Thick film resist composition and method for producing resist film using same

Abstract

Provided is a thick-film resist composition capable of forming a resist pattern with high rectangularity. The thick-film resist composition comprises a polymer (A), a deprotecting agent (B), a specific carboxylic acid compound (C), and a solvent (D).

Description

[Technical field]

[0001] The present invention relates to a thick-film resist composition used in the manufacture of semiconductor elements, semiconductor integrated circuits, and the like, and a method for producing a resist film using the same. [Background technology]

[0002] In the manufacturing process of devices such as semiconductors, microfabrication by lithography using resist is generally performed. The microfabrication process includes forming a thin resist layer on a semiconductor substrate such as a silicon wafer, covering the layer with a mask pattern corresponding to the pattern of the target device, exposing the layer to active light such as ultraviolet light through the mask pattern, developing the exposed layer to obtain a resist pattern, and etching the substrate using the obtained resist pattern as a protective film, thereby forming fine projections and recesses corresponding to the above-mentioned pattern.

[0003] While there is a demand for finer resist patterns, there is also a demand for thicker resist patterns with higher aspect ratios in order to accommodate high-energy ion implantation, etc. When forming a thick-film resist pattern, unlike a thin-film resist pattern, the performance and process conditions required of the composition are different, and therefore there is a particular difficulty in that the required shape cannot be formed by simply adjusting the viscosity of a thin-film resist composition to thicken the film. Patent Document 1 discusses a composition containing a chemically amplified polymer and a plurality of acid generators, with the aim of obtaining a composition that can form a pattern having a cross-sectional shape close to a rectangle even in a thick film. In order to ensure resistance to subsequent processes such as ion implantation and etching, the shape of the top of the resist pattern is important, and there is still a demand for resist compositions capable of forming the desired shape.

[0004] Studies have been conducted on improving development defects and resist pattern shapes by adding organic acids to thin-film resists. For example, Patent Document 2 studies the addition of maleic acid or the like to a thin-film resist composition with a film thickness of about 0.2 μm. Patent Document 3 studies how to obtain a thick-film resist pattern with a good shape in order to create a magnetic film pattern in a magnetic storage medium. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-109701 A [Patent Document 2] JP 2006-106693 A [Patent Document 3] JP 2007-206425 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have recognized that there remain one or more problems with thick film resist compositions and their use that require improvement. These problems include, for example: It is not possible to form a thick resist film. The rectangularity of the resist pattern is insufficient. There is a hollow at the top of the resist pattern wall. The shape near the top of the pattern is poor. Problems such as pattern breakage occur in post-development processes. When a substrate is processed using a thick resist pattern as a mask, the pattern breaks, and the substrate cannot be processed as intended. There are a large number of defects. The sensitivity obtained with the thick resist film is insufficient. Poor stability over time. The film thickness of the resist film decreases. The resist film or resist pattern is sensitive to heat. The exposure tolerance is small. The resist pattern peels off from the substrate. The present invention has been made based on the above-mentioned technical background, and provides a thick-film resist composition and a method for producing a resist film using the same. [Means for solving the problem]

[0007] The thick-film resist composition according to the present invention comprises a polymer (A), a deprotecting agent (B), 4-12 and a solvent (D), where The resist film formed from the thick film resist composition has a thickness of 0.8 to 20 μm, The carboxylic acid compound (C) is an unsaturated hydrocarbon containing one, two or three carboxy groups, The solvent (D) comprises an organic solvent (D1).

[0008] Further, a method for producing a resist film according to the present invention comprises the following steps: (1) applying the composition above a substrate; (2) The composition is heated to form a resist film having a thickness of 0.8 to 20 μm. Effect of the Invention

[0009] By using the thick-film resist composition of the present invention, one or more of the following effects can be expected. A thick resist film can be formed. A resist pattern with high rectangularity can be formed. The recessed shape at the top of the resist pattern wall can be reduced. The shape near the top of the pattern can be improved. A resist pattern with high resistance can be obtained in post-development processes (e.g. etching). A substrate can be processed using a thick resist pattern as a mask. The number of defects can be reduced. Good sensitivity can be obtained even with a thick resist film. Good stability over time. Reduction in the film thickness of the resist film can be suppressed. The heat resistance of the resist film or resist pattern is high. The exposure tolerance can be increased. Peeling of the resist pattern from the substrate can be suppressed. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a conceptual diagram showing a cross-sectional shape of a resist pattern. [Diagram 2]FIG. 2 is a conceptual diagram showing the wall tops of a resist pattern. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [Definition] In this specification, unless otherwise specifically stated, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "a" or "the" means "at least one." An element of a concept may be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of the elements as well as its use alone. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "C x-y ", "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown by structural formulas, the n or m in parentheses indicates the number of repeats. Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to a compound having that function (for example, in the case of a base generator, it is a compound that generates a base). There may be an embodiment in which the compound is dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, such a solvent is preferably contained in the composition according to the present invention as the solvent (D) or another component.

[0012] Hereinafter, an embodiment of the present invention will be described in detail.

[0013] Thick film resist composition The thick-film resist composition according to the present invention (hereinafter, sometimes referred to as the composition) comprises a polymer (A), a deprotecting agent (B), 4-12 and a solvent (D). The carboxylic acid compound (C) is an unsaturated hydrocarbon containing one, two or three carboxy groups, and the solvent (D) comprises an organic solvent (D1). The thick film resist composition refers to a resist composition capable of forming a thick resist film. In the present invention, the resist film formed from the thick film resist composition has a thickness of 0.8 to 20 μm (preferably 1 to 20 μm; more preferably 2 to 15 μm; even more preferably 7 to 15 μm; and even more preferably 9 to 12 μm). The viscosity of the composition according to the present invention is preferably 250 to 400 cP (more preferably 280 to 380 cP; further preferably 300 to 350 cP), where the viscosity is measured at 25° C. using a capillary viscometer. The composition according to the present invention is preferably a thick-film KrF chemically amplified resist composition or a thick-film positive chemically amplified resist composition, more preferably a thick-film KrF positive chemically amplified resist composition, where the term KrF used in the above preferred embodiment means that a KrF excimer laser is used when exposing a resist film formed from the resist composition.

[0014] (A) Polymer The composition according to the present invention comprises a polymer (A). The polymer (A) used in the present invention is one that reacts with an acid to increase its solubility in an alkaline aqueous solution. Such a polymer has, for example, an acid group protected by a protecting group, and when an acid is added from the outside, the protecting group is eliminated, thereby increasing the solubility in an alkaline aqueous solution. Such a polymer can be arbitrarily selected from those generally used in lithography methods.

