MASK BLANK, RESIST PATTERN FORMING PROCESS AND CHEMICALLY AMPLIFIED POSITIVE RESIST COMPOSITION

Abstract

A photomask blank has a resist film which is obtained by coating a chemically amplified positive resist composition comprising a polymer comprising phenolic hydroxy-containing repeat units and repeat units having a carboxy group which is protected with an acid labile group in the form of a tertiary hydrocarbyl group having an electron attractive moiety and/or hydroxy-substituted phenyl moiety bonded to the tertiary carbon, and an organic solvent. The resist film is processed to form a pattern with a high resolution, reduced LER, improved rectangularity, and pattern fidelity.

Claims

1. A mask blank comprising a resist film which is obtained by coating a chemically amplified positive resist composition, the resist composition comprising a base polymer containing a polymer comprising phenolic hydroxy group-containing repeat units having the formula (A1) and repeat units containing a carboxy group protected with an acid labile group, having the formula (A2), and an organic solvent, ##STR00335## wherein R.sup.A is hydrogen, fluorine, methyl or trifluoromethyl, X.sup.1 is a single bond, *—C(═O)—O— or *—C(═O)—NH—, * designates a point of attachment to the carbon atom in the backbone, A.sup.1 is a single bond or a C.sub.1-C.sub.10 saturated hydrocarbylene group in which some constituent —CH.sub.2— may be replaced by —O—, R.sup.1 is halogen, an optionally halogenated C.sub.2-C.sub.8 saturated hydrocarbylcarbonyloxy group, optionally halogenated C.sub.1-C.sub.6 saturated hydrocarbyl group, or optionally halogenated C.sub.1-C.sub.6 saturated hydrocarbyloxy group, a1 is an integer satisfying 0≤a1≤5+2a3−a2, a2 is an integer of 1 to 3, and a3 is an integer of 0 to 2, ##STR00336## wherein R.sup.A is hydrogen, fluorine, methyl or trifluoromethyl, X.sup.2 is a single bond, *—C(═O)—O—X.sup.21—, phenylene group, or naphthylene group, the phenylene group and naphthylene group may be substituted with an optionally fluorinated C.sub.1-C.sub.10 alkoxy moiety or halogen, X.sup.21 is a C.sub.1-C.sub.20 aliphatic hydrocarbylene group, phenylene group or naphthylene group, the aliphatic hydrocarbylene group may contain at least one moiety selected from an optionally fluorinated C.sub.1-C.sub.10 alkoxy moiety, hydroxy, ether bond, ester bond and lactone ring, * designates a point of attachment to the carbon atom in the backbone, R.sup.B and R.sup.C are each independently a C.sub.1-C.sub.10 hydrocarbyl group which may contain a heteroatom, R.sup.B and R.sup.C may bond together to form a ring with the carbon atom to which they are attached, R.sup.2 is each independently halogen, cyano group, C.sub.1-C.sub.5 acyl group, C.sub.1-C.sub.5 alkoxy group, C.sub.1-C.sub.5 fluorinated alkyl group, or C.sub.1-C.sub.5 fluorinated alkoxy group, R.sup.3 is each independently a C.sub.1-C.sub.10 hydrocarbyl group which may contain a heteroatom, b1 is an integer of 0 to 2, b2 is an integer of 0 to 2, b3 is an integer of 0 to 5, and b4 is an integer of 0 to 2, with the proviso that b1 and b2 are not equal to 0 at the same time.

2. The mask blank of claim 1 wherein the phenolic hydroxy group-containing unit is a repeat unit having the following formula (A1-1), and the unit containing a carboxy group protected with an acid labile group is a repeat unit having the following formula (A2-1): ##STR00337## wherein R.sup.A, R.sup.B, R.sup.C, X.sup.2, R.sup.2, R.sup.3, a2, b1, b2 and b3 are as defined above, with the proviso that b1 and b2 are not equal to 0 at the same time.

3. The mask blank of claim 1 wherein b2 is 1 or 2, and R.sup.2 is fluorine, trifluoromethyl or trifluoromethoxy.

4. The mask blank of claim 1 wherein the polymer further comprises repeat units having any one of the formulae (B1) to (B3): ##STR00338## wherein R.sup.A is as defined above, c and d are each independently an integer of 0 to 4, e is an integer of 0 to 5, f is an integer of 0 to 2, X.sup.3 is a single bond, *—C(═O)—O— or *—C(═O)—NH—, * designates a point of attachment to the carbon atom in the backbone, A.sup.3 is a single bond or a C.sub.1-C.sub.10 saturated hydrocarbylene group in which some constituent —CH.sub.2— may be replaced by —O—, R.sup.11 and R.sup.12 are each independently hydroxy, halogen, an optionally halogenated C.sub.2-C.sub.8 saturated hydrocarbylcarbonyloxy group, optionally halogenated C.sub.1-C.sub.8 saturated hydrocarbyl group, or optionally halogenated C.sub.1-C.sub.8 saturated hydrocarbyloxy group, R.sup.13 is an acetyl group, C.sub.1-C.sub.20 saturated hydrocarbyl group, C.sub.1-C.sub.20 saturated hydrocarbyloxy group, C.sub.2-C.sub.20 saturated hydrocarbylcarbonyloxy group, C.sub.2-C.sub.20 saturated hydrocarbyloxyhydrocarbyl group, C.sub.2-C.sub.20 saturated hydrocarbylthiohydrocarbyl group, halogen, nitro group or cyano group, R.sup.13 may also be hydroxy when f is 1 or 2.

5. The mask blank of claim 1 wherein the polymer further comprises repeat units having any one of the formulae (C1) to (C8): ##STR00339## ##STR00340## wherein R.sup.A is as defined above, Y.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, *—O—Y.sup.1—, *—C(═O)—O—Y.sup.1—, or *—C(═O)—NH—Y.sup.11—, Y.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, Y.sup.2 is a single bond or **—Y.sup.21—C(═O)—O—, Y.sup.21 is a C.sub.1-C.sub.20 hydrocarbylene group which may contain a heteroatom, Y.sup.3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *—O—Y.sup.31—, *—C(═O)—O—Y.sup.31—, or *—C(═O)—NH—Y.sup.31—, Y.sup.31 is a C.sub.1-C.sub.6 aliphatic hydrocarbylene group, phenylene group, fluorinated phenylene group, trifluoromethyl-substituted phenylene group, or C.sub.7-C.sub.20 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety, * designates a point of attachment to the carbon atom in the backbone, ** designates a point of attachment to the oxygen atom in the formula, Y.sup.4 is a single bond or C.sub.1-C.sub.30 hydrocarbylene group which may contain a heteroatom, k.sup.1 and k.sup.2 are each independently 0 or 1, k.sup.1 and k.sup.2 are 0 when Y.sup.4 is a single bond, R.sup.21 to R.sup.38 are each independently halogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom, R.sup.21 and R.sup.22 may bond together to form a ring with the sulfur atom to which they are attached, R.sup.23 and R.sup.24, R.sup.26 and R.sup.27, or R.sup.29 and R.sup.30 may bond together to form a ring with the sulfur atom to which they are attached, R.sup.HF is hydrogen or trifluoromethyl, and Xa.sup.− is a non-nucleophilic counter ion.

6. The mask blank of claim 1 wherein the resist composition further comprises a fluorinated polymer comprising repeat units of at least one type selected from repeat units having the following formula (D1), repeat units having the following formula (D2), repeat units having the following formula (D3), and repeat units having the following formula (D4) and optionally repeat units of at least one type selected from repeat units having the following formula (D5) and repeat units having the following formula (D6): ##STR00341## ##STR00342## wherein R.sup.B is each independently hydrogen, fluorine, methyl or trifluoromethyl, R.sup.C is each independently hydrogen or methyl, R.sup.101, R.sup.102, R.sup.104 and R.sup.105 are each independently hydrogen or a C.sub.1-C.sub.10 saturated hydrocarbyl group, R.sup.103, R.sup.106, R.sup.107 and R.sup.108 are each independently hydrogen, a C.sub.1-C.sub.15 hydrocarbyl group, C.sub.1-C.sub.15 fluorinated hydrocarbyl group, or acid labile group, when R.sup.103, R.sup.106, R.sup.107 and R.sup.108 each are a hydrocarbyl or fluorinated hydrocarbyl group, an ether bond or carbonyl moiety may intervene in a carbon-carbon bond, R.sup.109 is hydrogen or a C.sub.1-C.sub.5 straight or branched hydrocarbyl group in which a heteroatom-containing moiety may intervene in a carbon-carbon bond, R.sup.110 is hydrogen or a C.sub.1-C.sub.5 straight or branched hydrocarbyl group in which a heteroatom-containing moiety may intervene in a carbon-carbon bond, R.sup.111 is a C.sub.1-C.sub.20 saturated hydrocarbyl group in which at least one hydrogen atom is substituted by fluorine and in which some constituent —CH.sub.2— may be replaced by an ester bond or ether bond, x is an integer of 1 to 3, y is an integer satisfying 0≤y≤5+2z−x, z is 0 or 1, m is an integer of 1 to 3, Z.sup.1 is a C.sub.1-C.sub.20 (m+1)-valent hydrocarbon group or C.sub.1-C.sub.20 (m+1)-valent fluorinated hydrocarbon group, Z.sup.2 is a single bond, *—C(═O)—O— or *—C(═O)—NH—, * designates a point of attachment to the carbon atom in the backbone, and Z.sup.3 is a single bond, —O—, *—C(═O)—O—Z.sup.31—Z.sup.32— or *—C(═O)—NH—Z.sup.31—Z.sup.32—Z.sup.31 is a single bond or a C.sub.1-C.sub.10 saturated hydrocarbylene group, Z.sup.32 is a single bond, ester bond, ether bond or sulfonamide bond, * designates a point of attachment to the carbon atom in the backbone.

7. The mask blank of claim 1 wherein the resist composition further comprises a photoacid generator.

8. The mask blank of claim 7 wherein the photoacid generator has an anion having an acid strength (pKa) of −2.0 or larger.

9. The mask blank of claim 1 wherein the resist composition further comprises a quencher.

10. The mask blank of claim 1 wherein the resist film has a dissolution rate in overexposed region of at least 100 nm/sec.

11. The mask blank of claim 1 wherein the mask blank has an outermost surface prior to coating of the resist composition, the outermost surface being composed of a material containing at least one element selected from chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten and tin.

12. The mask blank of claim 11 which is of reflection type.

13. A resist pattern forming process comprising the steps of: exposing the resist film of the mask blank of claim 1 patternwise to high-energy radiation, and developing the exposed resist film in an alkaline developer.

14. The process of claim 13 wherein the high-energy radiation is EB.

15. A chemically amplified positive resist composition comprising a base polymer containing a polymer comprising phenolic hydroxy group-containing repeat units having the formula (A1) and repeat units containing a carboxy group protected with an acid labile group, having the formula (A2), an organic solvent, a photoacid generator, and a quencher, wherein a weight ratio of the photoacid generator to the quencher is less than 6/1, ##STR00343## wherein R.sup.A is hydrogen, fluorine, methyl or trifluoromethyl, X.sup.1 is a single bond, *—C(═O)—O— or *—C(═O)—NH—, * designates a point of attachment to the carbon atom in the backbone, A.sup.1 is a single bond or a C.sub.1-C.sub.10 saturated hydrocarbylene group in which some constituent —CH.sub.2— may be replaced by —O—, R.sup.1 is halogen, an optionally halogenated C.sub.2-C.sub.8 saturated hydrocarbylcarbonyloxy group, optionally halogenated C.sub.1-C.sub.6 saturated hydrocarbyl group, or optionally halogenated C.sub.1-C.sub.6 saturated hydrocarbyloxy group, a1 is an integer satisfying 0≤a1≤5+2a3−a2, a2 is an integer of 1 to 3, and a3 is an integer of 0 to 2, ##STR00344## wherein R.sup.A is hydrogen, fluorine, methyl or trifluoromethyl, X.sup.2 is a single bond, *—C(═O)—O—X.sup.21—, phenylene group, or naphthylene group, the phenylene group and naphthylene group may be substituted with an optionally fluorinated C.sub.1-C.sub.10 alkoxy moiety or halogen, X.sup.21 is a C.sub.1-C.sub.20 aliphatic hydrocarbylene group, phenylene group or naphthylene group, the aliphatic hydrocarbylene group may contain at least one moiety selected from an optionally fluorinated C.sub.1-C.sub.10 alkoxy moiety, hydroxy, ether bond, ester bond and lactone ring, * designates a point of attachment to the carbon atom in the backbone, R.sup.B and R.sup.C are each independently a C.sub.1-C.sub.10 hydrocarbyl group which may contain a heteroatom, R.sup.B and R.sup.C may bond together to form a ring with the carbon atom to which they are attached, R.sup.2 is each independently halogen, cyano group, C.sub.1-C.sub.5 acyl group, C.sub.1-C.sub.5 alkoxy group, C.sub.1-C.sub.5 fluorinated alkyl group, or C.sub.1-C.sub.5 fluorinated alkoxy group, R.sup.3 is each independently a C.sub.1-C.sub.10 hydrocarbyl group which may contain a heteroatom, b1 is an integer of 0 to 2, b2 is an integer of 0 to 2, b3 is an integer of 0 to 5, b4 is an integer of 0 to 2, b1 and b2 are not equal to 0 at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0079] 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. The terms “group” and “moiety” are interchangeable. In chemical formulae, the broken line designates a valence bond.

