Resist composition and patterning process

Abstract

A resist composition comprising a base polymer and a quencher in the form of an ammonium salt consisting of an ammonium cation having an iodized aromatic ring bonded to the nitrogen atom via a C.sub.1-C.sub.20 hydrocarbylene group and an anion derived from an iodized or brominated phenol offers a high sensitivity and minimal LWR or improved CDU, independent of whether it is of positive or negative tone.

Claims

1. A resist composition comprising a base polymer and a quencher, the quencher being an ammonium salt consisting of an ammonium cation having an iodine-substituted aromatic ring bonded to the nitrogen atom via a C.sub.1-C.sub.20 hydrocarbylene group which may contain at least one moiety selected from ester bond and ether bond and an anion derived from an iodine or bromine-substituted phenol.

2. The resist composition of claim 1 wherein the ammonium salt has the formula (A): ##STR00181## wherein m is an integer of 1 to 5, n is an integer of 0 to 4, l≤m+n≤5, p.sup.1 is 1, 2 or 3, p.sup.2 is 1 or 2, q is an integer of 1 to 5, r is an integer of 0 to 4, l≤q+r≤5, X.sup.B1 is iodine or bromine, X.sup.1 is a C.sub.1-C.sub.20 (p.sup.2+1)-valent hydrocarbon group which may contain at least moiety selected from ester bond and ether bond, R.sup.1 is a hydroxyl group, C.sub.1-C.sub.6 saturated hydrocarbyl group, C.sub.1-C.sub.6 saturated hydrocarbyloxy group, C.sub.2-C.sub.6 saturated hydrocarbylcarbonyloxy group, fluorine, chlorine, bromine, amino group, —NR.sup.1A—C(═O)—R.sup.1B, or —NR.sup.1A—C(═O)O—R.sup.1B, R.sup.1A is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group, R.sup.1B is a C.sub.1-C.sub.6 saturated hydrocarbyl, C.sub.2-C.sub.8 unsaturated aliphatic hydrocarbyl, C.sub.6-C.sub.12 aryl or C.sub.7-C.sub.13 aralkyl group, R.sup.2 is hydrogen, nitro, or a C.sub.1-C.sub.20 hydrocarbyl group which may contain at least one moiety selected from hydroxyl, carboxyl, thiol, ether bond, ester bond, nitro, cyano, halogen and amino moiety, in case of p.sup.1=1 or 2, two R.sup.2 may bond together to form a ring with the nitrogen atom to which they are attached, the ring optionally containing a double bond, oxygen, sulfur or nitrogen, or R.sup.2 and X.sup.1 may bond together to form a ring with the nitrogen atom to which they are attached, the ring optionally containing a double bond, oxygen, sulfur or nitrogen, R.sup.3 is a hydroxyl group, optionally fluorinated or chlorinated C.sub.1-C.sub.6 saturated hydrocarbyl group, optionally fluorinated or chlorinated C.sub.1-C.sub.6 saturated hydrocarbyloxy group, optionally fluorinated or chlorinated C.sub.2-C.sub.6 saturated hydrocarbyloxycarbonyl group, formyl group, optionally fluorinated or chlorinated C.sub.2-C.sub.6 saturated hydrocarbylcarbonyl group, optionally fluorinated or chlorinated C.sub.2-C.sub.6 saturated hydrocarbylcarbonyloxy group, optionally fluorinated or chlorinated C.sub.1-C.sub.4 saturated hydrocarbylsulfonyloxy group, C.sub.6-C.sub.10 aryl group, fluorine, chlorine, amino group, nitro group, cyano group, —NR.sup.3A—C(═O)—R.sup.3B, or NR.sup.3A—C(═O)—O—R.sup.3B, R.sup.3A is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group, R.sup.3B is a C.sub.1-C.sub.6 saturated hydrocarbyl group or C.sub.2-C.sub.8 unsaturated aliphatic hydrocarbyl group.

3. The resist composition of claim 1, further comprising an acid generator capable of generating a sulfonic acid, imide acid or methide acid.

4. The resist composition of claim 1 wherein the base polymer comprises recurring units having the formula (a1) or recurring units having the formula (a2): ##STR00182## wherein R.sup.A is each independently hydrogen or methyl, R.sup.11 and R.sup.12 each are an acid labile group, Y.sup.1 is a single bond, phenylene group, naphthylene group, or C.sub.1-C.sub.12 linking group containing at least one moiety selected from ester bond and lactone ring, and Y.sup.2 is a single bond or ester bond.

5. The resist composition of claim 4 which is a chemically amplified positive resist composition.

6. The resist composition of claim 1 wherein the base polymer is free of an acid labile group.

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

8. The resist composition of claim 1 wherein the base polymer comprises recurring units of at least one type selected from recurring units having the formulae (f1) to (f3): ##STR00183## wherein R.sup.A is each independently hydrogen or methyl, Z.sup.1 is a single bond, phenylene group, —O—Z.sup.11—, —C(═O)—Z.sup.11— or —C(═O)—NH—Z.sup.11—, Z.sup.11 is a C.sub.1-C.sub.6 aliphatic hydrocarbylene group or phenylene group, which may contain a carbonyl, ester bond, ether bond or hydroxyl moiety, Z.sup.2 is a single bond, —Z.sup.21—C(═O)—O—, —Z.sup.21—O— or —Z.sup.21—C(═O)—, Z.sup.21 is a C.sub.1-C.sub.12 saturated hydrocarbylene group which may contain a carbonyl moiety, ester bond or ether bond, Z.sup.3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z.sup.31—, —C(═O)—O—Z.sup.31—, or —C(═O)—NH—Z.sup.31—, —Z.sup.31 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 or hydroxyl moiety, R.sup.21 to R.sup.28 are each independently a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom, any two of R.sup.23, R.sup.24 and R.sup.25 or any two of R.sup.26, R.sup.27 and R.sup.28 may bond together to form a ring with the sulfur atom to which they are attached, A.sup.1 is hydrogen or trifluoromethyl, and M.sup.− is a non-nucleophilic counter ion.

9. The resist composition of claim 1, further comprising an organic solvent.

10. The resist composition of claim 1, father comprising a surfactant.

11. A process for forming a pattern comprising the steps of applying the resist composition of claim 1 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.

12. The process of claim 11 wherein the high-energy radiation is ArF excimer laser radiation of wavelength 193 nm or KrF excimer laser radiation of wavelength 248 nm.

13. The process of claim 11 wherein the high-energy radiation is EB or EUV of wavelength 3 to 15 nm.

Description

DESCRIPTION OF EMBODIMENTS

(1) As used herein, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. The notation (C.sub.n-C.sub.m) means a group containing from n to m carbon atoms per group. As used herein, the term “iodized” or “brominated” compound means an iodine or bromine-substituted compound. In chemical formulae, Me stands for methyl, and Ac for acetyl.