[0015] The polymer (A) preferably comprises a repeating unit selected from the group consisting of repeating units represented by formulae (P-1), (P-2), (P-3) and (P-4). [ka] Where: R p1 , R p3 , R p6 and R p8 are each independently hydrogen or C 1-4 It is alkyl (preferably hydrogen or methyl; more preferably hydrogen). R p2 and R p4 each independently represents a linear, branched or cyclic C 3-15 and alkyl (wherein the alkyl may be substituted with fluorine, and -CH2- in the alkyl may be replaced with -O-). Here, the "alkyl substituted with fluorine" means that H present in the alkyl is substituted with F. The substitution with fluorine means that all or a part of H present in the alkyl is substituted with F, and all may be substituted. In one embodiment of the present invention, R p2 and R p4 is not substituted by fluorine. p2 and R p4 The -CH2- in the alkyl of R is not replaced by -O-. p2 is preferably methyl, isopropyl, t-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl or ethyladamantyl (more preferably R p2 has a branched or cyclic structure; more preferably is t-butyl, ethylcyclopentyl, ethylcyclohexyl, or ethyladamantyl; even more preferably is t-butyl). R p4 is preferably C 3-10 (More preferably, C 3-8 ; More preferably, C3-5 ; even more preferably t-butyl). T 1 and T 2 are each independently a single bond or C 1-12 is a linking group (preferably a single bond). 1 or T 2 C 1-12 The linking groups in each of the above are independently alkylene, -COO-Rt-, -O-Rt-, or a linking group consisting of a combination of two or more of these, and preferably -COO-Rt-. Rt is alkylene or cycloalkylene (more preferably C 1-5 Alkylene; more preferably -CH2-, -(CH2)2-, or -(CH2)3-). R p5 , R p7 and R p9 are each independently 1-5 Alkyl (wherein -CH- in the alkyl may be replaced by -O-), preferably methyl or t-butyl, more preferably methyl. In one aspect of the invention, R p5 , R p7 and R p9 The -CH2- in the alkyl is not replaced by -O-. x1 is 1 to 3 (preferably 1, 2 or 3; more preferably 1). x2, x3 and x5 each independently represent 0 to 2 (preferably 0, 1 or 2; more preferably 0). x4 is 1 to 2 (preferably 0 or 1; more preferably 1).

[0016] These repeating units are appropriately blended depending on the purpose, and there are no particular limitations on the blending ratio thereof. However, it is preferable that they are blended so that the rate of increase in solubility in an alkaline aqueous solution due to the acid is appropriate. Based on all repeating units in the polymer, the ratio of repeating units of (P-1) and (P-2) is preferably 5 to 50 mol % (more preferably 10 to 40 mol %). In the polymer (A), the number of repeating units of the formulas (P-1), (P-2), (P-3), and (P-4) is n p1 , n p2 , n p3 , and n p4 Let us assume that. n p1 / (n p1 +n p2 +n p3 +n p4 ) is preferably 0 to 60% (more preferably 1 to 60%; even more preferably 5 to 50%; and even more preferably 10 to 30%). n p2 / (n p1 +n p2 +n p3 +n p4 ) is preferably 0 to 60% (more preferably 0 to 50%; even more preferably 5 to 50%; still more preferably 5 to 30%). In one embodiment of the present invention, n p2 / (n p1 +n p2 +n p3 +n p4 )=0%. n p3 / (n p1 +n p2 +n p3 +n p4 ) is preferably 0 to 90% (more preferably 5 to 80%; even more preferably 30 to 80%; still more preferably 50 to 70%). n p4 / (n p1 +n p2 +n p3 +n p4 ) is preferably 0 to 60% (more preferably 1 to 50%; even more preferably 5 to 40%; and even more preferably 10 to 30%). Preferably n p1 +n p2 >0%, i.e., n p1 and p2 At least one of is greater than 0%. More preferably, n p1 is greater than 0%. n p1 , n p2 , np3 , and n p4 is the following formula: 0%≦n p1 / (n p1 +n p2 +n p3 +n p4 )≦60%, 0%≦n p2 / (n p1 +n p2 +n p3 +n p4 )≦60%, 0%≦n p3 / (n p1 +n p2 +n p3 +n p4 ) ≤ 90%, and 0%≦n p4 / (n p1 +n p2 +n p3 +n p4 )≦60% is satisfied, And p1 +n p2 >0% It is preferable that the following is satisfied. Polymer (A) may contain repeating units other than those represented by formulas (P-1), (P-2), (P-3), and (P-4). Here, the total number n of all repeating units contained in polymer (A) is total But the following formula: 80%≦(n p1 +n p2 +n p3 +n p4 ) / n total It is preferable that the ratio satisfies ≦100%. (n p1 +n p2 +n p3 +n p4 ) / n total is more preferably 90 to 100% (even more preferably 95 to 100%). (n p1 +n p2 +n p3 +n p4 ) / n total= 100%, that is, it does not contain any repeating units other than those represented by formulae (P-1), (P-2), (P-3), and (P-4).

[0017] Specific examples of the polymer (A) are as follows. [ka]

[0018] The mass average molecular weight (Mw) of the polymer (A) is preferably 2,000 to 200,000 (more preferably 4,000 to 200,000; further preferably 8,000 to 30,000). The mass average molecular weight is determined by gel permeation chromatography in terms of polystyrene.

[0019] The polymer (A) may be one type or two or more types. The content of the polymer (A) is preferably from 20 to 45% by mass (more preferably from 25 to 40% by mass; further preferably from 30 to 35% by mass) based on the composition.

[0020] (B) Deprotection Agent The composition according to the present invention comprises a deprotecting agent (B). The deprotecting agent releases an acid when irradiated with light, and the acid acts on the polymer (A) to increase the solubility of the polymer (A) in an alkaline aqueous solution. For example, when the polymer (A) has an acid group protected by a protecting group, the protecting group is removed by the acid. The deprotecting agent used in the composition according to the present invention can be selected from conventionally known agents.

[0021] (B) The deprotecting agent releases an acid having an acid dissociation constant pKa(H2O) of preferably -20 to 1.4 (more preferably -16 to 1.4; even more preferably -16 to 1.2; still more preferably -16 to 1.1) upon exposure to light.