[0080] The abbreviations and acronyms have the following meaning. [0081] EB: electron beam [0082] EUV: extreme ultraviolet [0083] Mw: weight average molecular weight [0084] Mn: number average molecular weight [0085] Mw/Mn: molecular weight distribution or dispersity [0086] GPC: gel permeation chromatography [0087] PEB: post-exposure bake [0088] PAG: photoacid generator [0089] LER: line edge roughness

[0090] It is understood that for some structures represented by chemical formulae, there can exist enantiomers and diastereomers because of the presence of asymmetric carbon atoms. In such a case, a single formula collectively represents all such isomers. The isomers may be used alone or in admixture.

[0091] Mask Blank

[0092] One embodiment of the invention is a mask blank comprising a resist film which is obtained by coating a chemically amplified positive resist composition. The resist composition is defined as comprising a base polymer containing a polymer comprising phenolic hydroxy group-containing repeat units (also referred to as repeat units A1, hereinafter) and repeat units having a carboxy group which is protected with an acid labile group in the form of a tertiary hydrocarbyl group having an electron attractive moiety and/or hydroxy moiety-substituted phenyl group bonded to the tertiary carbon (also referred to as repeat units A2, hereinafter), and an organic solvent. The polymer turns alkali soluble as a result of the acid labile group being eliminated under the action of acid.

[0093] The repeat unit A1 has the formula (A1).

##STR00007##

[0094] In formula (A1), a1 is an integer satisfying 0≤a1≤5+2a3−a2, a2 is an integer of 1 to 3, and a3 is an integer of 0 to 2.

[0095] In formula (A1), R.sup.A is hydrogen, fluorine, methyl or trifluoromethyl.

[0096] In formula (A1), X.sup.1 is a single bond, *—C(═O)—O— or *—C(═O)—NH—. The asterisk (*) designates a point of attachment to the carbon atom in the backbone.

[0097] In formula (A1), A.sup.1 is a single bond or a C.sub.1-C.sub.10 saturated hydrocarbylene group in which some constituent —CH.sub.2— may be replaced by —O—. The saturated hydrocarbylene group may be straight, branched or cyclic and examples thereof include C.sub.1-C.sub.10 alkanediyl groups such as methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and structural isomers thereof, C.sub.3-C.sub.10 cyclic saturated hydrocarbylene groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and combinations thereof.

[0098] In formula (A1), R.sup.1 is halogen, an optionally halogenated C.sub.2-C.sub.8 saturated hydrocarbylcarbonyloxy group, optionally halogenated C.sub.1-C.sub.6 saturated hydrocarbyl group, or optionally halogenated C.sub.1-C.sub.6 saturated hydrocarbyloxy group. The saturated hydrocarbyl group and saturated hydrocarbyl moiety in the saturated hydrocarbylcarbonyloxy group and saturated hydrocarbyloxy group may be straight, branched or cyclic, and examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, and hexyl, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, and combinations thereof. A carbon count within the upper limit ensures good solubility in alkaline developer. Groups R.sup.1 may be identical or different when a1 is 2 or more.

[0099] Preferred examples of the repeat unit A1 wherein both X.sup.1 and A.sup.1 are a single bond include units derived from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, and 6-hydroxy-2-vinylnaphthalene. Of these, repeat units having the formula (A1-1) are more preferred.

##STR00008##

[0100] Herein R.sup.A and a2 are as defined above.

[0101] Preferred examples of the repeat unit A1 wherein X.sup.1 is other than a single bond are shown below, but not limited thereto. Herein R.sup.A is as defined above.

##STR00009## ##STR00010##

[0102] The repeat units A1 are preferably incorporated in a range of 10 to 95 mol %, more preferably 30 to 85 mol % based on the overall repeat units of the polymer in the base polymer. It is noted that when the polymer contains additional repeat units of at least one type selected from repeat units having formulae (B1) and (B2) contributing to high etching resistance, the additional repeat units having a phenolic hydroxy group as a substituent group, the sum of repeat units A1 and additional repeat units preferably falls in the above range. The repeat units A1 used herein may be of one type or a mixture of two or more types.

[0103] The repeat unit A2 has the following formula (A2).

##STR00011##

[0104] In formula (A2), R.sup.A is as defined above. X.sup.2 is a single bond, *—C(═O)—O—X.sup.21—, phenylene group, or naphthylene group. The phenylene group and naphthylene group may be substituted with an optionally fluorinated C.sub.1-C.sub.10 alkoxy group or halogen. X.sup.21 is a C.sub.1-C.sub.20 aliphatic hydrocarbylene group, phenylene group or naphthylene group, the aliphatic hydrocarbylene group may contain at least one moiety selected from an optionally fluorinated C.sub.1-C.sub.10 alkoxy moiety, hydroxy, ether bond, ester bond and lactone ring. The asterisk (*) designates a point of attachment to the carbon atom in the backbone.

[0105] The aliphatic hydrocarbylene group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include 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-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl, pentane-1,5-diyl, 2-methylbutane-1,2-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane-1,10-diyl; cycloalkanediyl groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; divalent polycyclic saturated hydrocarbylene groups such as adamantanediyl and norbornanediyl; and divalent groups obtained by combining the foregoing.

[0106] Examples of the unit having formula (A2) wherein X.sup.2 is a variant are illustrated below, but not limited thereto. Herein R.sup.A is as defined above, and the broken line designates a point of attachment to the carbon atom to which R.sup.B and R.sup.C are attached in formula (A2).

##STR00012## ##STR00013## ##STR00014## ##STR00015##

[0107] In formula (A2), R.sup.B and R.sup.C are each independently 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 include C.sub.1-C.sub.10 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl and n-octyl; and C.sub.3-C.sub.10 cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, norbornyl, tricyclodecanyl and adamantyl.

[0108] Also, R.sup.B and R.sup.C may bond together to form a ring with the carbon atom to which they are attached. Suitable rings include cyclopropane, cyclobutane, cyclopentane and cyclohexane rings, with cyclopentane and cyclohexane rings being preferred.

[0109] In formula (A2), R.sup.2 is each independently halogen, cyano group, C.sub.1-C.sub.5 acyl group, C.sub.1-C.sub.5 alkoxy group, C.sub.1-C.sub.5 fluorinated alkyl group, or C.sub.1-C.sub.5 fluorinated alkoxy group. Examples of the fluorinated alkyl group include fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, pentafluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl, and nonafluorobutyl. Examples of the fluorinated alkoxy group include fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, pentafluoropropoxy, 1,1,1,3,3,3-hexafluoro-2-propoxy and nonafluorobutoxy. Inter alia, R.sup.2 is preferably fluorine, C.sub.1-C.sub.5 fluorinated alkyl group, or C.sub.1-C.sub.5 fluorinated alkoxy group, more preferably fluorine, trifluoromethyl or trifluoromethoxy.

[0110] In formula (A2), R.sup.3 is each independently 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 groups R.sup.B and R.sup.C.

[0111] In formula (A2), b1 is an integer of 0 to 2, b2 is an integer of 0 to 2, b1 and b2 are not equal to 0 at the same time.

[0112] In formula (A2), b3 is an integer of 0 to 5, preferably 0 or 1.

[0113] In formula (A2), b4 is an integer of 0 to 2. The structure represents a benzene ring when b4=0, a naphthalene ring when b4=1, and an anthracene ring when b4=2. Inter alia, the benzene ring corresponding to b4=0 is preferred from the aspect of solvent solubility.

[0114] The preferred repeat unit A2 has the formula (A2-1).

##STR00016##

[0115] Herein R.sup.A, R.sup.B, R.sup.C, X.sup.2, R.sup.2, R.sup.3, b1, b2 and b3 are as defined above, with the proviso that b1 and b2 are not equal to 0 at the same time.

[0116] Examples of the repeat unit A2 are shown below, but not limited thereto. Herein, R.sup.A is as defined above.

##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## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##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## ##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## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215##

[0117] Since the acid labile group in the form of a tertiary hydrocarbyl group having a phenyl group attached to the tertiary carbon atom is extremely low in activation energy for acid-catalyzed deprotection reaction as compared with the acid labile group in the form of tertiary alkyl group, typically tert-butyl, deprotection reaction takes place even at a temperature around 50° C. When a polymer having an acid labile group with extremely low activation energy for deprotection reaction is used as the base polymer, the PEB temperature is too low, suggesting a difficulty to control the temperature uniformity or a difficulty to control the acid diffusion. If the distance of acid diffusion cannot be controlled, the dimensional uniformity or maximum resolution of patterns after development is degraded. An adequate PEB temperature is necessary for acid diffusion control. Most often a temperature in the range of 80 to 110° C. is adequate.

[0118] Another problem arising from the use of an acid labile group with low-activation energy is possible elimination of the acid labile group during polymerization in the case of a polymer with which a PAG is to be copolymerized. Although the PAG in the form of onium salt is basically neutral, the onium salt can be partially dissociated by the heat during polymerization. When a repeat unit having a phenolic hydroxy group is concurrently copolymerized, an exchange reaction takes place between the proton of the phenolic hydroxy group and the cation of the PAG to generate an acid whereby elimination of the acid labile group can occur. The elimination during polymerization becomes outstanding particularly when a low-activation energy acid labile group is used.

[0119] As mentioned above, the acid labile group in the form of a tertiary hydrocarbyl group having a phenyl group attached to the tertiary carbon atom has the advantage of satisfactory etching resistance due to the benzene ring. When a PAG is copolymerized, elimination of the acid labile group occurs during polymerization. When an electron attractive group is attached to a benzene ring, the activation energy for elimination of an acid labile group becomes high. It is believed that this is because the stability of a benzyl cation in a deprotection intermediate is lowered by the electron attractive group. It is possible to attach an electron attractive group to an acid labile group which is readily eliminatable, to hold down the reactivity of deprotection reaction to an optimum level.

[0120] When fluorine is introduced into an acid labile group to suppress swell during alkaline development, an improvement in resolution is expected. However, when fluorine is introduced into an acid labile group in the form of a tertiary alkyl group, the stability of intermediate cation during deprotection reaction is largely reduced by the electron attractive effect of fluorine. As a result, creation of olefin does not occur and deprotection reaction does not take place. However, the tertiary acid labile group having a fluorinated aromatic group provides the intermediate cation with optimum stability, shows adequate reactivity for deprotection, and exerts an etch resistance-enhancing effect.

[0121] Also, when a hydroxy group is introduced into an acid labile group, the dissolution rate of a resist film in the exposed region is accelerated. This enhances the dissolution contrast, contributing to a resolution improvement and defect reduction.

[0122] Since the acid labile group is also effective for controlling the influence of backward scattering during image writing, a pattern of rectangular profile is obtained without the risk of the pattern profile being inversely tapered in a sensitivity region of at least 50 μC, preferably at least 100 μC.