(2) The abbreviations and acronyms have the following meaning.

(3) EB: electron beam

(4) EUV: extreme ultraviolet

(5) Mw: weight average molecular weight

(6) Mn: number average molecular weight

(7) Mw/Mn: molecular weight distribution or dispersity

(8) GPC: gel permeation chromatography

(9) PEB: post-exposure bake

(10) PAG: photoacid generator

(11) LWR: line width roughness

(12) CDU: critical dimension uniformity

(13) Resist Composition

(14) The resist composition of the invention is defined as comprising a base polymer and a quencher in the form of an iodized aromatic ring-containing ammonium salt.

(15) Iodized Aromatic Ring-Containing Ammonium Salt

(16) The iodized aromatic ring-containing ammonium salt is a compound consisting of an ammonium cation having an iodine-substituted aromatic ring banded to the nitrogen atom via a C.sub.1-C.sub.20 hydrocarbylene group which may contain at least one moiety selected from ester bond and ether bond and an anion derived from an iodine or bromine-substituted phenol. Preferably the ammonium salt has the formula (A).

(17) ##STR00004##

(18) In formula (A), m is an integer of 1 to 5, n is an integer of 0 to 4, and 1≤m+n≤5. Preferably, m is 2, 3 or 4, and n is 0 or 1. The subscript p.sup.1 is 1, 2 or 3, p.sup.2 is 1 or 2, q is an integer of 1 to 5, r is an integer of 0 to 4, and 1≤q+r≤5. Preferably, q is 2 or 3, and r is 0, 1 or 2.

(19) In formula (A), X.sup.B1 is iodine or bromine.

(20) In formula (A), X.sup.1 is a C.sub.1-C.sub.20 (p.sup.2+1)-valent hydrocarbon group which may contain at least moiety selected from ester bond and ether bond. The hydrocarbon group may be saturated or unsaturated and straight, branched or cyclic. Examples include C.sub.1-C.sub.20 hydrocarbylene groups and trivalent groups obtained by eliminating one hydrogen atom from the hydrocarbylene groups. Suitable hydrocarbylene groups include alkanediyl groups such as methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-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, and dodecane-1,12-diyl; C.sub.3-C.sub.20 saturated cyclic hydrocarbylene groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; C.sub.2-C.sub.20 unsaturated aliphatic hydrocarbylene groups such as vinylene and propene-1,3-diyl; C.sub.6-C.sub.20 arylene groups such as phenylene and naphthylene; and combinations thereof.

(21) In formula (A), R.sup.1 is a hydroxyl group, C.sub.1-C.sub.6 saturated hydrocarbyl group, C.sub.1-C.sub.6 saturated hydrocarbyloxy group, C.sub.2-C.sub.6 saturated hydrocarbylcarbonyloxy group, fluorine, chlorine, bromine, amino group. —NR.sup.1A—C(═O)—R.sup.1B, or —NR.sup.1A—C(═O)—O—R.sup.1B. R.sup.1A is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group. R.sup.1B is a C.sub.1-C.sub.6 saturated hydrocarbyl, C.sub.2-C.sub.8 unsaturated aliphatic hydrocarbyl, C.sub.6-C.sub.12 aryl or C.sub.7-C.sub.13 aralkyl group.

(22) The C.sub.1-C.sub.6 saturated hydrocarbyl group may be straight, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, and cyclohexyl. Examples of the saturated hydrocarbyl moiety in the C.sub.1-C.sub.6 saturated hydrocarbyloxy group and C.sub.2-C.sub.6 saturated hydrocarbylcarbonyloxy group are as exemplified above for the saturated hydrocarbyl group.

(23) The C.sub.2-C.sub.8 unsaturated aliphatic hydrocarbyl group may be straight, branched or cyclic and examples thereof include vinyl, 1-propenyl, 2-propenyl, butenyl, hexenyl, and cyclohexenyl.

(24) Suitable C.sub.6-C.sub.12 aryl groups include phenyl, tolyl, xylyl, 1-naphthyl and 2-naphthyl. Suitable C.sub.7-C.sub.13 aralkyl groups include benzyl and phenethyl.

(25) Among others, R.sup.1 is preferably selected from fluorine, chlorine, bromine, hydroxyl, amino, C.sub.1-C.sub.3 saturated hydrocarbyl groups, C.sub.1-C.sub.3 saturated hydrocarbyloxy groups, C.sub.2-C.sub.4 saturated hydrocarbylcarbonyloxy groups, —NR.sup.1A—C(═O)—R.sup.1B, and NR.sup.1A—C(═O)—O—R.sup.1B. Groups R.sup.1 may be identical or different when n is 2 or more.

(26) In formula (A). R.sup.2 is hydrogen, nitro, or a C.sub.1-C.sub.20 hydrocarbyl group. 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 saturated cyclic 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 unsaturated cyclic aliphatic hydrocarbyl groups such as cyclohexenyl and norbornenyl; C.sub.2-C.sub.20 alkynyl groups such as ethynyl, propynyl and butynyl; 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 such as 2-cyclohexylethynyl and 2-phenylethynyl. The hydrocarbyl group may contain at least one moiety selected from hydroxyl, carboxyl, thiol, ether bond, ester bond, nitro, cyano, halogen and amino moiety.

(27) In case of p.sup.1=1 or 2, R.sup.2 may be the same or different. Also in case of p.sup.1=1 or 2, two R.sup.2 may bond together to form a ring with the nitrogen atom to which they are attached, the ring optionally containing a double bond, oxygen, sulfur or nitrogen, or R.sup.2 and X.sup.1 may bond together to form a ring with the nitrogen atom to which they are attached, the ring optionally containing a double bond, oxygen, sulfur or nitrogen.

(28) In formula (A), R.sup.3 is a hydroxyl group, optionally fluorinated or chlorinated C.sub.1-C.sub.6 saturated hydrocarbyl group, optionally fluorinated or chlorinated C.sub.1-C.sub.6 saturated hydrocarbyloxy group, optionally fluorinated or chlorinated C.sub.2-C.sub.6 saturated hydrocarbyloxycarbonyl group, formyl group, optionally fluorinated or chlorinated C.sub.2-C.sub.6 saturated hydrocarbylcarbonyl group, optionally fluorinated or chlorinated C.sub.2-C.sub.6 saturated hydrocarbylcarbonyloxy group, optionally fluorinated or chlorinated C.sub.1-C.sub.4 saturated hydrocarbylsulfonyloxy group. C.sub.6-C.sub.10 aryl group, fluorine, chlorine, amino group, nitro group, cyano group, —NR.sup.3A—C(═O)—R.sup.3B, or —NR.sup.3A—(═O)O—R.sup.3B. R.sup.3A is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group. R.sup.3B is a C.sub.1-C.sub.6 saturated hydrocarbyl group or C.sub.2-C.sub.8 unsaturated aliphatic hydrocarbyl group.