[0022] The deprotecting agent (B) is preferably represented by formula (B-1) or formula (B-2).

[0023] Formula (B-1) is as follows. B n+ Cation B n- Anion (B-1) Where: B n+ The cation is composed of at least one cation selected from the group consisting of cations represented by formulae (BC1) to (BC3), and has a valency of n (wherein n is 1 to 3) as a whole; B n- The anion is composed of at least one anion selected from the group consisting of anions represented by formulae (BA1) to (BA4), and has a valency of n as a whole. The n-valency is preferably monovalent or divalent, and more preferably monovalent.

[0024] Equation (BC1) is as follows: [ka] Where: R b1 are each independently 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, or C 6-12 It is aryloxy (preferably methyl, ethyl, t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy; more preferably, t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy). Each nb1 is independently 0, 1, 2, or 3. When all nb1 are 1, all R b1 In another preferred embodiment, nb1 is 0.

[0025] Specific examples of formula (BC1) are as follows: [ka]

[0026] Equation (BC2) is as follows. [ka] Where: R b2 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 Aryl (preferably R b2 is C 4-6 more preferably t-butyl or 1,1-dimethylpropyl; even more preferably t-butyl). b2 may be the same or different, and are preferably the same. Each nb2 is independently 0, 1, 2 or 3, and preferably 1.

[0027] Specific examples of formula (BC2) are as follows: [ka]

[0028] Equation (BC3) is as follows: [ka] Where: R b3 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 It is aryl (preferably methyl, ethyl, methoxy, or ethoxy; more preferably methyl or methoxy). R b4 are each independently 1-6 It is alkyl (preferably methyl, or ethyl; more preferably methyl). Each nb3 is independently 0, 1, 2 or 3, and more preferably 3.

[0029] Specific examples of formula (BC3) are as follows: [ka]

[0030] B n+ The cation is preferably selected from the group consisting of cations represented by formula (BC1) or (BC2) since it exerts a better effect.

[0031] Equation (BA1) is as follows: [ka] Where: R b5 are each independently 1-6 Fluorine-substituted alkyl, or C 1-6 For example, -CF3 means that the hydrogen of methyl (C1) is replaced by a fluorine atom. 1-6 All hydrogen atoms in the fluorine-substituted alkyl are replaced with fluorine atoms. b5 The alkyl portion of R is preferably methyl, ethyl or t-butyl (more preferably methyl). b5 is preferably a fluorine-substituted alkyl, more preferably -CF3.

[0032] Specific examples of formula (BA1) are as follows: [ka]

[0033] Equation (BA2) is as follows: [ka] Where: R b6 is C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorine-substituted acyl, or C 6-12 Fluorine-substituted alkoxyaryl (preferably C2-6 Fluorine-substituted alkyl; more preferably C 2-3 Fluorine-substituted alkyl; more preferably C3 fluorine-substituted alkyl). R b6 In the fluorine-substituted alkyl of the formula (I), all hydrogen atoms in the alkyl moiety are preferably substituted with fluorine atoms. b6 The alkyl portion of R is preferably methyl, ethyl, propyl, butyl, or pentyl (more preferably propyl, butyl, or pentyl; even more preferably butyl). b6 The alkyl portion of is preferably straight chain.

[0034] Specific examples of formula (BA2) are as follows: C4F9SO3 - , C3F7SO3 -

[0035] Equation (BA3) is as follows: [ka] Where: R b7 are each independently 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorine-substituted acyl, or C 6-12 Fluorine-substituted alkoxyaryl (preferably C 2-6 Fluorine-substituted alkyl). R b7 The alkyl portion of R is preferably methyl, ethyl, propyl, butyl, or pentyl (more preferably methyl, ethyl, or butyl; even more preferably butyl). b7 The alkyl portion of is preferably linear. Here, two R b7 may be bonded to each other to form a fluorine-substituted heterocyclic structure, in which case the heterocyclic ring may be a monocyclic or polycyclic ring, but is preferably a monocyclic structure having 5 to 8 members.

[0036] Specific examples of formula (BA3) are as follows: [ka]

[0037] Equation (BA4) is as follows: [ka] Where: R b8 is hydrogen, C 1-6 Alkyl, C 1-6 alkoxy, or hydroxy (preferably hydrogen, methyl, ethyl, methoxy, or hydroxy; more preferably hydrogen or hydroxy). L b is carbonyl, oxy or carbonyloxy (preferably carbonyl or carbonyloxy; more preferably carbonyl). Y b are each independently hydrogen or fluorine, and preferably at least one is fluorine. nb4 is an integer of 0 to 10, and is preferably 0. nb5 is an integer of 0 to 21, and is preferably 4, 5 or 6.

[0038] Specific examples of formula (BA4) are as follows: [ka]

[0039] B n- The anion is preferably selected from the group consisting of anions represented by formula (BA2) or (BA3) because it exerts a better effect. It is also preferable that the composition according to the present invention contains two kinds of deprotecting agents (B), each of which contains an anion represented by (BA2) and an anion represented by (BA3) as an anion.

[0040] Equation (B-2) is as follows. [ka] Where: R b9 is C 1-5 Fluorine-substituted alkyl (preferably C 1-4 more preferably, alkyl in which all hydrogens at C1 or C4 are replaced by fluorine). R b10 are each independently 3-10 alkenyl or alkynyl (wherein CH3- in the alkenyl and alkynyl may be replaced by phenyl, and -CH2- in the alkenyl and alkynyl may be replaced by at least one of -C(=O)-, -O- or phenylene); 2-10 Thioalkyl, C 5-10 A saturated heterocycle (preferably C 3-12 Alkenyl or alkynyl, C 3-5 Thioalkyl, C 5-6 More preferably, -C≡C-CH2-CH2-CH2-CH3, -CH=CH-C(=O)-O-tBu, -CH=CH-Ph, -S-CH(CH3)2, -CH=CH-Ph-O-CH(CH3)(CH2CH3) and piperidine). Here, tBu means t-butyl, and Ph means phenylene or phenyl. In the present invention, alkenyl means a monovalent group having one or more double bonds (preferably one). Similarly, alkynyl means a monovalent group having one or more triple bonds (preferably one). nb6 is 0, 1 or 2 (preferably 0 or 1; more preferably 0). In one preferred embodiment, nb6=1.

[0041] Specific examples of formula (B-2) include the following. [ka]

[0042] The molecular weight of the deprotecting agent (B) is preferably 400 to 2,500, and more preferably 400 to 1,500.