[0123] As understood from the foregoing, the specific polymer is used as the base polymer in a positive resist composition, especially chemically amplified positive resist composition, for the purpose of enhancing dissolution contrast and etch resistance while suppressing acid diffusion. There are obtained many advantages including a significantly high contrast of alkaline dissolution rate before and after light exposure, a high acid diffusion-suppressing effect, high resolution, and high pattern fidelity as well as satisfactory profile, reduced LER, improved etch resistance, and low defectiveness of patterns after development.

[0124] The repeat units A2 are preferably incorporated in a range of 2 to 50 mol %, more preferably 10 to 40 mol % based on the overall repeat units of the polymer in the base polymer.

[0125] Since the polymer is designed to have a carboxy group which is protected with an acid labile group, the dissolution rate of exposed region is improved due to the carboxylate framework. Then, the dissolution contrast between exposed and unexposed regions is optimized while maintaining a satisfactory resolution in the exposed region. As a consequence, a pattern with a minimal size difference is obtained independent of pattern density while suppressing the influence of develop loading. In the fabrication of masks wherein the development conditions employed therein are stronger than in the processing of wafer substrates, it is required to form a pattern with a minimal size difference while maintaining a satisfactory resolution and suppressing the influence of develop loading. Then the mask blank and chemically amplified positive resist composition of the invention are best suited for the processing of mask substrates.

[0126] In a preferred embodiment, the polymer in the base polymer further comprises repeat units of at least one type selected from repeat units having the formula (B1), repeat units having the formula (B2), and repeat units having the formula (B3), which are also referred to as repeat units B1, B2 and B3, respectively.

##STR00216##

[0127] In formulae (B1) and (B2), c and d are each independently an integer of 0 to 4.

[0128] In formulae (B1) and (B2), R.sup.11 and R.sup.12 are each independently a hydroxy group, halogen, an optionally halogenated C.sub.2-C.sub.8 saturated hydrocarbylcarbonyloxy group, optionally halogenated C.sub.1-C.sub.8 saturated hydrocarbyl group, or optionally halogenated C.sub.1-C.sub.8 saturated hydrocarbyloxy group. The saturated hydrocarbyl group, saturated hydrocarbyloxy group and saturated hydrocarbylcarbonyloxy group may be straight, branched or cyclic. Groups R.sup.11 may be identical or different when c is 2 or more. Groups R.sup.12 may be identical or different when d is 2 or more.

[0129] In formula (B3), R.sup.A is as defined above, e is an integer of 0 to 5, and f is an integer of 0 to 2.

[0130] In formula (B3), R.sup.13 is an acetyl group, C.sub.1-C.sub.20 saturated hydrocarbyl group, C.sub.1-C.sub.20 saturated hydrocarbyloxy group, C.sub.2-C.sub.20 saturated hydrocarbylcarbonyloxy group, C.sub.2-C.sub.20 saturated hydrocarbyloxyhydrocarbyl group, C.sub.2-C.sub.20 saturated hydrocarbylthiohydrocarbyl group, halogen, nitro group, or cyano group. R.sup.13 may also be hydroxy when f is 1 or 2. The saturated hydrocarbyl group, saturated hydrocarbyloxy group, saturated hydrocarbylcarbonyloxy group, saturated hydrocarbyloxyhydrocarbyl group and saturated hydrocarbylthiohydrocarbyl group may be straight, branched or cyclic. Groups R.sup.13 may be identical or different when e is 2 or more.

[0131] In formula (B3), X.sup.3 is a single bond, *—C(═O)—O— or *—C(═O)—NH—. The asterisk (*) designates a point of attachment to the carbon atom in the backbone.

[0132] In formula (B3), A.sup.3 is a single bond or a C.sub.1-C.sub.10 saturated hydrocarbylene group in which some constituent —CH.sub.2— may be replaced by —O—. The saturated hydrocarbylene group may be straight, branched or cyclic and examples thereof are as exemplified for A.sup.1 in formula (A1).

[0133] When repeat units of at least one type selected from repeat units B1 to B3 are incorporated, better performance is obtained because not only the aromatic ring possesses etch resistance, but the cyclic structure incorporated into the main chain also exerts the effect of improving resistance to etching and EB irradiation during pattern inspection step.

[0134] The repeat units B1 to B3 are preferably incorporated in a range of at least 5 mol % based on the overall repeat units of the polymer in the base polymer for obtaining the effect of improving etch resistance. Also, the repeat units B1 to B3 are preferably incorporated in a range of up to 30 mol %, more preferably up to 25 mol % based on the overall repeat units of the polymer in the base polymer. When the relevant units are free of functional groups or have a functional group other than hydroxy, their content of up to 30 mol % is preferred because the risk of forming development defects is eliminated. Each of the repeat units B1 to B3 may be of one type or a combination of plural types.

[0135] The total content of repeat units A1 and repeat units of at least one type selected from repeat units B1 to B3 is preferably at least 50 mol %, more preferably at least 60 mol %, even more preferably at least 65 mol % based on the overall repeat units of the polymer in the base polymer.

[0136] The polymer in the base polymer may further comprise repeat units of at least one type selected from repeat units having the formulae (C1) to (C8).

##STR00217## ##STR00218##

[0137] In formulae (C1) to (C8), R.sup.A is as defined above. Y.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, *—O—Y.sup.11—, *—C(═O)—O—Y.sup.1—, or *—C(═O)—NH—Y.sup.11— Y.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. Y.sup.2 is a single bond or **—Y.sup.21—C(═O)—O—. Y.sup.21 is a C.sub.1-C.sub.20 hydrocarbylene group which may contain a heteroatom. Y.sup.3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *—O—Y.sup.31—, *—C(═O)—O—Y.sup.31—, or *—C(═O)—NH—Y.sup.31— Y.sup.31 is a C.sub.1-C.sub.6 aliphatic hydrocarbylene group, phenylene group, fluorinated phenylene group, trifluoromethyl-substituted phenylene group, or C.sub.7-C.sub.20 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety. The asterisk (*) designates a point of attachment to the carbon atom in the backbone, and the double asterisk (**) designates a point of attachment to the oxygen atom in the formula. Y.sup.4 is a single bond or C.sub.1-C.sub.30 hydrocarbylene group which may contain a heteroatom. The subscripts k.sup.1 and k.sup.2 are each independently 0 or 1, k.sup.1 and k.sup.2 are 0 when Y.sup.4 is a single bond.

[0138] The repeat unit having formula (C4) or (C8) is a unit which generates an acid upon exposure to high-energy radiation, the acid having a sulfonyl group and being difluoromethylated at β-position thereof. The acid has an acid strength adequate for the deprotection of a polymer comprising repeat units A2. When a polymer comprising repeat units having formula (C4) or (C8) is used as a base polymer in a resist composition, it is possible to properly control the movement and diffusion of the generated acid.

[0139] A photoacid generator capable of generating an arene sulfonic acid upon exposure to high-energy radiation is also commonly used for the deprotection of a polymer comprising units protected with an acetal, tertiary alkyl or tert-butoxycarbonyl group. However, when an arene sulfonic acid-generating unit is introduced as the repeat unit in a base polymer with the intention of attaining the same effect as in the present invention, the resulting base polymer is not always dissolvable in a solvent because of low solvent solubility. In contrast, the polymer comprising repeat units having formula (C4) or (C8) is fully lipophilic and easy to prepare and handle, and a resist composition is readily prepared therefrom.

[0140] In formulae (C2) and (C6), Y.sup.2 is a single bond or —Y.sup.21—C(═O)—O— wherein Y.sup.21 is a C.sub.1-C.sub.20 hydrocarbylene group which may contain a heteroatom. Examples of the hydrocarbylene group Y.sup.21 are given below, but not limited thereto.

##STR00219##

[0141] In formulae (C2) and (C6), R.sup.HF is hydrogen or trifluoromethyl. Examples of the repeat units C2 and C6 wherein R.sup.HF is hydrogen are as exemplified in U.S. Pat. No. 8,105,748 (JP-A 2010-116550). Examples of the repeat units A2 and A6 wherein R.sup.HF is trifluoromethyl are as exemplified in U.S. Pat. No. 8,057,985 (JP-A 2010-077404). Examples of the repeat units C3 and C7 are as exemplified in U.S. Pat. No. 8,835,097 (JP-A 2012-246265) and U.S. Pat. No. 8,900,793 (JP-A 2012-246426).

[0142] In formulae (C1) and (C5), Xa.sup.− is a non-nucleophilic counter ion. Examples of the non-nucleophilic counter ion Xa.sup.− are as exemplified in U.S. Pat. No. 8,349,533 (JP-A 2010-113209) and U.S. Pat. No. 7,511,169 (JP-A 2007-145797).

[0143] In formulae (C4) and (C8), Y.sup.4 is a single bond or C.sub.1-C.sub.30 hydrocarbylene group which may contain a heteroatom. The hydrocarbylene group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include alkanediyl groups such as methanediyl, 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; cyclic saturated hydrocarbylene groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; 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.

[0144] 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 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, cyano moiety, fluorine, chlorine, bromine, iodine, carbonyl moiety, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (—C(═O)—O—C(═O)—), or haloalkyl moiety.

[0145] Preferred examples of the anion in the monomer from which repeat units C4 and C8 are derived are shown below, but not limited thereto.

##STR00220## ##STR00221## ##STR00222##

[0146] In formulae (C1) to (C8), R.sup.21 to R.sup.38 are each independently halogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom.

[0147] Suitable halogen atoms include fluorine, chlorine, bromine and iodine.

[0148] 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, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl; C.sub.3-C.sub.20 cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0.sup.2,6]decanyl, adamantyl, and adamantylmethyl; and C.sub.6-C.sub.20 aryl groups such as phenyl, naphthyl and anthracenyl. In the 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 a moiety containing a heteroatom such as oxygen, sulfur or nitrogen may intervene in a carbon-carbon bond, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (—C(═O)—O—C(═O)—) or haloalkyl.

[0149] Also, R.sup.21 and R.sup.22 may bond together to form a ring with the sulfur atom to which they are attached. R.sup.23 and R.sup.24, R.sup.26 and R.sup.27, or R.sup.29 and R.sup.30 may bond together to form a ring with the sulfur atom to which they are attached. Examples of the ring are shown below.

##STR00223##

[0150] Exemplary structures of the sulfonium cation in formulae (C2) to (C4) are shown below, but not limited thereto.

##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## ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274##

[0151] Exemplary structures of the iodonium cation in formulae (C5) to (C8) are shown below, but not limited thereto.

##STR00275## ##STR00276## ##STR00277##

[0152] Of the repeat units C1 to C8, repeat unit C4 is preferred for the processing of photomask blanks because its acid strength is most appropriate in designing the acid labile group on a polymer.

[0153] The repeat units C1 to C8 are capable of generating an acid upon exposure to high-energy radiation. The acid-generating units bound to a polymer enable to appropriately control acid diffusion and hence, to form a pattern with reduced LER. Since the acid-generating unit is bound to a polymer, the phenomenon that acid volatilizes from the exposed region and re-deposits on the unexposed region during bake in vacuum is suppressed. This is effective for reducing LER and for mitigating any geometric degradation due to an unwanted film thickness loss in the unexposed region.

[0154] The repeat units C1 to C8 are preferably incorporated in a range of 0.1 to 30 mol %, more preferably 0.5 to 20 mol % based on the overall repeat units of the polymer in the base polymer. The repeat units C1 to C8 used herein may be of one type or a mixture of two or more types.

[0155] The repeat units having an aromatic ring structure are preferably incorporated in a range of at least 65 mol %, more preferably at least 75 mol %, even more preferably at least 85 mol %, based on the overall repeat units of the polymer in the base polymer. In the case of a polymer not containing repeat units C1 to C8, it is preferred that all the repeat units have an aromatic ring structure.

[0156] The total content of repeat units A1, repeat units A2, and repeat units of at least one type selected from repeat units B1 to B3 is preferably at least 80 mol %, more preferably at least 85 mol % based on the overall repeat units of the polymer in the base polymer.