(29) Examples of the saturated hydrocarbyl groups represented by R.sup.3. R.sup.3A and R.sup.3B are as exemplified above for R.sup.1. Examples of the saturated hydrocarbyl moiety in the saturated hydrocarbyloxy group, saturated hydrocarbyloxycarbonyl group, saturated hydrocarbylcarbonyl group, saturated hydrocarbylcarbonyloxy group, and saturated hydrocarbylsulfonyloxy group are as exemplified above for the saturated hydrocarbyl group R. The C.sub.2-C.sub.8 unsaturated aliphatic hydrocarbyl group represented by R.sup.3B may be straight, branched or cyclic and examples thereof are as exemplified above for R.sup.1. Exemplary C.sub.6-C.sub.10 aryl groups include phenyl and naphthyl.

(30) Examples of the cation in the iodized aromatic ring-containing ammonium salt are shown below, but not limited thereto.

(31) ##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029##

(32) Examples of the anion in the iodized aromatic ring-containing ammonium salt aw shown below, but not limited thereto.

(33) ##STR00030## ##STR00031## ##STR00032##

(34) The ammonium salt having formula (A) may be synthesized, for example, by neutralization reaction of an iodized aromatic ring-containing amine compound capable of providing the cation of the ammonium salt and an iodized or brominated phenol.

(35) The inventive ammonium salt functions as a quencher having a sensitizing effect in a resist composition. While a conventional quencher functions to control acid diffusion to endow a resist material with a lower sensitivity for thereby reducing LWR or CDU, the inventive ammonium salt has an acid diffusion controlling effect due to the inclusion of nitrogen and iodine (of large atomic weight) in its cation, and a sensitizing effect due to the inclusion of fully EUV-absorptive iodine or bromine atom in its anion, both contributing to a high sensitivity.

(36) The inventive ammonium salt has an anion derived from an iodized or brominated phenol. The anion generates phenoxide radicals or secondary electrons upon light exposure. The generated radicals or secondary electrons promote decomposition of a sulfonium salt or iodonium salt, thereby endowing the resist composition with a high sensitivity.

(37) The ammonium salt is effective for suppressing acid diffusion in the exposed region because it is not photosensitive and is thus not decomposed upon light exposure. The ammonium salt is also effective for enhancing dissolution contrast because the iodized or brominated phenol dissolves in the alkaline developer.

(38) From the standpoints of sensitivity and acid diffusion suppressing effect, the iodized to aromatic ring-containing ammonium salt is preferably present in the resist composition 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 the base polymer to be described below.

(39) Base Polymer

(40) Where the resist composition is of positive tone, the base polymer comprises recurring units containing an acid labile group, preferably recurring units having the formula (a1) or recurring units having the formula (a2). These units are simply referred to as recurring units (a1) and (a2).

(41) ##STR00033##

(42) In formulae (a1) and (a2), R.sup.A is each independently hydrogen or methyl. R.sup.11 and R.sup.12 each are an acid labile group. Y.sup.1 is a single bond, phenylene or naphthylene group, or C.sub.1-C.sub.12 linking group containing at least one moiety selected from ester bond and lactone ring. Y.sup.2 is a single bond or ester bod. When the base polymer contains both recurring units (a1) and (a2), R.sup.11 and R.sup.12 may be the same or different.

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

(44) ##STR00034##

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

(46) ##STR00035##

(47) The acid labile groups represented by R.sup.11 and R.sup.12 in formulae (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).

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

(49) ##STR00036##

(50) 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 groups may be saturated or unsaturated and straight, branched or cyclic. Of the hydrocarbyl groups, C.sub.1-C.sub.40, especially C.sub.1-C.sub.20 alkyl groups are preferred. In formula (AL-1), “a” is an integer of 0 to 10, preferably 1 to 5.

(51) 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 groups may be saturated or unsaturated and straight, branched or cyclic. Of the hydrocarbyl groups, C.sub.1-C.sub.20 alkyl groups are preferred. Any two of R.sup.L2, R.sup.L3 and R.sup.L4 may bond together to form a ring, typically alicyclic, with the carbon atom or carbon and oxygen atoms to which they are attached, the ring containing 3 to 20 carbon atoms, preferably 4 to 16 carbon atoms.

(52) 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 groups may be saturated or unsaturated and straight, branched or cyclic. Of the hydrocarbyl groups, C.sub.1-C.sub.20 alkyl groups are preferred. Any two of R.sup.L5, R.sup.L6 and R.sup.L7 may bond together to form a ring, typically alicyclic, with the carbon atom to which they are attached, the ring containing 3 to 20 carbon atoms, preferably 4 to 16 carbon atoms.

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

(54) ##STR00037##

(55) Further, recurring units (c) having another adhesive group selected from hydroxyl (other than the foregoing phenolic hydroxyl), lactone ring, sultone ring, ether bond, ester bond, sulfonate bond, carbonyl, sulfonyl, cyano, and carboxyl groups may also be incorporated in the base polymer. Examples of suitable monomers from which recurring units (c) are derived are given below, but not limited thereto. Herein R.sup.A is as defined above.

(56) ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054##

(57) In another preferred embodiment, the base polymer may further comprise recurring units (d) selected from units of indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, and norbornadiene, or derivatives thereof. Suitable monomers are exemplified below.

(58) ##STR00055##

(59) Furthermore, recurring units (e) may be incorporated in the base polymer, which are derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindene, vinylpyridine, and vinylcarbazole.

(60) In a further embodiment, recurring units (f) derived from an onium salt having a polymerizable unsaturated bond may be incorporated in the base polymer. Specifically, the base polymer may comprise recurring units of at least one type selected from formulae (f1), (2) and (f3). These units are simply referred to as recurring units (f1), (2) and (3), which may be used alone or in combination of two or more types.

(61) ##STR00056##

(62) In formulae (f1) to (f3), R.sup.A is independently hydrogen or methyl. Z.sup.1 is a single bond, phenylene group, —O—Z.sup.11—, —C(═O)—O—Z.sup.11—, or —C(═O)—NH—Z.sup.11—, wherein Z.sup.11 is a C.sub.1-C.sub.6 aliphatic hydrocarbylene group or phenylene group, which may contain a carbonyl, ester bond, ether bond or hydroxyl moiety. Z.sup.2 is a single bond, —Z.sup.21—C(═O)—O—, —Z.sup.21—O— or —Z.sup.21—O—C(═O)—, wherein Z.sup.21 is a C.sub.1-C.sub.12 saturated hydrocarbylene group which may contain a carbonyl moiety, ester bond or ether bond. Z.sup.3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z.sup.31—, —C(═O)—O—Z.sup.31—, or —C(═O)—NH—Z.sup.31—, wherein Z.sup.31 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 or hydroxyl moiety. The aliphatic hydrocarbylene group may be saturated or unsaturated and straight, branched or cyclic. The saturated hydrocarbylene group may be straight, branched or cyclic.