[0043] The deprotecting agent (B) may be one type or two or more types, and a combination of two types is also a preferred embodiment. The content of the deprotecting agent (B) is preferably 0.05 to 10% by mass (more preferably 0.1 to 5% by mass; even more preferably 0.5 to 2% by mass) based on the total mass of the (A) polymer. For clarity, when two types of deprotecting agents (B) are used in combination, the above content refers to the sum of the two types of deprotecting agents (B).

[0044] (C) Carboxylic acid compounds The composition according to the present invention is 4-12 The number of carbon atoms in the carboxylic acid compound (C) includes the carboxylic acid moiety. For example, fumaric acid corresponds to a C4 carboxylic acid compound (C). The carboxylic acid compound (C) is an unsaturated hydrocarbon containing one, two or three (preferably one or two) carboxy groups. The carboxylic acid compound (C) has a double bond or triple bond between carbon atoms, and preferably has at least one double bond between carbon atoms. The pKa1 (H2O) of the carboxylic acid compound (C) is preferably 1.00 to 6.00 (more preferably 1.80 to 3.50; even more preferably 2.25 to 2.90). For clarity, the pKa of the carboxylic acid compound (C) is the first stage (pKa1), and if there is only one pKa, it is used.

[0045] The composition according to the present invention contains a carboxylic acid compound (C), and thus the shape of the top of the resist pattern described below can be made to have a small hollow and a high rectangular shape. Without being bound by theory, it is believed that the unsaturated fatty acid contained in the carboxylic acid compound (C) is difficult to decompose due to heat during resist film formation or exposure, and has high acidity (low pKa1), which enables control of the pattern shape. Without being bound by theory, it is believed that the carboxylic acid compound (C) quenches amines derived from the environment, and prevents amines derived from the environment from inhibiting the action of an acid (e.g., derived from the deprotecting agent (B)) that changes the alkali solubility of the polymer (A). Without being bound by theory, it is believed that the molecular weight of the carboxylic acid compound (C) is small, so that it can be unevenly distributed near the film surface as the solvent evaporates during heating during film formation, and that it can quench environmental amines near the film surface, which tend to have a large effect.

[0046] In a preferred embodiment, the carboxylic acid compound (C) is an aromatic carboxylic acid (C-1) represented by formula (c-1) or an aliphatic carboxylic acid (C-2) represented by formula (c-2).

[0047] Equation (c-1) is as follows. [ka] Where: Ar 11 is C 5-10 Ar is an aromatic hydrocarbon ring having the formula: 11 is preferably benzene or naphthalene (more preferably benzene). R 11 is OH or NH2, preferably OH. n11 is 0 or 1 (preferably 1). n12 is 0, 1 or 2 (preferably 1).

[0048] Specific examples of the aromatic carboxylic acid (C-1) include benzoic acid, 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, and the like, with 2-hydroxybenzoic acid being preferred.

[0049] Equation (c-2) is as follows. [ka] Where: L 21 is -C=C- or -C≡C-, preferably -C=C-. L 22 is -C=C- or -C≡C-, preferably -C=C-. n21 is 0, 1, 2 or 3 (preferably 0 or 1; more preferably 0). n22 is 0 or 1, preferably 0. n23 is 0, 1, 2 or 3 (preferably 0 or 1; more preferably 0).

[0050] Specific examples of the aliphatic carboxylic acid (C-2) include fumaric acid and maleic acid, with fumaric acid being preferred.

[0051] The molecular weight of the carboxylic acid compound (C) is preferably 80-200, and more preferably 90-140.

[0052] The carboxylic acid compound (C) may be one type or two or more types. The content of the carboxylic acid compound (C) is preferably 0.01 to 5 mass% (more preferably 0.03 to 4 mass%; even more preferably 0.10 to 2 mass%; still more preferably 0.12 to 1.00 mass%) based on the polymer (A).

[0053] (D) Solvent The composition according to the present invention comprises a solvent (D). The solvent (D) comprises an organic solvent (D1). The content of the organic solvent (D1) is preferably 80 to 100 mass% (more preferably 95 to 100 mass%; even more preferably 98 to 100 mass%; still more preferably 100 mass%) based on the solvent (D).

[0054] The organic solvent (D1) is not particularly limited as long as it can dissolve each of the components to be mixed, and can be arbitrarily selected from those generally used in lithography. Specifically, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (hereinafter sometimes referred to as PGME) and propylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PGMEA) and propylene glycol monoethyl ether acetate; lactate esters such as methyl lactate and ethyl lactate (hereinafter sometimes referred to as EL); aromatic hydrocarbons such as toluene and xylene; amides such as N,N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone, etc. can be mentioned. These can be used alone or in a mixture of two or more kinds. In a preferred embodiment, the solvent (D) contains, as an organic solvent (D1), at least one selected from the group consisting of ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, lactate ester, aromatic hydrocarbon, amide, and lactone.

[0055] In relation to other layers or films, it is also one embodiment that the (D) solvent does not substantially contain water. For example, the amount of water in the (D) solvent as a whole is preferably 0.1 mass% or less, more preferably 0.01 mass% or less, and even more preferably 0.001 mass% or less. It is also one suitable embodiment that the (D) solvent does not contain water (0 mass%).

[0056] The content of the (D) solvent is preferably 50 to 80 mass % (more preferably 55 to 75 mass %; further preferably 60 to 70 mass %) based on the composition.

[0057] (E) Quencher The composition according to the present invention contains a quencher (E). The quencher (E) has the effect of suppressing the diffusion of the acid derived from the deprotecting agent (B) generated in the exposed area, and suppressing the deactivation of the acid on the resist film surface due to components such as amines contained in the air. Furthermore, the pH of the composition can be controlled by adjusting the amount of the quencher (E). The quencher (E) has a structure different from that of the carboxylic acid compound (C). The quencher (E) is preferably an amine compound (E1) or a carboxylate (E2). When the quencher (E) is a carboxylate (E2), it releases an acid upon irradiation with light, but the acid does not directly act on the polymer. In this respect, it is different from the deprotecting agent (B), which has a direct effect on the polymer by removing the protecting group of the polymer with the released acid.