[0157] The polymer may further comprise (meth)acrylate units protected with an acid labile group and/or (meth)acrylate units having an adhesive group such as a lactone structure or a hydroxy group other than phenolic hydroxy, as commonly used in the art. These repeat units are effective for fine adjustment of properties of a resist film, but not essential.

[0158] Examples of the (meth)acrylate unit having an adhesive group include repeat units having the following formula (B4), repeat units having the following formula (B5), and repeat units having the following formula (B6), which are also referred to as repeat units B4, B5, and B6, respectively. While these units do not exhibit acidity, they may be used as auxiliary units for providing adhesion to substrates or adjusting solubility.

##STR00278##

[0159] In formulae (B4) to (B6), R.sup.A is as defined above. R.sup.41 is —O— or methylene. R.sup.42 is hydrogen or hydroxy. R.sup.43 is a C.sub.1-C.sub.4 saturated hydrocarbyl group, and g is an integer of 0 to 3.

[0160] When the repeat units B4 to B6 are included, their content is preferably 0 to 20 mol %, more preferably 0 to 10 mol % based on the overall repeat units of the polymer. Each of the repeat units B4 to B6 may be of one type or a combination of plural types.

[0161] The polymer may be synthesized by combining suitable monomers optionally protected with a protective group, copolymerizing them in the standard way, and effecting deprotection reaction if necessary. The copolymerization reaction is preferably radical or anionic polymerization though not limited thereto. For the polymerization reaction, reference may be made to JP-A 2004-115630, for example.

[0162] The polymer should preferably have a Mw of 1,000 to 50,000, and more preferably 2,000 to 20,000. A Mw of at least 1,000 eliminates the risk that pattern features are rounded at their top, inviting degradations of resolution and LER. A Mw of up to 50,000 eliminates the risk that LER is degraded when a pattern with a line width of up to 100 nm is formed. As used herein, Mw is measured by GPC versus polystyrene standards using tetrahydrofuran (THF) or dimethylformamide (DMF) solvent.

[0163] The polymer preferably has a narrow molecular weight distribution or dispersity (Mw/Mn) of 1.0 to 2.0, more preferably 1.0 to 1.9, even more preferably 1.0 to 1.8. A polymer with such a narrow dispersity eliminates the risk that foreign particles are left on the pattern after development and the pattern profile is aggravated.

[0164] The base polymer is designed such that the dissolution rate in alkaline developer is preferably up to 10 nm/min, more preferably up to 7 nm/min, even more preferably up to 5 nm/min. In the advanced generation of lithography wherein the coating film on the substrate is in a thin film range of up to 100 nm, the influence of pattern film thickness loss during alkaline development becomes strong. When the polymer has an alkaline dissolution rate of greater than 10 nm/min, pattern collapse occurs, i.e., a small size pattern cannot be formed. The problem becomes outstanding in the fabrication of photomasks requiring to be defectless and having a tendency of strong development process. It is noted that the dissolution rate of a base polymer in alkaline developer is computed by spin coating a 16.7 wt % solution of a polymer in propylene glycol monomethyl ether acetate (PGMEA) solvent onto a 8-inch silicon wafer, baking at 100° C. for 90 seconds to form a film of 1,000 nm thick, developing the film in a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (TMAH) at 23° C. for 100 seconds, and measuring a loss of film thickness.

[0165] Fluorinated Polymer

[0166] The positive resist composition may further comprise a fluorinated polymer which contains repeat units of at least one type selected from repeat units having the formula (D1), repeat units having the formula (D2), repeat units having the formula (D3), and repeat units having the formula (D4), and which may contain repeat units of at least one type selected from repeat units having the formula (D5) and repeat units having the formula (D6), for the purposes of enhancing contrast, preventing chemical flare of acid upon exposure to high-energy radiation, preventing mixing of acid from an anti-charging film in the step of coating an anti-charging film-forming material on a resist film, and suppressing unexpected unnecessary pattern degradation. It is noted that repeat units having formulae (D1), (D2), (D3), (D4), (D5), and (D6) are also referred to as repeat units D1, D2, D3, D4, D5, and D6, respectively, hereinafter. Since the fluorinated polymer also has a surface active function, it can prevent insoluble residues from re-depositing onto the substrate during the development step and is thus effective for preventing development defects.

##STR00279## ##STR00280##

[0167] In formulae (D1) to (D6), R.sup.B is each independently hydrogen, fluorine, methyl or trifluoromethyl. R.sup.C is each independently hydrogen or methyl. R.sup.101, R.sup.102, R.sup.104 and R.sup.105 are each independently hydrogen or a C.sub.1-C.sub.10 saturated hydrocarbyl group. R.sup.103, R.sup.106, R.sup.107 and R.sup.108 are each independently hydrogen, a C.sub.1-C.sub.15 hydrocarbyl group or fluorinated hydrocarbyl group, or an acid labile group, with the proviso that an ether bond or carbonyl moiety may intervene in a carbon-carbon bond in the hydrocarbyl groups or fluorinated hydrocarbyl groups represented by R.sup.103, R.sup.106, R.sup.107 and R.sup.108. R.sup.109 is hydrogen or a C.sub.1-C.sub.5 straight or branched hydrocarbyl group in which a heteroatom-containing moiety may intervene in a carbon-carbon bond. R.sup.110 is hydrogen or a C.sub.1-C.sub.5 straight or branched hydrocarbyl group in which a heteroatom-containing moiety may intervene in a carbon-carbon bond. R.sup.111 is a C.sub.1-C.sub.20 saturated hydrocarbyl group in which at least one hydrogen is substituted by fluorine and some constituent —CH.sub.2— may be replaced by an ester bond or ether bond. The subscript x is an integer of 1 to 3, y is an integer satisfying: 0≤y≤5+2z−x, z is 0 or 1, and m is an integer of 1 to 3. Z.sup.1 is a C.sub.1-C.sub.20 (m+1)-valent hydrocarbon group or C.sub.1-C.sub.20 (m+1)-valent fluorinated hydrocarbon group. Z.sup.2 is a single bond, *—C(═O)—O— or *—C(═O)—NH— wherein * designates a point of attachment to the carbon atom in the backbone. Z.sup.3 is a single bond, —O—, *—C(═O)—O—Z.sup.31—Z.sup.32— or *—C(═O)—NH—Z.sup.31—Z.sup.32—, wherein Z.sup.31 is a single bond or a C.sub.1-C.sub.10 saturated hydrocarbylene group, Z.sup.32 is a single bond, ester bond, ether bond or sulfonamide bond, and * designates a point of attachment to the carbon atom in the backbone.

[0168] Examples of the C.sub.1-C.sub.10 saturated hydrocarbyl group represented by R.sup.101, R.sup.102, R.sup.104 and R.sup.105 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, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl, and C.sub.3-C.sub.10 cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornyl. Inter alia, C.sub.1-C.sub.6 saturated hydrocarbyl groups are preferred.

[0169] Examples of the C.sub.1-C.sub.18 hydrocarbyl group represented by R.sup.103, R.sup.106, R.sup.107 and R.sup.108 include C.sub.1-C.sub.15 alkyl, C.sub.2-C.sub.15 alkenyl and C.sub.2-C.sub.15 alkynyl groups, with the C.sub.1-C.sub.15 alkyl groups being preferred. Suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl and n-pentadecyl. The fluorinated hydrocarbyl groups correspond to the foregoing hydrocarbyl groups in which some or all carbon-bonded hydrogen atoms are substituted by fluorine atoms.

[0170] Examples of the C.sub.1-C.sub.20 (m+1)-valent hydrocarbon group Z.sup.1 include the foregoing C.sub.1-C.sub.20 alkyl groups and C.sub.3-C.sub.20 cyclic saturated hydrocarbyl groups, with m number of hydrogen atoms being eliminated. Examples of the C.sub.1-C.sub.20 (m+1)-valent fluorinated hydrocarbon groups include the foregoing (m+1)-valent hydrocarbon groups, with at least one hydrogen being substituted by fluorine.

[0171] Examples of the repeat units D1 to D4 are given below, but not limited thereto. Herein R.sup.B is as defined above.

##STR00281## ##STR00282## ##STR00283##

[0172] Examples of the C.sub.1-C.sub.5 hydrocarbyl groups R.sup.109 and R.sup.11 include alkyl, alkenyl and alkynyl groups, with the alkyl groups being preferred. Suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and n-pentyl. In these groups, a moiety containing a heteroatom such as oxygen, sulfur or nitrogen may intervene in a carbon-carbon bond.

[0173] In formula (D5), —OR.sup.110 is preferably a hydrophilic group. In this case, R.sup.110 is preferably hydrogen or a C.sub.1-C.sub.5 alkyl group in which oxygen intervenes in a carbon-carbon bond.

[0174] Z.sup.2 is preferably *—C(═O)—O— or *—C(═O)—NH—. Also preferably R.sup.C is methyl. The inclusion of carbonyl in Z.sup.2 enhances the ability to trap the acid originating from the anti-charging film. A polymer wherein R.sup.C is methyl is a robust polymer having a high glass transition temperature (Tg) which is effective for suppressing acid diffusion. As a result, the resist film is improved in stability with time, and neither resolution nor pattern profile is degraded.

[0175] Examples of the repeat unit D5 are given below, but not limited thereto. Herein R.sup.C is as defined above.

##STR00284## ##STR00285## ##STR00286##

[0176] The C.sub.1-C.sub.10 saturated hydrocarbylene group Z.sup.3 may be straight, branched or cyclic and examples thereof include 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-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, and 1,1-dimethylethane-1,2-diyl.

[0177] The C.sub.1-C.sub.20 saturated hydrocarbyl group having at least one hydrogen substituted by fluorine, represented by R.sup.111, may be straight, branched or cyclic. Examples thereof correspond to the above exemplified C.sub.1-C.sub.20 alkyl and C.sub.3-C.sub.20 cyclic saturated hydrocarbyl groups in which at least one hydrogen is substituted by fluorine.

[0178] Examples of the repeat unit D6 are given below, but not limited thereto. Herein R.sup.C is as defined above.

##STR00287## ##STR00288## ##STR00289## ##STR00290##

[0179] The repeat units D1 to D4 are preferably incorporated in an amount of 15 to 95 mol %, more preferably 20 to 85 mol % based on the overall repeat units of the fluorinated polymer. The repeat unit D5 and/or D6 is preferably incorporated in an amount of 5 to 85 mol %, more preferably 15 to 80 mol % based on the overall repeat units of the fluorinated polymer. Each of repeat units D1 to D6 may be used alone or in admixture.

[0180] The fluorinated polymer may comprise additional repeat units as well as the repeat units D1 to D6. Suitable additional repeat units include those described in U.S. Pat. No. 9,091,918 (JP-A 2014-177407, paragraphs [0046]-[0078]). When the fluorinated polymer comprises additional repeat units, their content is preferably up to 50 mol % based on the overall repeat units.

[0181] The fluorinated polymer may be synthesized by combining suitable monomers optionally protected with a protective group, copolymerizing them in the standard way, and effecting deprotection reaction if necessary. The copolymerization reaction is preferably radical or anionic polymerization though not limited thereto. For the polymerization reaction, reference may be made to JP-A 2004-115630.

[0182] The fluorinated polymer should preferably have a Mw of 2,000 to 50,000, and more preferably 3,000 to 20,000. A fluorinated polymer with a Mw of less than 2,000 helps acid diffusion, degrading resolution and detracting from age stability. A polymer with too high Mw has a reduced solubility in solvent, with a risk of leaving coating defects. The fluorinated polymer preferably has a dispersity (Mw/Mn) of 1.0 to 2.2, more preferably 1.0 to 1.7.

[0183] In the positive resist composition, the fluorinated polymer is preferably used in an amount of 0.01 to 30 parts, more preferably 0.1 to 20 parts, even more preferably 0.5 to 10 parts by weight per 80 parts by weight of the base polymer.