(63) In formulae (f1) to (f3), R.sup.21 to R.sup.28 are each independently 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 include C.sub.1-C.sub.20 alkyl groups, C.sub.6-C.sub.20 aryl groups, and C.sub.7-C.sub.20 aralkyl groups. In these groups, some or all of the hydrogen atoms may be substituted by C.sub.1-C.sub.10 saturated hydrocarbyl moiety, halogen, trifluoromethyl, cyano, nitro, hydroxyl, mercapto, C.sub.1-C.sub.10 saturated hydrocarbyloxy moiety, C.sub.2-C.sub.10 saturated hydrocarbyloxycarbonyl moiety, or C.sub.2-C.sub.10 saturated hydrocarbylcarbonyloxy moiety, and some carbon atom may be replaced by a carbonyl moiety, ether bond or ester bond. Any two of R.sup.23, R.sup.24 and R.sup.25 or any two of R.sup.26, R.sup.27 and R.sup.28 may bond together to form a ring with the sulfur atom to which they are attached. Exemplary rings are the same as will be described later for the ring that R.sup.101 and R.sup.102 in formula (1-1), taken together, form with the sulfur atom to which they are attached.

(64) In formula (2), A.sup.1 is hydrogen or trifluoromethyl.

(65) 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(pefluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide; methide ions such as is (trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide.

(66) Also included are sulfonate ions having fluorine substituted at α-position as represented by the formula (f1-1) and sulfonate ions having fluorine substituted at α-position and trifluoromethyl at β-position as represented by the formula (f1-2).

(67) ##STR00057##

(68) 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 are the same as will be exemplified later for the hydrocarbyl group R.sup.107 in formula (1A′).

(69) In formula (f1-2), R.sup.32 is hydrogen, or a C.sub.1-C.sub.30 hydrocarbyl group, C.sub.2-C.sub.30 hydrocarbylcarbonyl group, or aryloxy 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 are the same as will be exemplified later for the hydrocarbyl group R.sup.107 in formula (1A′).

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

(71) ##STR00058## ##STR00059## ##STR00060##

(72) Examples of the cation in the monomer from which recurring unit (2) or (f3) is derived are the same as will be shown later for the cation in the sulfonium salt having formula (1-1).

(73) Examples of the anion in the monomer from which recurring unit (2) is derived are shown below, but not limited thereto. R.sup.A is as defined above.

(74) ##STR00061## ##STR00062## ##STR00063##

(75) Examples of the anion in the monomer from which recurring unit (f) is derived are shown below, but not limited thereto. R.sup.A is as defined above.

(76) ##STR00064## ##STR00065##

(77) 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 recurring units (f) is used, the blending of an acid generator of addition type may be omitted.

(78) The base polymer for formulating the positive resist composition comprises recurring units (a1) or (a2) having an acid labile group as essential component and additional recurring units (b), (c), (d), (e), and (f) as optional components. A fraction of units (a1), (a2), (b), (c), (d), (e), and (f) is: preferably 0≤a1<1.0, 0≤a2<1.0, 0<a1+a2<1.0, 0≤b≤0.9, 0≤c≤0.9, 0≤d≤0.8, 0≤e≤0.8, and 0≤f≤0.5; more preferably 0≤a1≤0.9, 0≤a2≤0.9, 0.1≤a1+a2≤0.9, 0≤b≤0.8, 0≤c≤0.8, 0≤d≤0.7, 0≤e≤0.7, and 0≤f≤0.4; and even more preferably 0≤a1≤0.8, 0≤a2≤0.8, 0.1≤a1+a2≤0.8, 0≤b≤0.75, 0≤c≤0.75, 0≤d≤0.6, 0≤e≤0.6, and 0≤f≤0.3. Notably, f=f1+f2+f3, meaning that unit (f) is at least one of units (f1) to (3), and a1+a2+b+c+d+e+f=1.0.

(79) For the base polymer for formulating the negative resist composition, an acid labile group is not necessarily essential. The base polymer comprises recurring units (b), and optionally recurring units (c), (d), (e), and/or (f). A fraction of these units is: preferably 0<b≤1.0, 0≤c≤0.9, 0≤d≤0.8, 0≤e≤0.8, and 0≤f≤0.5; more preferably 0.2≤b≤1.0, 0≤c≤0.8, 0≤d≤0.7, 0≤e≤0.7, and 0≤f≤0.4; and even more preferably 0.3≤b≤1.0, 0≤c≤0.75, 0≤d≤0.6, 0≤e≤0.6, and 0≤f≤0.3. Notably, f=f1+f2+f3, meaning that unit (f) is at least one of units (f1) to (f3), and b+c+d+e+f=1.0.

(80) 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 recurring 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, 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 polymerization temperature is 50 to 80° C., and the reaction time is 2 to 100 hours, more preferably 5 to 20 hours.

(81) Where a monomer having a hydroxyl group is copolymerized, the hydroxyl 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 hydroxyl group may be replaced by an acetyl, formyl, pivaloyl or similar group prior to polymerization, and the polymerization be followed by alkaline hydrolysis.

(82) 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.

(83) 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. With too low a Mw, the resist composition may become less heat resistant. A polymer with too high a Mw may lose alkaline solubility and give rise to a footing phenomenon after pattern formation.

(84) 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.

(85) It is understood that a blend of two or more polymers which differ in compositional ratio, Mw or Mw/Mn is acceptable.

(86) Acid Generator

(87) 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 the compound having formula (A) functions as a quencher and the inventive resist composition functions as a chemically amplified positive or negative resist composition. The acid generator is typically a compound (PAG) capable of generating an acid upon exposure 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).

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

(89) ##STR00066##

(90) In formulae (1-1) and (1-2) R.sup.101, R.sup.102, R.sup.103, R.sup.104 and R.sup.105 are each independently 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 include those exemplified above for R.sup.21 to R.sup.28 in formulae (f1) to (f3).

(91) R.sup.101 and R.sup.102 may bond together to form a ring with the sulfur atom to which they are attached. Preferred examples of the ring are shown by the following structure

(92) ##STR00067##
Herein the broken line designates an attachment to R.sup.103.

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

(94) ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096##

(95) Examples of the cation in the iodonium salt having formula (1-2) are shown below, but not limited thereto.