[0058] Examples of the amine compound (E1) include (i) ammonia, (ii) Primary aliphatic amines having 1 to 16 carbon atoms and derivatives thereof, such as methylamine, ethylamine, isopropylamine, tert-butylamine, cyclohexylamine, ethylenediamine, tetraethylenediamine, etc. (iii) Secondary aliphatic amines having 2 to 32 carbon atoms and derivatives thereof, such as dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, N,N-dimethylmethylenediamine, etc. (iv) Tertiary aliphatic amines having 3 to 48 carbon atoms and derivatives thereof, such as trimethylamine, triethylamine, dimethylethylamine, tricyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, tris[2-(dimethylamino)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, etc. (v) Aromatic amines having 6 to 30 carbon atoms and their derivatives, such as aniline, benzylamine, naphthylamine, N-methylaniline, 2-methylaniline, 4-aminobenzoic acid, phenylalanine, etc. (vi) Heterocyclic amines having 5 to 30 carbon atoms and derivatives thereof, such as pyrrole, oxazole, thiazole, imidazole, 4-methylimidazole, pyridine, methylpyridine, butylpyridine, etc. Examples include: As the amine compound (E1), (iv) is a preferred form. In (iv), tris[2-(2-methoxyethoxy)ethyl] is a preferred form.

[0059] The molecular weight of the amine compound (E1) is preferably 17-500, and more preferably 60-400. The base dissociation constant pKb(H2O) of the amine compound (E1) is preferably -12 to 5, and more preferably 1 to 4.

[0060] The carboxylate (E2) releases an acid having an acid dissociation constant pKa(H2O) of preferably 1.5 to 8, more preferably 1.5 to 5, upon exposure to light. In a preferred embodiment, the carboxylate (E2) is represented by the formula (e-2). C m+ Cation C m- Anion Formula (e-2) It is expressed as: Where: C m+The cation is composed of at least one cation selected from the group consisting of cations represented by formulae (EC1) and (EC2), and has a valency of m (wherein m is 1 to 3) as a whole; C m- The anions consist of at least one anion represented by formula (EA) and have a valency of m as a whole. The m-valent is preferably monovalent or divalent, and more preferably monovalent.

[0061] Equation (EC1) is as follows: [ka] Where: R e1 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 It is aryl (preferably methyl, ethyl, t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy; more preferably t-butyl, methoxy, ethoxy, phenylthio, phenyloxy; even more preferably t-butyl or methoxy). Each ne1 is independently 0, 1, 2, or 3. When all ne1s are 1 and all R e1 In another preferred embodiment, n1 is equal to n2. In another preferred embodiment, n1 is 0.

[0062] Specific examples of formula (EC1) are as follows: [ka]

[0063] Equation (EC2) is as follows: [ka] Where: R e2 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12Aryl (preferably R e2 is C 4-6 More preferably, R is t-butyl or 1,1-dimethylpropyl; and even more preferably, R is t-butyl. e2 may be the same or different, and it is more preferable that they are the same. Each ne2 is independently 0, 1, 2 or 3, and preferably 1.

[0064] Specific examples of formula (EC2) are as follows: [ka]

[0065] The formula (EA) is as follows: [ka] Where: X is C 1-20 It may be linear, branched or cyclic, but is preferably linear or cyclic. 1-4 It is preferable that 1-2 ), preferably has one double bond in the chain or is saturated. If it is cyclic, it may be an aromatic monocyclic ring or a saturated monocyclic or polycyclic ring, if it is a monocyclic ring, it is preferably a six-membered ring, and if it is a polycyclic ring, it is preferably an adamantane ring. X is preferably methyl, ethyl, propyl, butyl, ethane, phenyl, cyclohexane, or adamantane (more preferably methyl, phenyl, or cyclohexane; even more preferably phenyl). R e3 are each independently OH, C 1-6 Alkyl, or C 6-10 It is aryl (preferably OH, methyl, ethyl, 1-propyl, 2-propyl, t-butyl, or phenyl; more preferably OH). ne3 is 1, 2 or 3 (preferably 1 or 2; more preferably 1). ne4 is 0, 1 or 2 (preferably 0 or 1; more preferably 1).

[0066] Specific examples of formula (EA) are as follows: [ka]

[0067] The molecular weight of the carboxylate (E2) is preferably 300 to 1,400, and more preferably 300 to 1,200.

[0068] The quencher (E) may be of one type or of two or more types. The content of the quencher (E) is preferably from 0.001 to 5% by mass (more preferably from 0.05 to 2% by mass; further preferably from 0.01 to 1% by mass) based on the polymer (A).

[0069] (F) Surfactant The composition according to the present invention may contain a surfactant (F). The surfactant (F) can improve the applicability of the composition. Examples of the surfactant (F) include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0070] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; acetylene glycol derivatives such as polyoxyethylene fatty acid diesters, polyoxy fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, acetylene alcohol, acetylene glycol, polyethoxylates of acetylene alcohol, and polyethoxylates of acetylene glycol; fluorine-containing surfactants such as Fluorad (trade name, Sumitomo 3M), Megafac (trade name, DIC), and Sulfuron (trade name, Asahi Glass); and organic siloxane surfactants such as KF-53 (trade name, Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0071] Examples of the anionic surfactant include ammonium salts or organic amine salts of alkyldiphenyl ether disulfonic acids, ammonium salts or organic amine salts of alkyldiphenyl ether sulfonic acids, ammonium salts or organic amine salts of alkylbenzene sulfonic acids, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfates, and ammonium salts or organic amine salts of alkyl sulfates.

[0072] Further, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauric acid amidopropyl hydroxysulfone betaine, and the like.

[0073] The surfactant (F) can be used alone or in combination of two or more kinds. The content of the surfactant (F) is preferably from 0.01 to 5 mass %, more preferably from 0.05 to 1 mass %, based on the polymer (A).

[0074] (G) Additives The composition according to the present invention may contain an additive (G) other than (A) to (F). The additive (G) is preferably at least one selected from the group consisting of a surface smoothing agent, a plasticizer, a dye, a contrast enhancing agent, an acid, a base, a radical generator, a substrate adhesion enhancing agent, and an antifoaming agent. The content of the additive (G) is preferably 0.01 to 10 mass %, more preferably 0.1 to 2 mass %, based on the polymer (A). A preferred embodiment of the composition according to the present invention is one in which no additive (G) is contained (0 mass %).

[0075] Method for producing resist film The method for producing a resist film according to the present invention comprises the following steps: (1) applying a composition according to the present invention over a substrate; (2) The composition is heated to form a resist film having a thickness of 0.8 to 20 μm. The present invention relates to a method for producing a semiconductor device comprising the steps of: An embodiment of the manufacturing method according to the present invention will now be described.