[0184] Organic Solvent

[0185] The chemically amplified positive resist composition may further comprise an organic solvent. The organic solvent used herein is not particularly limited as long as the components are soluble therein. Examples of the organic solvent are described in JP-A 2008-111103, paragraphs [0144] to [0145] (U.S. Pat. No. 7,537,880). Specifically, exemplary solvents include ketones such as cyclohexanone and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; 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 (EL), ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, and propylene glycol mono-t-butyl ether acetate; and lactones such as γ-butyrolactone (GBL), and mixtures thereof. Where an acid labile group of acetal form is used, a high-boiling alcohol solvent such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol or 1,3-butanediol may be added to accelerate deprotection reaction of acetal.

[0186] Of the above organic solvents, it is recommended to use 1-ethoxy-2-propanol, PGMEA, PGME, cyclohexanone, EL, GBL, and mixtures thereof.

[0187] In the positive resist composition, the organic solvent is preferably used in an amount of 200 to 10,000 parts, more preferably 400 to 5,000 parts by weight per 80 parts by weight of the base polymer. The organic solvent may be used alone or in admixture.

[0188] Photoacid Generator

[0189] The positive resist composition may further comprise a photoacid generator (PAG). The PAG used herein may be any compound capable of generating an acid upon exposure to high-energy radiation. Suitable PAGs include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acid generators.

[0190] Suitable PAGs include nonafluorobutane sulfonate, partially fluorinated sulfonates described in JP-A 2012-189977, paragraphs [0247]-[0251], partially fluorinated sulfonates described in JP-A 2013-101271, paragraphs [0261]-[0265], and those described in JP-A 2008-111103, paragraphs [0122]-[0142] and JP-A 2010-215608, paragraphs [0080]-[0081]. Among others, arylsulfonate and alkanesulfonate type PAGs are preferred because they generate acids having an appropriate strength to deprotect the acid labile group in the repeat units having formula (A2).

[0191] The preferred PAGs are compounds having a sulfonium anion of the structure shown below.

##STR00291## ##STR00292## ##STR00293## ##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300## ##STR00301## ##STR00302## ##STR00303## ##STR00304## ##STR00305##

[0192] Preferred examples of the cation that pairs with the anion include sulfonium cations having the formula (E) and iodonium cations having the formula (F).

##STR00306##

[0193] In formulae (E) and (F), R.sup.201 to R.sup.205 are each independently halogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom.

[0194] Suitable halogen atoms include fluorine, chlorine, bromine and iodine.

[0195] 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, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl; C.sub.3-C.sub.20 cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0.sup.2,6]decanyl, adamantyl, and adamantylmethyl; and C.sub.6-C.sub.20 aryl groups such as phenyl, naphthyl and anthracenyl. In the 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 a moiety containing a heteroatom such as oxygen, sulfur or nitrogen may intervene in a carbon-carbon bond, so that the group may contain a hydroxy, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (—C(═O)—O—C(═O)—) or haloalkyl moiety.

[0196] Also, R.sup.201 and R.sup.202 may bond together to form a ring with the sulfur atom to which they are attached. Examples of the ring are as exemplified above for the ring that R.sup.23 and R.sup.24, R.sup.26 and R.sup.27, or R.sup.29 and R.sup.30 in formulae (C1) to (C8), taken together, form with the sulfur atom to which they are attached.

[0197] Examples of the sulfonium cation having formula (E) are as exemplified above for the sulfonium cation in formulae (C2) to (C4). Examples of the iodonium cation having formula (F) are as exemplified above for the iodonium cation in formulae (C5) to (C8).

[0198] Preferably, the PAG generates an acid having a pKa value of −2.0 or larger. The upper limit of pKa is preferably 2.0. Notably, the pKa value is computed using pKa DB in software ACD/Chemsketch ver: 9.04 of Advanced Chemistry Development Inc.

[0199] An appropriate amount of the PAG used is 1 to 30 parts, more preferably 2 to 20 parts by weight per 80 parts by weight of the base polymer. The PAG may be used alone or in admixture.

[0200] Quencher

[0201] The positive resist composition preferably contains a quencher or acid diffusion-suppressing agent. The 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. Inter alia, tris[2-(methoxymethoxy)ethyl]amine, tris[2-(methoxymethoxy)ethyl]amine-N-oxide, dibutylaminobenzoic acid, morpholine derivatives, and imidazole derivatives are preferred. Addition of a basic compound is effective for further suppressing the diffusion rate of acid in the resist film or correcting the pattern profile.

[0202] Onium salts such as sulfonium salts, iodonium salts and ammonium salts of carboxylic acids which are not fluorinated at α-position as described in U.S. Pat. No. 8,795,942 (JP-A 2008-158339) may also be used as the quencher. While an α-fluorinated sulfonic acid, imide acid, and methide acid are necessary to deprotect the acid labile group, an α-non-fluorinated carboxylic acid is released by salt exchange with an α-non-fluorinated onium salt. An α-non-fluorinated carboxylic acid functions as a quencher because it does not induce substantial deprotection reaction.

[0203] Examples of the onium salt of α-non-fluorinated carboxylic acid include compounds having the formula (G1).

R.sup.301—CO.sub.2.sup.−Mq.sup.+  (G1)

[0204] In formula (G1), R.sup.301 is hydrogen or a C.sub.1-C.sub.40 hydrocarbyl group which may contain a heteroatom, exclusive of the hydrocarbyl group in which the hydrogen bonded to the carbon atom at α-position of the sulfo group is substituted by fluorine or fluoroalkyl.

[0205] The hydrocarbyl group may be saturated or unsaturated and straight, branched or cyclic. Examples thereof include C.sub.1-C.sub.40 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; C.sub.3-C.sub.40 cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0.sup.2,6]decanyl, adamantyl, and adamantylmethyl; C.sub.2-C.sub.40 alkenyl groups such as vinyl, allyl, propenyl, butenyl and hexenyl; C.sub.3-C.sub.40 cyclic unsaturated aliphatic hydrocarbyl groups such as cyclohexenyl; C.sub.6-C.sub.40 aryl groups such as phenyl, naphthyl, alkylphenyl groups (e.g., 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-n-butylphenyl), dialkylphenyl groups (e.g., 2,4-dimethylphenyl and 2,4,6-triisopropylphenyl), alkylnaphthyl groups (e.g., methylnaphthyl and ethylnaphthyl), dialkylnaphthyl groups (e.g., dimethylnaphthyl and diethylnaphthyl); and C.sub.7-C.sub.40 aralkyl groups such as benzyl, 1-phenylethyl and 2-phenylethyl.

[0206] In the hydrocarbyl groups, some hydrogen may be substituted by a moiety containing a heteroatom such as oxygen, sulfur, nitrogen or halogen, and some —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, cyano moiety, carbonyl moiety, ether bond, thioether bond, ester bond, sulfonic ester bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride (—C(═O)—O—C(═O)—), or haloalkyl moiety. Suitable heteroatom-containing hydrocarbyl groups include heteroaryl groups such as thienyl; alkoxyphenyl groups such as 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-tert-butoxyphenyl, 3-tert-butoxyphenyl; alkoxynaphthyl groups such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl and n-butoxynaphthyl; dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl; and aryloxoalkyl groups, typically 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl and 2-(2-naphthyl)-2-oxoethyl.

[0207] In formula (G1), Mq is an onium cation. The onium cation is preferably selected from sulfonium, iodonium and ammonium cations, more preferably sulfonium and iodonium cations. Exemplary sulfonium cations are as exemplified above for the sulfonium cation in formulae (C2) to (C4). Exemplary iodonium cations are as exemplified above for the iodonium cation in formulae (C5) to (C8).

[0208] Examples of the anion of the salt having formula (G1) are shown below, but not limited thereto.

##STR00307## ##STR00308## ##STR00309##

[0209] A sulfonium salt of iodized benzene ring-containing carboxylic acid having the formula (G2) is also useful as the quencher.

##STR00310##

[0210] In formula (G2), R.sup.401 is hydroxy, fluorine, chlorine, bromine, amino, nitro, cyano, or a C.sub.1-C.sub.6 saturated hydrocarbyl, C.sub.1-C.sub.6 saturated hydrocarbyloxy, C.sub.2-C.sub.6 saturated hydrocarbylcarbonyloxy or C.sub.1-C.sub.4 saturated hydrocarbylsulfonyloxy group, in which some or all hydrogen may be substituted by halogen, or —N(R.sup.401A)—C(═O)—R.sup.401B, or —N(R.sup.401A)—C(═O)—O—R.sup.401B. R.sup.401A is hydrogen or a C.sub.1-C.sub.6 saturated hydrocarbyl group. R.sup.401B is a C.sub.1-C.sub.6 saturated hydrocarbyl or C.sub.2-C.sub.8 unsaturated aliphatic hydrocarbyl group.

[0211] In formula (G2), p is an integer of 1 to 5, q is an integer of 0 to 3, and r is an integer of 1 to 3. L.sup.1 is a single bond, or a C.sub.1-C.sub.20 (r+1)-valent linking group which may contain at least one moiety selected from ether bond, carbonyl moiety, ester bond, amide bond, sultone ring, lactam ring, carbonate bond, halogen, hydroxy moiety, and carboxy moiety. The saturated hydrocarbyl, saturated hydrocarbyloxy, saturated hydrocarbylcarbonyloxy, and saturated hydrocarbylsulfonyloxy groups may be straight, branched or cyclic. Groups R.sup.401 may be the same or different when q and/or r is 2 or 3.

[0212] In formula (G2), R.sup.402, R.sup.403 and R.sup.404 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 include C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.6-C.sub.20 aryl, and C.sub.7-C.sub.20 aralkyl groups. In these groups, some or all hydrogen may be substituted by hydroxy, carboxy, halogen, oxo, cyano, nitro, sultone ring, sulfo, or sulfonium salt-containing moiety, or some —CH.sub.2— may be replaced by an ether bond, ester bond, carbonyl moiety, amide bond, carbonate moiety or sulfonic ester bond. Also R.sup.402 and R.sup.403 may bond together to form a ring with the sulfur atom to which they are attached.

[0213] Examples of the compound having formula (G2) include those described in U.S. Pat. No. 10,295,904 (JP-A 2017-219836). These compounds exert a sensitizing effect due to remarkable absorption and an acid diffusion-controlling effect.

[0214] A nitrogen-containing carboxylic acid salt compound having the formula (G3) is also useful as the quencher.

##STR00311##

[0215] In formula (G3), R.sup.501 to R.sup.504 are each independently hydrogen, -L.sup.2-CO.sub.2.sup.−, or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom. R.sup.501 and R.sup.502, R.sup.502 and R.sup.503, or R.sup.503 and R.sup.504 may bond together to form a ring with the carbon atom to which they are attached. L.sup.2 is a single bond or a C.sub.1-C.sub.20 hydrocarbylene group which may contain a heteroatom. R.sup.505 is hydrogen or a C.sub.1-C.sub.20 hydrocarbyl group which may contain a heteroatom.

[0216] In formula (G3), the ring R is a C.sub.2-C.sub.6 ring containing the carbon and nitrogen atoms in the formula, in which some or all of the carbon-bonded hydrogen atoms may be substituted by a C.sub.1-C.sub.20 hydrocarbyl group or -L.sup.2-CO.sub.2— and in which some carbon may be replaced by sulfur, oxygen or nitrogen. The ring may be alicyclic or aromatic and is preferably a 5- or 6-membered ring. Suitable rings include pyridine, pyrrole, pyrrolidine, piperidine, pyrazole, imidazoline, pyridazine, pyrimidine, pyrazine, imidazoline, oxazole, thiazole, morpholine, thiazine, and triazole rings.

[0217] The carboxylic onium salt having formula (G3) has at least one -L.sup.2-CO.sub.2.sup.−. That is, at least one of R.sup.501 to R.sup.504 is -L.sup.2-CO.sub.2.sup.−, and/or at least one of hydrogen atoms bonded to carbon atoms in the ring R is substituted by -L.sup.2-CO.sub.2.sup.−.

[0218] In formula (G3), Q.sup.+ is a sulfonium, iodonium or ammonium cation, with the sulfonium cation being preferred. Examples of the sulfonium cation are as exemplified above for the cation in formula (E).

[0219] Examples of the anion in the compound having formula (G3) are shown below, but not limited thereto.