(96) ##STR00097## ##STR00098##

(97) In formulae (1-1) and (1-2), X.sup.− is an anion of the following formula (1A), (1B), (1C) or (1D).

(98) ##STR00099##

(99) In formula (1A), 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 include those exemplified later for R.sup.107 in formula (1A′).

(100) Of the anions of formula (1A), an anion having the formula (1A′) is preferred.

(101) ##STR00100##

(102) In formula (1A′), R.sup.106 is hydrogen or trifluoromethyl, preferably trifluoromethyl.

(103) R.sup.107 is a C.sub.1-C.sub.38 hydrocarbyl group which may contain a heteroatom. As the heteroatom, oxygen, nitrogen, sulfur and halogen atoms are preferred, with oxygen being most preferred. Of the hydrocarbyl groups R.sup.107, those groups of 6 to 30 carbon atoms are preferred from the aspect of achieving a high resolution in forming patterns of small feature size. The hydrocarbyl groups may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, and eicosanyl; cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl, tetracyclododecanylmethyl, and dicyclohexylmethyl; unsaturated aliphatic hydrocarbyl groups such as allyl and 3-cyclohexenyl; aryl groups such as phenyl, 1-naphthyl and 2-naphthyl: and aralkyl groups such as benzyl and diphenylmethyl. In these groups, some or all hydrogen may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some carbon may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonic acid ester bond, carbonate moiety, lactone ring, sultone ring, carboxylic anhydride 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.

(104) With respect to the synthesis of the sulfonium salt having an anion of formula (1A′), reference may be made to JP-A 2007-145797, JP-A 2008-106045, JP-A 2009-007327, and JP-A2009-258695. 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.

(105) Examples of the anion having formula (1A) are shown below, bat not limited thereto.

(106) ##STR00101## ##STR00102## ##STR00103## ##STR00104##

(107) In formula (1B), 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. Examples thereof are as exemplified above for R.sup.107 in formula (1A′). Preferably R.sup.fb1 and R.sup.fb2 are fluorine or C.sub.1-C.sub.4 straight fluorinated alkyl groups. Also, R.sup.fb1, and R.sup.fb2 may bond together to form a ring with the linkage: —CF.sub.2SO.sub.2—N.sup.−—SO.sub.2—CF.sub.2— to which they are attached. It is preferred that a combination of R.sup.fb1 and R.sup.fb2 be a fluorinated ethylene or fluorinated propylene group.

(108) In formula (1C), 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. Examples thereof are as exemplified above for R.sup.107. Preferably R.sup.fc1, R.sup.fc2 and R.sup.fc3 are fluorine or C.sub.1-C.sub.4 straight fluorinated alkyl groups. Also, R.sup.fc1 and R.sup.fc2 may bond together to form a ring with the linkage: —CF.sub.2—SO.sub.2—C.sup.−—SO.sub.2—CF.sub.2— to which they are attached. It is preferred that a combination of R.sup.fc1 and R.sup.fc2 be a fluorinated ethylene or fluorinated propylene group.

(109) In formula (1D), Rn 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. Examples thereof are as exemplified above for R.sup.107.

(110) With respect to the synthesis of the sulfonium salt having an anion of formula (D), reference may be made to JP-A 2010-215608 and JP-A 2014-133723.

(111) Examples of the anion having formula (1D) are shown below, but not limited thereto.

(112) ##STR00105##

(113) Notably, the compound having the anion of formula (1D) does not have fluorine at the α-position relative to the sulfo group, but two trifluoromethyl groups at the β-position. For this reason, it has a sufficient acidity to sever the acid labile groups in the base polymer. Thus the compound is an effective PAG.

(114) Another preferred PAG is a compound having the formula (2).

(115) ##STR00106##

(116) In formula (2), R.sup.201 and R.sup.202 are each independently 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 the same as described above for the ring that R.sup.101 and R.sup.102 in formula (1-1), taken together, form with the sulfur atom to which they are attached.

(117) The hydrocarbyl groups R.sup.201 and R.sup.202 may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0.sup.2,6]decanyl, and adamantyl; and aryl groups such as phenyl, naphthyl and anthracenyl. In these groups, some hydrogen may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some carbon may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonic acid ester bond, carbonate moiety, lactone ring, sultone ring, carboxylic anhydride or haloalkyl moiety.

(118) The hydrocarbylene group R.sup.203 may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include alkanediyl groups such as methylene, ethylene, 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; cyclic saturated hydrocarbylene groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl and adamantanediyl; and 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. In these groups, some hydrogen may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, or some carbon may be replaced by a moiety containing a heteroatom such as oxygen, sulfur or nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonic acid ester bond, carbonate, lactone ring, sultone ring, carboxylic anhydride or haloalkyl moiety. Of the heteroatoms, oxygen is preferred.

(119) In formula (2), 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.

(120) In formula (2), 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, and k is an integer of 0 to 3.

(121) Of the PAGs having formula (2), those having formula (2′) are preferred.

(122) ##STR00107##

(123) In formula (2′), 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.107 in formula (1A′). The subscripts x and y are each independently an integer of 0 to 5, and z is an integer of 0 to 4.

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

(125) Of the foregoing PAGs, those having an anion of formula (1A′) or (1D) are especially preferred because of reduced acid diffusion and high solubility in the resist solvent. Also those having formula (2′) are especially preferred because of extremely reduced acid diffusion.

(126) 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 (3-1) and (3-2).

(127) ##STR00108##

(128) In formulae (3-1) and (3-2), u is an integer of 1 to 3, s is an integer of 1 to 5, and t is an integer of 0 to 3, and 1≤s+t≤5. Preferably, s is 1, 2 or 3, more preferably 2 or 3, and t is 0, 1 or 2.

(129) In formulae (3-1) and (3-2). X.sup.B1 is iodine or bromine, and may be the same or different when u and/or s is 2 or more.

(130) 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.

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

(132) R.sup.401 is a hydroxyl group, carboxyl group, fluorine, chlorine, bromine, amino group, or a C.sub.1-C.sub.20 saturated hydrocarbyl, C.sub.1-C.sub.20 saturated hydrocarbyloxy, C.sub.2-C.sub.10 saturated hydrocarbyloxycarbonyl, C.sub.2-C.sub.20 saturated hydrocarbylcarbonyloxy or C.sub.1-C.sub.20 saturated hydrocarbylsulfonyloxy group, which may contain fluorine, chlorine, bromine, hydroxyl, amino or ether bond, or —NR.sup.401A—C(═O)—R.sup.401B or —NR.sup.401A—C(═O)—O—R.sup.401B. R.sup.401A is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group which may contain halogen, hydroxyl, 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.401B is a C.sub.1-C.sub.6 aliphatic hydrocarbyl or C.sub.6-C.sub.12 aryl group, which may contain halogen, hydroxyl, 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 saturated hydrocarbyl, saturated hydrocarbyloxy, saturated to hydrocarbyloxycarbonyl, saturated hydrocarbylcarbonyl, and saturated hydrocarbylcarbonyloxy groups may be straight, branched or cyclic. Groups R.sup.401 may be the same or different when u and/or t is 2 or more. Of these, R.sup.401 is preferably hydroxyl, —NR.sup.401A—C(═O)—R.sup.401B, —NR.sup.401A—C(═O)—O—R.sup.401B, fluorine, chlorine, bromine, methyl or methoxy.