[0076] Process (1) The composition according to the present invention is applied by a suitable method above a substrate (e.g., silicon / silicon dioxide coated substrate, silicon nitride substrate, silicon wafer substrate, glass substrate, ITO substrate, etc.). Here, in the present invention, above includes the case where it is formed directly above and the case where it is formed via another layer. For example, a planarizing film or resist underlayer film may be formed directly above the substrate, and the composition according to the present invention may be applied directly above it. It is more preferable to apply the composition according to the present invention directly above the substrate (without via another layer). The application method is not particularly limited, and examples include coating methods using a spinner or coater.

[0077] Process (2) After application of the composition, the composition is heated to form a resist film having a thickness of 0.8 to 20 μm. The heating in (2) is performed, for example, by using a hot plate. The heating temperature is preferably 100 to 250° C. (more preferably 100 to 200° C.; further preferably 100 to 160° C.). The temperature here refers to the heating atmosphere, for example, the heating surface temperature of a hot plate. The heating time is preferably 30 to 300 seconds (more preferably 60 to 240 seconds). The heating is preferably performed in air or nitrogen gas atmosphere. The thickness of the resist film is selected depending on the purpose, but when the composition according to the present invention is used, a pattern with a better shape can be formed when a thick coating film is formed. Therefore, the thickness of the resist film is preferably thick, and is preferably 1 to 20 μm (more preferably 2 to 15 μm; even more preferably 7 to 15 μm; even more preferably 9 to 12 μm).

[0078] In addition, the following process (3) Exposing the resist film; (4) Develop the resist film A resist pattern can be produced by a method comprising the steps of: (1) and (2) are carried out before the step (3) for clarity. The numbers in parentheses indicating the steps indicate the order. The same applies hereinafter.

[0079] Process (3) The resist film is exposed through a predetermined mask. The wavelength of light used for exposure is not particularly limited, but it is preferable to expose with light having a wavelength of 13.5 to 248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), extreme ultraviolet light (wavelength 13.5 nm), etc. can be used, and KrF excimer laser is preferable. These wavelengths allow a range of ±1%. After exposure, post exposure bake (PEB) can also be performed as necessary. The temperature of post exposure bake is preferably 80 to 150°C, more preferably 100 to 140°C, and the heating time is 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0080] Process (4) The exposed resist film is developed using a developer. As the development method, a method conventionally used for developing photoresists, such as a paddle development method, an immersion development method, and a swing immersion development method, can be used. As the developer, an aqueous solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium silicate, an organic amine such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, or triethylamine, or a quaternary amine such as tetramethylammonium hydroxide (TMAH), is used, and preferably a 2.38 mass % TMAH aqueous solution. A surfactant can also be added to the developer. The temperature of the developer is preferably 5 to 50°C, more preferably 25 to 40°C, and the development time is preferably 10 to 300 seconds, more preferably 30 to 60 seconds. After development, water washing or rinsing treatment can be performed as necessary. When a positive resist composition is used, the exposed portion is removed by development to form a resist pattern. This resist pattern can be further fined by using, for example, a shrink material.

[0081] When a thick-film resist pattern is formed using a chemically amplified resist, particularly when the aspect ratio is high, hollows may form at the top of the walls of the resist pattern (the details of the hollows will be explained using figures in the examples). In a preferred embodiment, the distance between the perpendicular line from the end point of the top of the resist pattern to the substrate and the perpendicular line from the most recessed point of the side surface of the resist pattern to the substrate (hereinafter sometimes referred to as the recess width) is 50 nm or less (more preferably 0 to 45 nm; even more preferably 0 to 20 nm; even more preferably 0 to 1 nm). In the present invention, the recess can be suppressed, and a pattern with high rectangularity can be formed. By suppressing the recessed portion, the resistance of the pattern can be strengthened in the subsequent process, which is advantageous.

[0082] In addition, the following process (5) Processing using the resist pattern as a mask A processed substrate can be produced by the method comprising the steps of: In one embodiment of the present invention, it is preferable that no metal (e.g., plating) is applied to the spaces (grooves) between the resist patterns. In other words, it is preferable that no metal (e.g., plating) is filled between the resist patterns.

[0083] Process (5) The formed resist pattern is preferably used to process an underlayer film or a substrate (more preferably a substrate). Specifically, various substrates serving as the base can be processed using the resist pattern as a mask by dry etching, wet etching, ion implantation, metal plating, or the like. It is more preferable to etch the substrate by dry etching using the resist pattern of the present invention as a mask. The resist pattern according to the present invention can be thickened, and therefore can also be used for substrate processing using ion implantation. When processing the underlayer film using a resist pattern, the processing may be performed in stages. For example, the BARC layer may be processed using a resist pattern, the SOC film may be processed using the BARC pattern, and the substrate may be processed using the SOC pattern.

[0084] Thereafter, if necessary, the substrate is further processed, and preferably a step of forming wiring on the processed substrate is carried out to manufacture a device. These processes can be carried out by applying known methods. If necessary, the substrate is cut into chips, connected to a lead frame, and packaged with resin. In the present invention, this packaged product is called a device. Examples of devices include semiconductor elements, liquid crystal display elements, organic EL display elements, plasma display elements, and solar cell elements, and preferably semiconductor elements.

[0085] By using the thick film resist composition of the present invention, it is possible to control the pattern shape of the resist pattern to be formed. Therefore, from another aspect, the present invention provides the following method. A method for controlling the pattern shape by forming a resist pattern using the thick film resist composition of the present invention. A method for controlling (preferably reducing) the embedding width of a resist pattern by forming a resist pattern using the thick film resist composition of the present invention. A method for controlling the bite width of a resist pattern to 50 nm or less by forming a resist pattern using the thick film resist composition of the present invention. The details of the thick-film resist composition in the above method are as described above. Also, the details of the methods for producing the resist film, resist pattern, processed substrate, and device are as described above. EXAMPLES