##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316## ##STR00317##

[0220] Weak acid betaine compounds are also useful as the quencher. Non-limiting examples thereof are shown below.

##STR00318##

[0221] 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.

[0222] When used, the quencher is preferably added in an amount of 0 to 50 parts, more preferably 0.1 to 40 parts by weight per 80 parts by weight of the base polymer. The quencher may be used alone or in admixture.

[0223] When the chemically amplified positive resist composition contains both the PAG and the quencher, the weight ratio of the PAG to the quencher is preferably less than 6/1, more preferably less than 5/1, even more preferably less than 4/1. As long as the weight ratio of the PAG to the quencher is in the range, the resist composition is able to fully suppress acid diffusion, leading to improved resolution and dimensional uniformity.

[0224] Surfactant

[0225] The positive resist composition may contain any conventional surfactants for facilitating to coat the composition to the substrate. A number of surfactants are known in the art as described in JP-A 2004-115630, and any suitable one may be chosen therefrom. The amount of surfactant added is preferably 0 to 5 parts by weight per 80 parts by weight of the base polymer. It is noted that the surfactant need not be added when the positive resist composition contains a fluorinated polymer as mentioned above, which also plays the role of a surfactant.

[0226] From the standpoint of improving the develop loading effect, the chemically amplified positive resist composition is preferably designed such that a resist film formed therefrom in an over-exposed region may have a dissolution rate in alkaline developer of at least 100 nm/sec, more preferably at least 200 nm/sec, even more preferably at least 300 nm/sec. As long as the dissolution rate is at least 100 nm/sec, the resist film is uniformly dissolved in alkaline developer independent of a pattern layout difference in the case of a grouped/isolated pattern, and the variation of line width can be minimized. It is noted that the dissolution rate of an over-exposed region is computed by spin coating the positive resist composition onto a 8-inch silicon wafer, baking at 110° C. for 60 seconds to form a resist film of 90 nm thick, exposing the resist film to KrF excimer laser radiation in a sufficient energy dose to complete deprotection reaction on the polymer, baking at 110° C. for 60 seconds, developing the film in a 2.38 wt % TMAH aqueous solution at 23° C., and measuring a loss of film thickness by means of a resist development analyzer.

[0227] Also preferably, the resist film formed from the positive resist composition in an unexposed region has a dissolution rate in alkaline developer of up to 10 nm/min, more preferably up to 8 nm/min, even more preferably up to 6 nm/min. Where the resist film is in the thin film range of up to 100 nm, the influence of pattern film thickness loss in alkaline developer becomes greater. If the dissolution rate in unexposed region is more than 10 nm/min, pattern collapse will occur, failing to form a small size pattern. The problem becomes outstanding in the fabrication of photomasks requiring to be defectless and having a tendency of strong development process. It is noted that the dissolution rate of an unexposed region is computed by spin coating the positive resist composition onto a 6-inch silicon wafer, baking at 110° C. for 240 seconds to form a resist film of 80 nm thick, developing the film in a 2.38 wt % TMAH aqueous solution at 23° C. for 80 seconds, and measuring a loss of film thickness.

[0228] Mask Blank

[0229] The mask blank includes a substrate and the resist film thereon. Examples of the mask substrate include Cr, CrO, CrON, MoSi.sub.2, Si, SiO, SiO.sub.2, SiON, SiONC, CoTa, NiTa, TaBN, and SnO.sub.2. The resist composition is applied onto a substrate by a suitable coating technique such as spin coating. The coating is prebaked on a hot plate at a temperature of preferably 60 to 150° C. for 1 to 20 minutes, more preferably at 80 to 140° C. for 1 to 10 minutes. The resulting resist film is generally 0.03 to 2 μm thick.

[0230] The mask blank is typically a photomask blank having a light-shielding film of chromium-based material. It may be either a photomask blank for binary masks or a photomask blank for phase shift masks. In the case of the binary mask-forming photomask blank, the light-shielding film may include an antireflection layer of chromium-based material and a light-shielding layer. In one example, the antireflection layer on the surface layer side is entirely composed of a chromium-based material. In an alternative example, only a surface side portion of the antireflection layer on the surface layer side is composed of a chromium-based material and the remaining portion is composed of a silicon compound-based material which may contain a transition metal. In the case of the phase shift mask-forming photomask blank, it may include a phase shift film and a chromium-based light-shielding film thereon.

[0231] Photomask blanks having an outermost layer of chromium base material are well known as described in JP-A 2008-026500 and JP-A 2007-302873 and the references cited therein. Although the detail description is omitted herein, the following layer construction may be employed when a light-shielding film including an antireflective layer and a light-shielding layer is composed of chromium base materials.

[0232] In the example where a light-shielding film including an antireflective layer and a light-shielding layer is composed of chromium base materials, layers may be stacked in the order of an antireflective layer and a light-shielding layer from the outer surface side, or layers may be stacked in the order of an antireflective layer, a light-shielding layer, and an antireflective layer from the outer surface side. Each of the antireflective layer and the light-shielding layer may be composed of multiple sub-layers. When the sub-layers have different compositions, the composition may be graded discontinuously or continuously from sub-layer to sub-layer. The chromium base material used herein may be metallic chromium or a material consisting of metallic chromium and a light element such as oxygen, nitrogen or carbon. Examples used herein include metallic chromium, chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium oxycarbide, chromium nitride carbide, and chromium oxide nitride carbide.

[0233] The reflection type mask blank of the invention includes a substrate, a multilayer reflective film formed on one major surface (front surface) of the substrate, for example, a multilayer reflective film of reflecting exposure radiation such as EUV radiation, and an absorber film formed on the multilayer reflective film, for example, an absorber film of absorbing exposure radiation such as EUV radiation to reduce reflectivity. From the reflection type mask blank (reflection type mask blank for EUV lithography), a reflection type mask (reflection type mask for EUV lithography) having an absorber pattern (patterned absorber film) formed by patterning the absorber film is produced. The EUV radiation used in the EUV lithography has a wavelength of 13 to 14 nm, typically about 13.5 nm.

[0234] The multilayer reflective film is preferably formed contiguous to one major surface of a substrate. An underlay film may be disposed between the substrate and the multilayer reflective film as long as the benefits of the invention are not lost. The absorber film may be formed contiguous to the multilayer reflective film while a protective film (protective film for the multilayer reflective film) may be disposed between the multilayer reflective film and the absorber film, preferably contiguous to the multilayer reflective film, more preferably contiguous to the multilayer reflective film and the absorber film. The protective film is used for protecting the multilayer reflective film in a cleaning, tailoring or otherwise processing step. Also preferably, the protective film has an additional function of protecting the multilayer reflective film or preventing the multilayer reflective film from oxidation during the step of patterning the absorber film by etching. Besides, an electroconductive film, which is used for electrostatic chucking of the reflection type mask to an exposure tool, may be disposed below the other major surface (back side surface) which is opposed to the one major surface of the substrate, preferably contiguous to the other major surface. It is provided herein that a substrate has one major surface which is a front or upper side surface and another major surface which is a back or lower side surface. The terms “front and back” sides or “upper and lower” sides are used for the sake of convenience. One or another major surface may be either of the two major surfaces (film-bearing surfaces) of a substrate, and in this sense, front and back or upper and lower are exchangeable. Specifically, the multilayer reflective film may be formed by any of the methods of JP-A 2021-139970 and the references cited therein.

[0235] Pattern Forming Process

[0236] A further embodiment of the invention is a resist pattern forming process comprising the steps of applying the chemically amplified positive resist composition onto a mask blank to form a resist film thereon, exposing the resist film patternwise to high-energy radiation, and developing the exposed resist film in an alkaline developer.

[0237] After coating, the resist film is exposed to a desired pattern of high-energy radiation. Examples of the high-energy radiation include UV, deep-UV, excimer laser radiation (KrF, ArF, etc.), EUV, x-ray, γ-ray, synchrotron radiation, and EB. Exposure using EUV or EB is preferred herein.

[0238] When UV, deep-UV, excimer laser, EUV, x-ray, 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 1 to 500 mJ/cm.sup.2, more preferably 10 to 400 mJ/cm.sup.2. When EB is used as the high-energy radiation, the resist film is exposed thereto directly in a dose of preferably 1 to 500 μC/cm.sup.2, more preferably 10 to 400 μC/cm.sup.2.

[0239] The exposure may be performed by conventional lithography whereas the immersion lithography of holding a liquid, typically water between the resist film and the mask may be employed if desired. In the case of immersion lithography, a protective film which is insoluble in water may be formed on the resist film.

[0240] After the exposure, the resist film may be baked (PEB) on a hotplate preferably at 60 to 150° C. for 1 to 20 minutes, more preferably at 80 to 140° C. for 1 to 10 minutes.

[0241] After the exposure or PEB, the resist film is developed in a developer in the form of an aqueous alkaline solution for preferably 0.1 to 3 minutes, more preferably 0.5 to 2 minutes by conventional techniques such as dip, puddle and spray techniques. A typical developer is a 0.1 to 5 wt %, preferably 2 to 3 wt % aqueous solution of tetramethylammonium hydroxide (TMAH) or another alkali. In this way, the desired pattern is formed on the substrate.

[0242] The mask blank and positive resist composition of the invention are useful in forming a resist pattern having a satisfactory resolution, pattern fidelity and reduced LER. The positive resist composition is also useful in forming a resist pattern on a substrate which is prone to the influence of back scattering during EB writing and which is difficult to form a resist pattern of rectangular profile thereon. Examples of such substrate include substrates having sputter deposited on their outermost surface a layer of metallic chromium or a chromium compound containing one or more light elements such as oxygen, nitrogen and carbon, and substrates having an outermost layer of SiO, SiO.sub.x, or a tantalum, molybdenum, cobalt, nickel, tungsten or tin compound. The mask blank and positive resist composition most effectively work for the mask blank of reflection type.

[0243] The resist pattern forming process is successful in forming patterns having a high resolution, minimized influence of develop loading, and a reduced size difference independent of a pattern density (grouped or isolated) even on a substrate (typically mask blank of transmission or reflection type) whose outermost surface is made of a material tending to affect resist pattern profile by backward scattering during EB writing, such as a chromium, silicon or tantalum-containing material.

EXAMPLES

[0244] Examples of the invention are given below by way of illustration and not by way of limitation. The abbreviation “pbw” is parts by weight. For copolymers, the compositional ratio is a molar ratio and Mw is determined by GPC versus polystyrene standards.

[1] Synthesis of Polymer

Synthesis Example 1-1: Synthesis of Polymer P-2

[0245] In nitrogen atmosphere, a 300-mL dropping cylinder was charged with 43.4 g of 4-acetoxystyrene, 6.8 g of acenaphthylene, 29.8 g of 2-(4-fluorophenyl)propan-2-yl methacrylate, 8.2 g of dimethyl 2,2′-azobis(2-methylpropionate) (tradename V-601 by Fujifilm Wako Pure Chemical), and 124 g of methyl ethyl ketone (MEK) solvent to form a monomer solution. In nitrogen atmosphere, a 500-mL flask was charged with 62 g of MEK and heated at 80° C. The monomer solution was added dropwise to the flask over 4 hours. After the completion of dropwise addition, the polymerization solution was continuously stirred for 18 hours while maintaining its temperature at 80° C. Thereafter, the polymerization solution was cooled to room temperature and added dropwise to 1,300 g of hexane for precipitation. The copolymer precipitated was collected by filtration and washed twice with 500 g of hexane. In a 1-L flask under nitrogen atmosphere, the copolymer was dissolved in a mixture of 144 g of THF and 48 g of methanol. 22.3 g of ethanol amine was added to the solution, which was stirred at 60° C. for 3 hours. The reaction solution was concentrated under reduced pressure. The concentrate was dissolved in a mixture of 240 g of ethyl acetate and 60 g of water. The solution was transferred to a separatory funnel, to which 11.1 g of acetic acid was added, followed by separatory operation. The lower layer was distilled off, after which 60 g of water and 14.8 g of pyridine were added to the organic layer, followed by separatory operation. The lower layer was distilled off, after which 60 g of water was added to the organic layer. This was followed by 5 cycles of water washing and separation. The organic layer after separation was concentrated and dissolved in 130 g of acetone. The acetone solution was added dropwise to 1,200 g of water for crystallization and precipitation. The precipitate was filtered, washed with water, and suction filtered for 2 hours. The precipitate was dissolved in 130 g of acetone again. The acetone solution was added dropwise to 1,200 g of water for crystallization and precipitation. The precipitate was subjected to filtration, water washing and drying, obtaining 50.7 g of a polymer as white solid. The polymer designated Polymer P-2 was analyzed by .sup.1H-NMR, .sup.13C-NMR and GPC, with the results shown below.