(133) In formulae (3-1) and (3-2). 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, or 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.

(134) R.sup.402, R.sup.403. R.sup.404, R.sup.405 and R.sup.406 are each independently 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 include C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.20 aryl, and C.sub.7-C.sub.20 aralkyl groups. In these groups, some or all of the hydrogen atoms may be substituted by hydroxyl, carboxyl, halogen, cyano, nitro, mercapto, sultone, sulfone, or sulfonium salt-containing moieties, and some carbon may be replaced by an ether bond, ester bond, carbonyl moiety, amide bond, carbonate moiety or sulfonic acid ester bond. Any two of R.sup.402, R.sup.403 and R.sup.404 may bond together to form a ring with the sulfur atom to which they are attached. Exemplary rings are the same as described above for the ring that R.sup.101 and R.sup.102 in formula (1-1), taken together, form with the sulfur atom to which they are attached.

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

(136) Examples of the anion in the onium salts having formulae (3-1) and (3-2) are shown below, but not limited thereto. Herein X.sup.B1 is as defined above.

(137) ##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##

(138) ##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##

(139) 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. When the base polymer includes recurring units (f) and/or the acid generator of addition type is added, the resist composition functions as a chemically amplified resist composition.

(140) Organic Solvent

(141) 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 γ-butyrolactone, which may be used alone or in admixture.

(142) 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.

(143) Other Components

(144) With the foregoing components, other components such as a surfactant, dissolution inhibitor, and crosslinker may be blended in any desired combination to formulate a chemically amplified positive or negative resist composition. This positive or negative resist composition has a very high sensitivity in that the dissolution rate in developer of the base polymer in exposed areas is accelerated by catalytic reaction. In addition, the resist film has a high dissolution contrast, resolution, exposure latitude, and process adaptability, and provides a good pattern profile after exposure, and minimal proximity bias because of restrained acid diffusion. By virtue of these advantages, the composition is fully useful in commercial application and suited as a pattern-forming material for the fabrication of VLSIs.

(145) 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. While the surfactant may be used alone or in admixture, it is preferably added in an amount of 0.0001 to 10 parts by weight per 100 parts by weight of the base polymer.

(146) In the case of positive resist compositions, 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 hydroxyl groups on the molecule, in which an average of from 0 to 100 mol % of all the hydrogen atoms on the phenolic hydroxyl groups are replaced by acid labile groups or a compound having at least one carboxyl group on the molecule, in which an average of 50 to 100 mol % of all the hydrogen atoms on the carboxyl 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 hydroxyl or carboxyl 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]).

(147) In the positive resist composition, 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. The dissolution inhibitor may be used alone or in admixture.

(148) In the case of negative resist compositions, 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 alkenyl ether 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.

(149) 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, tetramethoxymethylurea, tetramethylolurea compounds having 1 to 4 methylol groups methoxymethylated and mixtures thereof, and tetramethoxyethyl urea.

(150) 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 alkenyl ether 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.

(151) In the negative resist composition, 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. The crosslinker may be used alone or in admixture.

(152) In the resist composition of the invention, a quencher other than the ammonium salt compound having formula (A) may be blended. 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 carboxyl group, nitrogen-containing compounds with sulfonyl group, nitrogen-containing compounds with hydroxyl 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 hydroxyl group, ether bond, ester bond, lactone ring, cyano group, or sulfonic acid 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.

(153) Onium salts such as sulfonium salts, iodonium salts and ammonium salts of sulfonic acids which are not fluorinated at α-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 other quencher. While an α-fluorinated sulfonic acid, imide acid, and methide acid are necessary to deprotect the acid labile group of carboxylic acid ester, an α-non-fluorinated sulfonic acid and a carboxylic acid are released by salt exchange with an α-non-fluorinated onium salt. An α-non-fluorinated sulfonic acid and a carboxylic acid function as a quencher because they do not induce deprotection reaction. Since the quencher in the form of a sulfonium salt or iodonium salt is photo-decomposable, the quencher function is reduced in the exposed region whereas acid activity is improved. This results in an improved contrast.

(154) The iodized aromatic ring-containing ammonium salt has an outstanding acid diffusion suppressing effect in the exposed region as well as in the unexposed region. In the exposed region, an iodized or brominated phenol is detached from an amine compound containing an iodized aromatic ring and dissolved in the alkaline developer while forming a salt with the alkaline developer. This prevents any drop of dissolution rate in the over-exposed region. Using the iodized aromatic ring-containing ammonium salt in combination with the quencher in the form of an onium salt, the desired properties including low acid diffusion and high contrast are achieved in a good balance.

(155) 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 after coating 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.

(156) 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. The other quencher may be used alone or in admixture.

(157) To the resist composition, a water repellency improver may also be added for improving the water repellency on surface of a resist film as spin coated. The water repellency improver may be used in the topcoatless immersion lithography. Suitable water repellency improvers include polymers having a fluoroalkyl group and polymers having a specific structure with 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 to be added to the resist composition should be soluble in the alkaline developer and organic solvent developer. The water repellency improver of specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue is well soluble in the developer. A polymer having an amino group or amine salt copolymerized as recuing units 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. The water repellency improver may be used alone or in admixture. 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.

(158) 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.

(159) Pattern Forming Process

(160) 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 coating, exposure, and development. If necessary, any additional steps may be added.

(161) For example, 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 hot plate at a temperature of 60 to 150° C. for 10 seconds to 30 minutes, preferably at 80 to 120° C. for 30 seconds to 20 minutes. The resulting resist film is generally 0.01 to 2 μm thick.

(162) The resist film is then exposed to a desired pattern of high-energy radiation such as UV, deep-UV, EB, EUV, x-ray, soft x-ray, excimer laser light. γ-ray or synchrotron radiation. When UV, deep-V, EUV, x-ray, soft x-ray, excimer laser light, γ-ray or synchrotron radiation is used as the high-energy radiation, the resist film is exposed thereto 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 n/cm.sup.2. When EB is used as the high-energy radiation, the resist film is exposed thereto through a mask having a desired pattern or directly in a dose of preferably about 0.1 to 100 μC/cm.sup.2, more preferably about 0.5 to 50 μC/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, so x-ray, γ-ray or synchrotron radiation, especially in micropatterning using EB or EUV.

