (4.40) DAA (500) 2 P-1 PAG-2 cQ-2 PGMEA (3000) 90 33 3.2 (100) (24.8) (4.50) DAA (500) 3 P-5 PAG-1 cQ-1 PGMEA (3000) 110 38 4.0 (100) (24.1) (4.40) DAA (500)

[0225] It is demonstrated in Tables 1 and 2 that resist compositions comprising Sulfonium Salt A offer a high sensitivity and improved CDU.

[0226] Japanese Patent Application No. 2023-019260 is incorporated herein by reference. Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.