[0086] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0087] Preparation of Composition 1 PGME and PGMEA are mixed in a mass ratio of 70:30 (=PGME:PGMEA) to obtain a mixed solvent. Polymer A1 (33.451 parts by mass), deprotection agent B1 (0.067 parts by mass), deprotection agent B2 (0.375 parts by mass), quencher E1 (0.007 parts by mass), carboxylic acid compound C1 (0.05 parts by mass), and surfactant F1 (0.051 parts by mass) are added to this mixed solvent (66.0 parts by mass), and the mixture is stirred at room temperature for 30 minutes to obtain a solution. It is visually confirmed that each component is completely dissolved. The obtained solution is filtered through a 0.05 μm filter to obtain composition 1. Polymer A1: p-hydroxystyrene / styrene / t-butyl acrylate copolymer (Mw=20,000, random copolymer) [ka] Deprotection agent B1: The following compound (GOKYO FOOD & CHEMICAL) [ka] Deprotection agent B2: The following compound (GOKYO FOOD & CHEMICAL) [ka] Carboxylic acid compound C1: 2-hydroxybenzoic acid · Quencher E1: Tris[2-(2-methoxyethoxy)ethyl]amine Surfactant F1: MEGAFAC R-2011 (DIC)

[0088] Preparation of Compositions 2 to 5 and Comparative Compositions 1 to 5 Compositions 2 to 5 and comparative compositions 1 to 5 are prepared in the same manner as composition 1 above, except that the carboxylic acid compound C1 is a compound shown in Table 1 and the amount of the compound added is changed so that the molar ratio to polymer A1 is the same as that of composition 1. In Table 1, the pKa1 of each carboxylic acid compound is shown in parentheses next to the compound, and the evaluation of the top of the pattern is shown based on the measured value and the criteria described below. [Table 1]

[0089] Example of resist pattern formation Using a coater developer Mark8 (Tokyo Electron), the composition prepared above is dropped onto an 8 cm Si wafer and spin-coated. This wafer is heated at 140°C for 90 seconds using a hot plate under atmospheric conditions to form a resist film. The thickness of the resist film at this point is measured using an optical interference film thickness measuring device M-1210 (SCREEN) to be 10.5 μm. The resist film is exposed using a KrF stepper FPA3000-EX5 (Canon). The exposed wafer is heated (PEB) at 110°C for 90 seconds using a hot plate under atmospheric conditions. The resist film is then paddle developed in a 2.38% by mass TMAH aqueous solution for 60 seconds, washed with DIW, and spin-dried at 1,000 rpm. This forms a trench pattern with a line width of 15 μm, a space width of 3 μm, and a top width of 9 μm. The line width and space width are measured at the bottom of the pattern. This pattern shape is shown diagrammatically in Figure 1. A resist pattern 12 is formed on a substrate 11, and the line width 13, space width 14, and top width 15 are as shown in Figure 1. Figure 2 is a schematic enlarged view of a pattern wall top 16, which will be described later. The exposure energy (mJ / cm) used to obtain a pattern of this shape 2 When Composition 1 is used, the sensitivity is 108 (mJ / cm 2 The sensitivity of compositions 2 to 5 is shown in Table 2. The sensitivity here refers to the sensitivity of the initial composition described below.

[0090] Pattern wall top evaluation A slice of the sample created in the resist pattern formation example is prepared, and the vertical cross section of the pattern is observed with a scanning electron microscope (SEM). The degree to which the pattern is hollowed out inward from the top (digging-in width) is evaluated. A specific explanation is given using Figure 2. Figure 2 shows a schematic of a wall top 21. A line is drawn perpendicular to the substrate from the end point of the top of the pattern. A line is drawn perpendicular to the substrate from the most hollowed-out point on the side of the pattern. The distance between each line is the embedding width. The evaluation criteria are as follows: A: The bite width is less than 1 nm B: The bite width is 1 to 50 nm. C: The bite width is greater than 50 nm. The evaluation results are shown in Table 1.

[0091] Evaluation of stability over time Immediately after preparing each composition, a trench pattern with a line width of 15 μm, a space width of 3 μm, and a top width of 9 μm is formed in the same manner as in the above-mentioned resist pattern formation example, and the sensitivity is measured. This is defined as the sensitivity of the initial composition. Each composition is stored at 40°C for 30 days. Using these, a trench pattern with a line width of 15 μm, a space width of 3 μm, and a top width of 9 μm is formed in the same manner as in the resist pattern formation example, and the sensitivity is measured. This is the sensitivity of the composition over time. The stability over time is evaluated by calculating (sensitivity of aged composition) / (sensitivity of initial composition). The evaluation criteria are as follows: Stable: Sensitivity changes less than 10% Unstable: Sensitivity changes by 10% or more The evaluation results are shown in Table 2.

[0092] Film loss evaluation Using a coater developer Mark8, the composition is dropped onto an 8 cm Si wafer and spin-coated. This wafer is heated at 140°C for 90 seconds using a hot plate under atmospheric conditions to form a resist film. The thickness of the resist film at this point is measured using an M-1210 and this is the initial film thickness. The resist film is formed as described above, and then exposed using a KrF stepper FPA3000-EX5. The wafer is subjected to PEB at 110°C for 90 seconds using a hot plate under atmospheric conditions. The resist film is developed for 60 seconds using a 2.38% by mass TMAH aqueous solution. This forms a trench pattern with a line width of 15 μm and a space width of 3 μm. The wafer is spin-dried at 1,000 rpm. The thickness of the resist film at this point is measured using an M-1210, and this is taken as the post-exposure film thickness. If the film thickness after exposure / initial film thickness<99%, it is evaluated as no film loss, and if the film thickness after exposure / initial film thickness≧99%, it is evaluated as having film loss. The evaluation results are shown in Table 2.

[0093] Exposure tolerance (EL) evaluation A composition not containing a carboxylic acid compound (C) is prepared as a control, and a trench pattern with a line width of 15 μm, a space width of 3 μm, and a top width of 9 μm is formed in the same manner as in the above-mentioned resist pattern formation example, and the sensitivity is measured (this sensitivity is called the reference sensitivity). A trench pattern is formed with a space width of ±2% (i.e., 2.94 to 3.06 μm) using a composition containing a carboxylic acid compound (C) shown in Table 2 in the same manner as in the above-mentioned resist pattern formation example, the sensitivity is measured, and the change in sensitivity is calculated. EL = Sensitivity change / Reference sensitivity x 100 The EL of each composition is calculated as follows: The results are shown in Table 2.