##STR00319##

Synthesis Examples 1-2 to 1-28 and Comparative Synthesis Example 1-1: Synthesis of Polymers P-1, P-3 to P-28 and Comparative Polymer cP-1

[0246] Polymers P-1, P-3 to P-28 and Comparative Polymer cP-1 were synthesized by the same procedure as in Synthesis Example 1-1 except that the type and amount (mol %) of monomers were changed. In Table 1, the incorporation ratio is a molar ratio.

TABLE-US-00001 TABLE 1 Incorporation Incorporation Incorporation Incorporation ratio ratio ratio ratio Unit 1 (mol %) Unit 2 (mol %) Unit 3 (mol %) Unit 4 (mol %) Mw Mw/Mn P-1 A-1 60.0 C-1 40.0 5,500 1.63 P-2 A-1 60.0 B-1 10.0 C-1 30.0 5,400 1.63 P-3 A-1 60.0 B-2 15.0 C-1 25.0 5,100 1.59 P-4 A-1 60.0 B-2 10.0 C-1 30.0 5,200 1.60 P-5 A-1 60.0 B-3 10.0 C-1 30.0 5,100 1.65 P-6 A-1 60.0 B-4 10.0 C-1 30.0 5,300 1.64 P-7 A-1 60.0 B-2 10.0 C-2 30.0 5,600 1.63 P-8 A-1 60.0 B-2 10.0 C-3 35.0 5,200 1.64 P-9 A-1 60.0 B-2 10.0 C-4 30.0 6,100 1.65 P-10 A-1 60.0 B-2 10.0 C-5 30.0 5,600 1.64 P-11 A-1 60.0 B-2 10.0 C-6 30.0 5,300 1.68 P-12 A-1 60.0 B-2 10.0 C-7 30.0 5,200 1.67 P-13 A-1 65.0 B-2 10.0 C-8 30.0 5,700 1.68 P-14 A-1 60.0 B-2 10.0 C-9 30.0 5,600 1.67 P-15 A-2 60.0 B-2 15.0 C-10 25.0 5,500 1.66 P-16 A-2 60.0 B-2 15.0 C-11 25.0 5,400 1.65 P-17 A-2 60.0 B-2 15.0 C-12 25.0 5,800 1.67 P-18 A-2 60.0 B-2 15.0 C-13 25.0 5,700 1.65 P-19 A-2 60.0 B-2 15.0 C-14 25.0 5,600 1.64 P-20 A-2 60.0 B-2 15.0 C-15 25.0 5,500 1.64 P-21 A-2 60.0 B-2 15.0 C-16 25.0 5,600 1.63 P-22 A-2 60.0 B-2 15.0 C-17 25.0 5,700 1.66 P-23 A-3 60.0 B-2 10.0 C-1 30.0 7,600 1.76 P-24 A-1 50.0 B-2 10.0 C-1 30.0 C-11 10.0 5,700 1.64 P-25 A-2 55.0 B-2 10.0 C-1 20.0 C-11 15.0 5,700 1.65 P-26 A-2 55.0 B-2 10.0 C-1 20.0 C-15 15.0 5,800 1.67 P-27 A-2 70.0 C-1 30.0 6,100 1.68 P-28 A-2 70.0 C-2 30.0 6,300 1.71 CP-1 A-1 80.0 B-2 12.0 C-1 8.0 5,100 1.65

[0247] The structure of repeat units incorporated in the polymers is shown below.

##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324##

[0248] The dissolution rate of a polymer in alkaline developer was determined by spin coating a 16.7 wt % solution of the polymer in propylene glycol monomethyl ether acetate (PGMEA) solvent onto a 8-inch silicon wafer, baking at 100° C. for 90 seconds to form a film of 1,000 nm thick, developing the film in a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (TMAH) at 23° C. for 100 seconds, and measuring a loss of film thickness. Polymers P-1 to P-28 showed a dissolution rate of up to 10 nm/min whereas Comparative Polymer cP-1 showed a dissolution rate of 20 nm/min.

Synthesis Examples 2-1 to 2-6 and Comparative Synthesis Examples 1-2 to 1-5: Synthesis of Polymers AP-1 to AP-6 and Comparative Polymers cP-2 to cP-5

[0249] Polymers AP-1 to AP-6 and Comparative Polymers cP-2 to cP-5 were synthesized by the same procedure as Synthesis Example 1-1 except that the monomers were changed. Polymers AP-1 to AP-6 and Comparative Polymers cP-2 to cP-5 showed a dissolution rate in alkaline developer of up to 10 nm/min.

##STR00325## ##STR00326## ##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331##

[2] Preparation of Chemically Amplified Positive Resist Compositions

Examples 1-1 to 1-48 and Comparative Examples 1-1 to 1-6

[0250] Chemically amplified positive resist compositions were prepared by dissolving selected components in an organic solvent in accordance with the formulation shown in Tables 2 to 4, and filtering the solution through a UPE filter with a pore size of 20 nm. The organic solvent was a mixture of 650 pbw of PGMEA, 1,810 pbw of EL, and 1,810 pbw of PGME.

TABLE-US-00002 TABLE 2 Resist Polymer 1 Polymer 2 Photoacid generator Quencher Additive composition (pbw) (pbw) (pbw) (pbw) (pbw) Example 1-1  R-1 P-1 — PAG-A (8) Q-1 — (80) PAG-B (3) (10.0) 1-2  R-2 P-1 — PAG-A (8) Q-1 D-1 (80) PAG-B (3) (10.0) (1.5) 1-3  R-3 P-1 — PAG-A (8) Q-1 D-2 (80) PAG-B (3) (10.0) (1.5) 1-4  R-4 P-1 — PAG-A (8) Q-1 D-3 (80) PAG-B (3) (10.0) (3.0) 1-5  R-5 P-1 — PAG-A (8) Q-1 D-4 (80) PAG-B (3) (10.0) (1.5) 1-6  R-6 P-1 — PAG-C (8) Q-1 D-5 (80) PAG-B (3) (10.0) (1.5) 1-7  R-7 P-1 — PAG-C (8) Q-2 D-1 (80) PAG-B (3) (10.0) (1.5) 1-8  R-8 P-1 — PAG-C (8) Q-3 D-1 (80) PAG-B (3) (10.0) (1.5) 1-9  R-9 P-2 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-10 R-10 P-2 — PAG-C (16) Q-1 D-1 (80) PAG-B (3) (13.0) (1.5) 1-11 R-11 P-3 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-12 R-12 P-4 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-13 R-13 P-5 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-14 R-14 P-6 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-15 R-15 P-7 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-16 R-16 P-8 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-17 R-17 P-9 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-18 R-18 P-10 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-19 R-19 P-11 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-20 R-20 P-12 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-21 R-21 P-13 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-22 R-22 P-14 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-23 R-23 P-15 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-24 R-24 P-16 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-25 R-25 P-17 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-26 R-26 P-18 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5)

TABLE-US-00003 TABLE 3 Resist Polymer 1 Polymer 2 Photoacid generator Quencher Additive composition (pbw) (pbw) (pbw) (pbw) (pbw) Example 1-27 R-27 P-19 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-28 R-28 P-20 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-29 R-29 P-21 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-30 R-30 P-22 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-31 R-31 P-23 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-32 R-32 P-24 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-33 R-33 P-25 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-34 R-34 P-26 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-35 R-35 P-4 P-10 PAG-C (5) Q-1 D-1 (40) (40) PAG-B (3) (8.0) (1.5) 1-36 R-36 P-4 P-16 PAG-C (5) Q-1 D-1 (40) (40 PAG-B (3) (8.0) (1.5) 1-37 R-37 P-16 P-18 PAG-C (5) Q-1 D-1 (40) (40) PAG-B (3) (8.0) (1.5) 1-38 R-38 AP-1 — — Q-1 D-1 (80) (5.0) (1.5) 1-39 R-39 AP-1 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (12.0) (1.5) 1-40 R-40 AP-1 P-4 PAG-C (5) Q-1 D-1 (80) (40) PAG-B (3) (10.0) (1.5) 1-41 R-41 AP-2 P-4 PAG-C (5) Q-1 D-1 (80) (40) PAG-B (3) (10.0) (1.5) 1-42 R-42 AP-3 P-4 PAG-C (8) Q-1 D-1 (40) (40) PAG-B (3) (8.0) (1.5) 1-43 R-43 AP-4 P-4 PAG-C (8) Q-1 D-1 (40) (40) PAG-B (3) (8.0) (1.5) 1-44 R-44 AP-5 P-4 PAG-C (5) Q-1 D-1 (40) (40) PAG-B (3) (7.0) (1.5) 1-45 R-45 AP-6 P-4 PAG-C (5) Q-1 D-1 (40) (40) PAG-B (3) (7.0) (1.5) 1-46 R-46 AP-5 P-27 PAG-C (8) Q-1 D-1 (40) (40) PAG-B (3) (5.0) (1.5) 1-47 R-47 AP-6 P-28 PAG-C (8) Q-1 D-1 (40) (40) PAG-B (3) (5.0) (1.5) 1-48 R-48 P-4 — PAG-C (8) Q-1 D-1 (80) PAG-B (3) (1.9) (1.5)

TABLE-US-00004 TABLE 4 Resist Polymer 1 Polymer 2 Photoacid generator Quencher Additive composition (pbw) (pbw) (pbw) (pbw) (pbw) Comparative 1-1 CR-1 cP-1 — PAG-C (5) Q-1 D-1 Example (80) PAG-B (3) (8.0) (1.5) 1-2 CR-2 cP-2 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-3 CR-3 cP-3 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-4 CR-4 cP-4 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-5 CR-5 cP-5 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (8.0) (1.5) 1-6 CR-6 cP-5 — PAG-C (5) Q-1 D-1 (80) PAG-B (3) (1.8) (1.5)

[0251] In Tables 2 to 4, quenchers Q-1 to Q-3, photoacid generators PAG-A to PAG-C, and fluorinated polymers D-1 to D-5 have the structures shown below.

##STR00332## ##STR00333## ##STR00334##

[3] EB Lithography Test

Examples 2-1 to 2-48 and Comparative Examples 2-1 to 2-6

[0252] There was furnished a reflection type mask blank for EUV lithography. Namely, a mask blank was furnished by forming a multilayer reflective film of 40 Mo/Si layers having a thickness of 284 nm on a low thermal expansion glass substrate of 6 inch squares, then successively depositing thereon a Ru film of 3.5 nm thick as a protective film, a TaN film of 70 nm thick as an absorber layer, and a CrN film of 6 nm thick as a hard mask.

[0253] Using a coater/developer system ACT-M (Tokyo Electron Ltd.), each of the positive resist compositions (R-1 to R-48, CR-1 to CR-6) was spin coated onto the mask blank and prebaked on a hotplate at 110° C. for 600 seconds to form a resist film of 80 nm thick. The thickness of the resist film was measured by an optical film thickness measurement system Nanospec (Nanometrics Inc.). Measurement was made at 81 points in the plane of the blank substrate excluding a peripheral band extending 10 mm inward from the blank periphery, and an average film thickness and a film thickness range were computed therefrom.

[0254] The resist film was exposed to EB using an EB writer system EBM-5000Plus (NuFlare Technology Inc., accelerating voltage 50 kV), then baked (PEB) at 110° C. for 600 seconds, and developed in a 2.38 wt % TMAH aqueous solution, thereby yielding a positive pattern.