(163) After the exposure, the resist film may be baked (PEB) on a hot plate at 60 to 150° C. for 10 seconds to 30 minutes, preferably at 80 to 120° C. for 30 seconds to 20 minutes.

(164) 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 resist, 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. Inversely in the case of negative resist, the exposed area of resist film is insolubilized and the unexposed area is dissolved in the developer.

(165) In an alternative embodiment, a negative pattern may be formed via organic solvent development using a positive resist composition comprising a base polymer having an acid labile group. 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.

(166) 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. The solvents may be used alone or in admixture.

(167) 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 may be reduced.

(168) 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 surface as a result of the acid catalyst diffusing from the resist layer 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

(169) Examples of the invention are given below by way of illustration and not by way of limitation. The abbreviation “pbw” is parts by weight.

(170) Quenchers 1 to 32 used in resist compositions have the following structure. Notably, Quenchers 1 to 32 were synthesized by neutralization reaction of an iodized aromatic ring-containing amine compound providing the cation shown below with an iodized or brominated phenol providing the anion shown below.

(171) ##STR00172## ##STR00173## ##STR00174## ##STR00175##

Synthesis Example

Synthesis of Base Polymers (Polymers 1 to 4)

(172) Base polymers were prepared by combining suitable monomers, effecting copolymerization reaction thereof in tetrahydrofuran (TH) solvent, pouring the reaction solution into methanol for crystallization, repeatedly washing with hexane, isolation, and drying. The resulting polymers, designated Polymers 1 to 4, were analyzed for composition by .sup.1H-NMR spectroscopy, and for Mw and Mw/Mn by GPC versus polystyrene standards using THF solvent.

(173) ##STR00176## ##STR00177##

Examples 1 to 40 and Comparative Examples 1 to 7

(174) (1) Preparation of Resist Compositions

(175) Resist compositions were prepared, under LED illumination with UV of wavelength 400 nm and shorter cut off, by dissolving the polymer and selected components in a solvent in accordance with the recipe shown in Tables 1 to 4, and filtering through a filter having a pore size of 0.2 tn. The solvent contained 100 ppm of surfactant Polyfox PF-636 (Omnova Solutions Inc.). The resist compositions of Examples 1 to 23, Examples 25 to 40, and Comparative Examples 1 to 6 were of positive tone, while the resist compositions of Example 24 and Comparative Example 7 were of negative tone.

(176) The components in Tables 1 to 4 are as identified below.

(177) Organic Solvents:

(178) PGMEA (propylene glycol monomethyl ether acetate)

(179) CyH (cyclohexanone)

(180) PGME (propylene glycol monomethyl ether)

(181) DAA (diacetone alcohol)

(182) Acid Generators: PAG 1 to PAG 6 of the Following Structural Formulae

(183) ##STR00178##
Comparative Quenchers 1 to 7 of the Following Structural Formulae

(184) ##STR00179##
Blend Quenchers 1 to 3 of the Following Structural Formulae

(185) ##STR00180##
(2) EUV Lithography Test

(186) Each of the resist compositions in Tables 1 to 4 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 105° C. for 60 seconds to form a resist film of 60 nm thick. Using an EUV scanner NXE3300 (ASML, NA 0.33, σ 0.9/0.6, quadrupole illumination), the resist film was exposed to EUV through a mask bearing a hole pattern at a pitch 46 nm (on-wafer size) and +20% bias. The resist film was baked (PEB) on a hotplate at the temperature shown in Tables 1 to 4 for 60 seconds and developed in a 2.38 wt % TMAH aqueous solution for 30 seconds to form a hole pattern having a size of 23 nm in Examples 1 to 23, Examples 25 to 40, and Comparative Examples 1 to 6 or a dot pattern having a size of 23 nm in Example 24 and Comparative Example 7.

(187) The resist pattern was observed under CD-SEM (CG-5000, Hitachi High-Technologies Corp.). The exposure dose that provides a hole or dot pattern having a size of 23 nm is reported as sensitivity. The size of 50 holes or dots in that dose was measured, from which a size variation (3σ) was computed and reported as CDU.

(188) The resist composition is shown in Tables 1 to 4 together with the sensitivity and CDU of EUV lithography.

(189) TABLE-US-00001 TABLE 1 Acid Organic PEB Polymer generator Quencher solvent temp, Sensitivity CDU Example (pbw) (pbw) (pbw) (pbw) (° C.) (mJ/cm.sup.2) (nm) 1 Polymer 1 PAG 1 Quencher 1 PGMEA (400) 100 26 2.5 (100) (30) (11.32) CyH (2,000) PGME (100) 2 Polymer 1 PAG 2 Quencher 2 PGMEA (400) 100 27 2.6 (100) (30) (9.11) CyH (2,000) PGME (100) 3 Polymer 1 PAG 2 Quencher 3 PGMEA (400) 100 27 2.5 (100) (30) (14.55) CyH (2,000) PGME (100) 4 Polymer 1 PAG 2 Quencher 4 PGMEA (400) 100 26 2.6 (100) (30) (11.15) CyH (2,000) PGME (100) 5 Polymer 1 PAG 2 Quencher 5 PGMEA (400) 100 26 2.7 (100) (30) (8.50) CyH (2,000) PGME (100) 6 Polymer 1 PAG 2 Quencher 6 PGMEA (400) 100 24 2.5 (100) (30) (8.84) CyH (2.000) PGME (100) 7 Polymer 1 PAG 2 Quencher 7 PGMEA (400) 100 23 2.5 (100) (30) (11.53) CyH (2,000) PGME (100) 8 Polymer 1 PAG 2 Quencher 8 PGMEA (400) 100 24 .2.2 (100) (30) (10.97) CyH (2000) PGME (100) 9 Polymer 1 PAG 2 Quencher 9 PGMEA (400) 100 24 2.6 (100) (30) (11.16) CyH (2,000) PGME (100) 10 Polymer 1 PAG 2 Quencher 10 PGMEA (400) 100 24 2.5 (100) (30) (10.20) CyH (2,000) PGME (100) 11 Polymer 1 PAG 2 Quencher 11 PGMEA (400) 100 24 2.6 (100) (30) (11.97) CyH (2,000) PGME (100) 12 Polymer 1 PAG 2 Quencher 12 PGMEA (400) 100 24 2.5 (100) (30) (11.98) CyH (2,000) PGME (100) 13 Polymer 1 PAG 2 Quencher 13 PGMEA (400) 100 24 2.5 (100) (30) (10.83) CyH (2.000) PGME (100) 14 Polymer 1 PAG 2 Quencher 14 PGMEA (400) 100 25 2.6 (100) (30) (10.83) CyH (2,000) PGME (100) 15 Polymer 1 PAG 2 Quencher 15 PGMEA (400) 100 24 2.3 (100) (30) (9.73) CyH (2.000) PGME (100) 16 Polymer 1 PAG 2 Quencher 16 PGMEA (400) 100 24 2.4 (100) (30) (11.83) CyH (2,000) PGME (100) 17 Polymer 1 PAG 2 Quencher 17 PGMEA (400) 100 24 2.3 (100) (30) (10.69) CyH (2,000) PGME (100) 18 Polymer 2 — Quencher 7 PGMEA (400) 100 25 2.2 (100) (11.53) CyH (2,000) PGME (100) 19 Polymer 3 — Quencher 7 PGMEA (400) 100 23 2.1 (100) (11.53) CyH (2,000) PGME (100)