[0255] The resist pattern was evaluated as follows. The patterned mask blank was observed under a top-down scanning electron microscope (TD-SEM). The optimum dose (Eop) was defined as the exposure dose (μC/cm.sup.2) which provided a 1:1 resolution at the top and bottom of a 200-nm 1:1 line-and-space (LS) pattern. The LS resolution (or maximum resolution) was defined as the minimum line width of a L/S pattern that could be resolved at the optimum dose. The edge roughness (LER) of a 200-nm LS pattern was measured under SEM. The develop loading was evaluated by forming a 200-nm LS pattern at the dose (μC/cm.sup.2) capable of resolving a 1:1 LS pattern of 200 nm design at a ratio 1:1 and a 200-nm LS pattern including dummy patterns having a density of 15%, 25%, 33%, 45%, 50%, 55%, 66%, 75%, 85%, and 95% arranged around the center pattern, measuring the size of spaces under SEM, and comparing the size difference among grouped and isolated patterns. Also, the pattern was visually observed to judge whether or not the profile was rectangular. For the evaluation of pattern fidelity, when a square hole pattern of size 120 nm and density 36% was placed, an area loss (%) at one corner of the square hole was computed. A smaller value indicates that the hole profile is more rectangular.

[0256] The dissolution rate of an over-exposed region was determined by spin coating the resist solution onto a 8-inch silicon wafer, baking at 110° C. for 60 seconds to form a resist film of 90 nm thick, exposing the resist film to KrF excimer laser radiation in a dose (mJ/cm.sup.2) capable of resolving a 200-nm 1:1 LS pattern at a ratio 1:1, baking at 110° C. for 60 seconds, developing the film in a 2.38 wt % TMAH aqueous solution at 23° C., and measuring a loss of film thickness by means of a resist development rate analyzer (RDA-800 by Litho Tech Japan Corp.). The results are shown in Tables 5 to 7.

TABLE-US-00005 TABLE 5 Develop Dissolution rate Optimum Maximum loading in over-exposed Resist dose resolution LER variation Pattern Area loss region composition (μC/cm.sup.2) (nm) (nm) (Δnm) profile (%) (nm/s) Example 2-1  R-1 200 35 4.6 1.7 rectangular 10 980 2-2  R-2 190 35 4.7 1.6 rectangular 11 1,000 2-3  R-3 190 35 4.5 1.6 rectangular 11 1,000 2-4  R-4 190 35 4.6 1.5 rectangular 11 1,000 2-5  R-5 190 35 4.4 1.4 rectangular 11 1,000 2-6  R-6 200 35 4.6 1.3 rectangular 11 1,000 2-7  R-7 175 35 4.5 1.5 rectangular 11 1,000 2-8  R-8 185 35 4.6 1.4 rectangular 11 1,000 2-9  R-9 210 30 4.4 1.5 rectangular 9 880 2-10 R-10 190 30 4.4 1.4 rectangular 9 880 2-11 R-11 230 35 4.7 1.7 rectangular 10 780 2-12 R-12 220 30 4.4 1.5 rectangular 9 850 2-13 R-13 210 30 4.6 1.6 rectangular 9 850 2-14 R-14 210 30 4.5 1.5 rectangular 9 850 2-15 R-15 220 30 4.4 1.4 rectangular 9 850 2-16 R-16 220 30 4.5 1.5 rectangular 9 850 2-17 R-17 220 30 4.5 1.6 rectangular 9 850 2-18 R-18 220 30 4.4 1.5 rectangular 9 850 2-19 R-19 220 30 4.5 1.6 rectangular 9 850 2-20 R-20 220 30 4.6 1.5 rectangular 9 850 2-21 R-21 220 30 4.7 1.6 rectangular 9 850 2-22 R-22 220 30 4.5 1.4 rectangular 9 850 2-23 R-23 200 30 4.6 1.5 rectangular 9 880 2-24 R-24 200 30 4.6 1.6 rectangular 9 880 2-25 R-25 200 30 4.7 1.7 rectangular 9 880 2-26 R-26 200 30 4.5 1.6 rectangular 9 880 2-27 R-27 200 30 4.6 1.7 rectangular 9 880 2-28 R-28 200 30 4.6 1.6 rectangular 9 880 2-29 R-29 200 30 4.5 1.6 rectangular 9 880 2-30 R-30 200 30 4.5 1.5 rectangular 9 880

TABLE-US-00006 TABLE 6 Develop Dissolution rate Optimum Maximum loading in over-exposed Resist dose resolution LER variation Pattern Area loss region composition (μC/cm.sup.2) (nm) (nm) (Δnm) profile (%) (nm/s) Example 2-31 R-31 200 35 4.7 1.7 rectangular 10 1,100 2-32 R-32 200 30 4.5 1.6 rectangular 9 1,050 2-33 R-33 200 30 4.6 1.5 rectangular 9 950 2-34 R-34 200 30 4.5 1.5 rectangular 9 950 2-35 R-35 210 30 4.7 1.6 rectangular 9 900 2-36 R-36 210 30 4.6 1.5 rectangular 9 900 2-37 R-37 210 30 4.5 1.7 rectangular 9 950 2-38 R-38 200 30 4.6 1.6 rectangular 9 800 2-39 R-39 200 30 4.5 1.6 rectangular 9 800 2-40 R-40 200 30 4.6 1.7 rectangular 9 820 2-41 R-41 200 30 4.7 1.6 rectangular 9 780 2-42 R-42 220 30 4.6 1.8 rectangular 9 600 2-43 R-43 220 30 4.5 1.8 rectangular 9 600 2-44 R-44 220 30 4.6 1.7 rectangular 9 600 2-45 R-45 220 30 4.5 1.7 rectangular 9 600 2-46 R-46 120 30 4.6 1.8 rectangular 9 550 2-47 R-47 120 30 4.6 1.8 rectangular 9 550 2-48 R-48 45 40 5.1 1.8 rectangular 11 840

TABLE-US-00007 TABLE 7 Develop Dissolution rate Optimum Maximum loading in over-exposed Resist dose resolution LER variation Pattern Area loss region composition (μC/cm.sup.2) (nm) (nm) (Δnm) profile (%) (nm/s) Comparative 2-1 CR-1 210 60 5.5 1.7 rounded top 18 850 Example 2-2 CR-2 200 55 5.2 3.5 inversely 16 40 tapered 2-3 CR-3 190 55 5.4 1.9 inversely 16 850 tapered 2-4 CR-4 240 65 5.4 1.8 inversely 16 850 tapered 2-5 CR-5 220 65 5.4 1.8 inversely 16 870 tapered 2-6 CR-6 47 60 5.9 1.9 inversely 18 870 tapered

[0257] All the chemically amplified positive resist compositions (R-1 to R-48) within the scope of the invention show satisfactory resolution, reduced LER, pattern rectangularity, pattern fidelity, and controlled values of develop loading. A comparison of R-12 with R-48 reveals that the resolution in the low-sensitivity region of 50 μC or more is further improved. Of the comparative resist compositions (CR-1 to CR-6), composition CR-1 has so high a polymer dissolution rate in unexposed region that the pattern shows a rounded top profile and degraded resolution. Composition CR-2 has so low an over-exposed region dissolution rate that the control of develop loading is insufficient. In compositions CR-3 to CR-5, because the design of base polymers is insufficient, not all resolution, LER and pattern rectangularity are met although the develop loading is fully controlled. Composition CR-5 is not optimum in the reactivity of acid labile group as compared with CR-6, and the resolution is degraded under the influence of back scattering in a high-dose region with a higher level of exposure energy.

[4] Evaluation of Etching Resistance

Examples 3-1, 3-2 and Comparative Example 3-1

[0258] Using a coater/developer system ACT-M (Tokyo Electron Ltd.), each of the chemically amplified positive resist compositions (R-12, R-24, CR-5) was spin coated onto a 6-inch mask blank of reflection type for EUV lithography and prebaked on a hotplate at 110° C. for 600 seconds to form a resist film of 90 nm thick. The film thickness was measured by an optical film thickness measurement system NanoSpec (Nanometrics Inc.). Measurement was carried out at 81 in-plane points on the blank substrate excluding an outer rim portion extending 10 mm inward from the periphery. From these measurements, an average film thickness and a film thickness range were computed. Using a dry etching equipment UNAXIS G4, the coated blank was dry etched under the conditions shown below. A film thickness loss rate (Å/sec) was computed from the thickness of the remaining film at the end of etching. The results are shown in Table 8. [0259] RF1 (RIE): pulse 700 V [0260] RF2 (ICP): CW 400 W [0261] Pressure: 6 mTorr [0262] Cl.sub.2: 185 sccm [0263] O.sub.2: 55 sccm [0264] He: 9.25 sccm [0265] Etching time: 75 sec

TABLE-US-00008 TABLE 8 Film thickness Resist loss rate, composition Å/sec Example 3-1 R-12 6.3 Example 3-2 R-24 6.5 Comparative CR-5 8.5 Example 3-1

[0266] The chemically amplified positive resist compositions used in mask blanks showed satisfactory etching resistance.

[5] Evaluation of Different Substrates

Reference Examples 1-1 to 1-4 and Comparative Reference Examples 1-1 to 1-4

[0267] There was furnished a transmission type mask blank for ArF lithography. Namely, a mask blank was furnished by forming a MoSiON film of 75 nm thick on a synthetic quartz substrate (one side 6 inches) as a phase shift layer and a CrN film of 44 nm thick thereon as a light-shielding layer. Using a coater/developer system ACT-M (Tokyo Electron Ltd.), each of the positive resist compositions (R-12, R-24, R-40, R-41, CR-2 to CR-5) was spin coated onto the mask blank and prebaked on a hotplate at 110° C. for 600 seconds to form a resist film of 80 nm thick. The thickness of the resist film was measured by an optical film thickness measurement system Nanospec (Nanometrics Inc.). Measurement was carried out at 81 in-plane points on the blank substrate excluding an outer rim portion extending 10 mm inward from the periphery. From these measurements, an average film thickness and a film thickness range were computed.

[0268] The resist film was exposed to EB using an EB writer system EBM-5000Plus (NuFlare Technology Inc., accelerating voltage 50 kV), then baked (PEB) at 110° C. for 600 seconds, and developed in a 2.38 wt % TMAH aqueous solution, thereby yielding a positive pattern.

[0269] The resist pattern was evaluated for optimum dose, maximum resolution, LER, develop loading, pattern profile, and pattern fidelity by the same methods as in [3] EB lithography test. The results are shown in Table 9.

TABLE-US-00009 TABLE 9 Optimum Maximum Develop loading Resist dose resolution LER variation Area loss composition (μC/cm.sup.2) (nm) (nm) (Δnm) Pattern profile (%) Reference 1-1 R-12 220 30 4.5 1.5 rectangular 9 Example 1-2 R-24 200 30 4.6 1.6 rectangular 9 1-3 R-40 200 30 4.6 1.6 rectangular 9 1-4 R-41 200 30 4.7 1.6 rectangular 9 Comparative 1-1 CR-2 200 50 5.1 3.5 inversely tapered 14 Reference 1-2 CR-3 190 50 5.2 2.0 inversely tapered 14 Example 1-3 CR-4 240 50 5.2 2.0 inversely tapered 14 1-4 CR-5 220 60 5.3 1.8 inversely tapered 14

[0270] When the mask blank is of transmission type, the difference in resolution from Comparative Reference Examples is small because the influence of backward scattering is mitigated as compared with the reflection type mask blank. This suggests that the mask blank and chemically amplified positive resist composition of the invention are useful particularly when applied to the reflection type.

[0271] This accounts for the design of base polymers. The polymer obtained by combining phenolic hydroxy group-containing units with acrylic units containing an acid labile group having an optimized reactivity with acid succeeds in optimization of a pattern profile owing to the phenolic hydroxy group-containing units, optimization of an exposed region dissolution rate owing to acrylic units, and suppression of backward scattering. As a result, satisfactory resolution, LER, pattern rectangularity, pattern fidelity, etching resistance, and develop loading control are achieved.

[0272] The mask blank and the resist pattern forming process using the positive resist composition are useful in photolithography for the fabrication of semiconductor devices and the processing of photomask blanks of reflection type.

[0273] Japanese Patent Application No. 2022-077283 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.