(190) TABLE-US-00002 TABLE 2 Acid Organic PEB Polymer generator Quencher solvent temp, Sensitivity CDU Example (pbw) (pbw) (pbw) (pbw) (° C.) (mJ/cm.sup.2) (nm) 20 Polymer 3 PAG 3 Quencher 7 PGMEA 100 22 2.4 (100) (30) (11.53) (2,000) DAA (500) 21 Polymer 3 PAG 4 Quencher 7 PGMEA (400) 100 23 2.4 (100) (30) (11.53) CyH (2,000) PGME (100) 22 Polymer 3 PAG 5 Quencher 7 PGMEA (400) 100 22 2.6 (100) (30) (11.53) CyH (2,000) PGME (100) 23 Polymer 3 PAG 6 Quencher 7 PGMEA (400) 100 23 2.5 (100) (30) (11.53) CyH (2,000) PGME (100) 24 Polymer 4 PAG 1 Quencher 7 PGMEA (400) 100 28 3.2 (100) (30) (11.53) CyH (2,000) PGME (100) 25 Polymer 1 PAG 2 Quencher 18 PGMEA (400) 100 25 2.4 (100) (30) (10.83) CyH (2.000) PGME (100) 26 Polymer 1 PAG 2 Quencher 19 PGMEA (400) 100 24 2.6 (100) (30) (11.61) CyH (2,000) PGME (100) 27 Polymer 1 PAG 2 Quencher 20 PGMEA (400) 100 25 2.5 (100) (30) (10.69) CyH (2000) PGME (100) 28 Polymer 1 PAG 2 Quencher 21 PGMEA (400) 100 25 2.6 (100) (30) (10.71) CyH (2,000) PGME (100) 29 Polymer 1 PAG 2 Quencher 22 PGMEA (400) 100 24 2.2 (100) (30) (10.83) CyH (2,000) PGME (100) 30 Polymer 1 PAG 2 Quencher 23 PGMEA (400) 100 24 2.5 (100) (30) (11.01) CyH (2,000) PGME (100) 31 Polymer 1 PAG 2 Quencher 24 PGMEA (400) 100 25 2.6 (100) (30) (10.69) CyH (2,000) PGME (100) 32 Polymer 1 PAG 2 Quencher 25 PGMEA (400) 100 26 2.6 (100) (30) (11.25) CyH (2.000) PGME (100) 33 Polymer 1 PAG 2 Quencher 26 PGMEA (400) 100 26 2.5 (100) (30) (15.97) CyH (2,000) PGME (100) 34 Polymer 1 PAG 2 Quencher 27 PGMEA (400) 100 25 2.6 (100) (30) (10.81) CyH (2.000) PGME (100) 35 Polymer 1 PAG 2 Quencher 28 PGMEA (400) 100 25 2.6 (100) (30) (10.95) CyH (2,000) PGME (100) 36 Polymer 1 PAG 2 Quencher 29 PGMEA (400) 100 25 2.5 (100) (30) (11.09) CyH (2,000) PGME (100) 37 Polymer 1 PAG 2 Quencher 30 PGMEA 100 24 2.6 (100) (30) (5.65) (2,000) Blend DAA (500) Quencher 1 (2.36) 38 Polymer 1 PAG 2 Quencher 31 PGMEA 100 24 2.6 (100) (30) (5.87) (2,000) Blend DAA (500) Quencher 2 (2.36)

(191) TABLE-US-00003 TABLE 3 Acid Organic PEB Polymer generator Quencher Solvent temp. Sensitivity CDU Example (pbw) (pbw) (pbw) (pbw) (° C.) (mJ/cm.sup.2) (nm) 39 Polymer 1 PAG 2 Quencher 32 PGMEA (2,000) 100 28 3.5 (100) (30) (8.95) DAA (500) 40 Polymer 1 PAG 2 Blend PGMEA (2,000) 100 26 3.5 (100) (30) Quencher 3 DAA (500) (3.82) Quencher 31 (4.48)

(192) TABLE-US-00004 TABLE 4 Acid Organic PEB Comparative Polymer generator Quencher solvent temp, Sensitivity CDU Example (pbw) (pbw) (pbw) (pbw) (° C.) (mJ/cm.sup.2) (nm) 1 Polymer 1 PAG 1 Comparative PGMEA (400) 100 28 3.5 (100) (30) Quencher 1 CyH (2,000) (1.20) PGME (100) 2 Polymer 1 PAG 1 Comparative PGMEA (400) 100 28 3.2 (100) (30) Quencher 2 CyH (2,000) (1.20) PGME (100) 3 Polymer 1 PAG 1 Comparative PGMEA (400) 100 30 3.1 (100) (30) Quencher 3 CyH (2,000) (3.89) PGME (100) 4 Polymer 1 PAG 1 Comparative PGMEA (400) 100 28 2.8 (100) (30) Quencher 4 CyH (2,000) (3.20) PGME (100) 5 Polymer 1 PAG 1 Comparative PGMEA (400) 100 38 3.0 (100) (30) Quencher 5 CyH (2,000) (3.20) PGME (100) 6 Polymer 1 PAG 1 Comparative PGMEA (400) 100 26 3.3 (100) (30) Quencher 6 CyH (2,000) (3.20) PGME (100) 2,4,6-triiocloplienol (4.71) 7 Polymer 4 PAG 1 Comparative PGMEA (400) 120 30 4.9 (100) (30) Quencher 7 CyH (2,000) (3.65) PGME (100)

(193) It is demonstrated in Tables 1 to 4 that resist compositions comprising an iodized aromatic ring-containing ammonium salt form patterns having a high sensitivity and a reduced value of CDU.

(194) Japanese Patent Application No. 2019-148848 is incorporated herein by reference.

(195) 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.