[0094] Peeling evaluation A resist pattern is formed in the same manner as in the above resist pattern formation example, except that a trench pattern with a line width of 15 μm and a space width of 20 μm is formed. The interface between the Si wafer and the resist wall is observed with a CD-SEM at a magnification of 50K. If peeling is confirmed, it is evaluated as present, and if not, it is evaluated as absent. The evaluation results are shown in Table 2. [Table 2]

[0095] Preparation of Composition 21 PGME and PGMEA are mixed in a mass ratio of 70:30 (=PGME:PGMEA) to obtain a mixed solvent. Polymer A1 (33.447 parts by mass), deprotection agent B1 (0.067 parts by mass), deprotection agent B2 (0.375 parts by mass), quencher E1 (0.01 parts by mass), and surfactant F1 (0.051 parts by mass) are added to this mixed solvent (66.0 parts by mass). Carboxylic acid compound C1 (2-hydroxybenzoic acid) is added to this in an amount of 0.015% by mass relative to polymer A1, and the mixture is stirred at room temperature for 30 minutes to obtain a solution. It is visually confirmed that each component is completely dissolved. The obtained solution is filtered through a 0.05 μm filter to obtain composition 21.

[0096] Preparation of compositions 22 to 26 Compositions 22 to 26 are obtained in the same manner as in the preparation of composition 21, except that the amount of carboxylic acid compound C1 added is changed as shown in Table 3. [Table 3]

[0097] Formation of resist patterns and evaluation of pattern wall tops A resist pattern is formed in the same manner as above to form a trench pattern with a line width of 15 μm and a space width of 3 μm. The sensitivity of each pattern is shown in Table 3. The top of the pattern wall is also evaluated in the same manner, and the evaluation results are shown in Table 3.

[0098] Preparation of composition 31 Composition 31 is obtained in the same manner as in the preparation of composition 21, except that the carboxylic acid compound C1 is changed to fumaric acid and the amount added is changed to 0.0126% by mass with respect to the polymer A1. In Example 21 (0.015% by mass of 2-hydroxybenzoic acid relative to polymer A) and Example 31 (0.126% by mass of fumaric acid relative to polymer A), the amount of carboxylic acid compound C added to each composition was equimolar.

[0099] Preparation of compositions 32 to 36 Compositions 32 to 36 are obtained by carrying out the same preparation as composition 31, except that the amount of fumaric acid added is changed as shown in Table 4. [Table 4]

[0100] Formation of resist patterns and evaluation of pattern wall tops A resist pattern is formed in the same manner as above to form a trench pattern with a line width of 15 μm and a space width of 3 μm. The sensitivity of each pattern is shown in Table 4. The top of the pattern wall is also evaluated in the same manner, and the evaluation results are shown in Table 4. [Explanation of symbols]

[0101] 11. Substrate 12. Resist pattern 13. Line Width 14.Space width 15.Top width 16. Pattern wall top 21. Wall top 22.Bite width

Claims

1. Polymer (A), deprotecting agent (B), carboxylic acid compound (C) of C ４－１２ and a thick film resist composition comprising a solvent (D); Here The resist film formed from the thick film resist composition has a film thickness of 0.8 to 20 μm, The carboxylic acid compound (C) is an unsaturated hydrocarbon containing 1, 2 or 3 carboxy groups, The solvent (D) comprises an organic solvent (D1).

2. The composition according to claim 1, wherein the carboxylic acid compound (C) is an aromatic carboxylic acid (C-1) represented by formula (c-1) or an aliphatic carboxylic acid (C-2) represented by formula (c-2). 【Chemical 1】 (Here Ar １１ is an aromatic hydrocarbon ring of C ５－１０ and R １１ is OH or NH ２ and n11 is 0 or 1, and n12 is 0, 1 or 2) 【Chemical Formula 2】 (Here L ２１ is -C=C- or -C≡C-, L ２２ is -C=C- or -C≡C-, n21 is 0, 1, 2 or 3, n22 is 0 or 1, and n23 is 0, 1, 2 or 3)

3. The composition according to claim 1, further comprising a quencher (E).

4. The pKa1 (H ２ O) of the carboxylic acid compound (C) is from 1.00 to 6.00, and the composition according to claim 1.

5. The composition according to claim 1, wherein the solvent (D) is selected from the group consisting of ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, lactate ester, aromatic hydrocarbon, amide, and lactone.

6. The composition according to claim 1, wherein the polymer (A) comprises a repeating unit selected from the group consisting of repeating units represented by formula (P-1), (P-2), (P-3) and (P-4). 【Chemical Formula 3】 (Here R ｐ１ , R ｐ３ , R ｐ６ and R ｐ８ are each independently hydrogen or C １－４ is alkyl, R ｐ２ and R ｐ４ each independently represents a linear, branched or cyclic C ３－１５ alkyl (wherein the alkyl may be substituted by fluorine, and -CH ２ - in the alkyl may be replaced by -O-), T １ and T ２ are each independently a single bond or a linking group of C １－１２ and are R ｐ５ 、 R ｐ７ and R ｐ９ are each independently C １－５ alkyl (wherein -CH ２ - in the alkyl may be replaced by -O-), and x1 is 1 to 3, x2, x3 and x5 are each independently 0 to 2, x4 is 1 to 2)

7. The composition according to claim 1, wherein the deprotecting agent (B) is represented by formula (B-1) or formula (B-2). B ｎ＋ Cation B ｎ－ Anion (B-1) (Here B ｎ＋ The cation is a cation represented by formula (BC1): 【Chemical Formula 4】 (Here R ｂ１ is, independently of each other, C １－６ alkyl, C １－６ alkoxy, C ６－１２ aryl, C ６－１２ arylthio, or C ６－１２ aryloxy, and nb1 is each independently 0, 1, 2 or 3), The cation represented by formula (BC2): 【Chemical Formula 5】 (Here R ｂ２ is, independently of one another, C １－６ alkyl, C １－６ alkoxy, or C ６－１２ aryl, and nb2 is each independently 0, 1, 2 or 3), and The cation represented by formula (BC3): ​ (Here R ｂ３ is, independently of each other, C １－６ alkyl, C １－６ alkoxy, or C ６－１２ aryl, and R ｂ４ is, independently of one another, C １－６ alkyl and nb3 is each independently 0, 1, 2 or 3) Consisting of at least one cation selected from the group consisting of; and having an overall n-valence (here, n is 1 to 3); B ｎ－ The anion is an anion represented by formula (BA1): 【Chemical Formula 7】 (Here, R ｂ５ is, independently of one another, C １－６ fluorine-substituted alkyl, or C １－６ alkyl), The anion represented by formula (BA2): [Chemical 8] (Here, R ｂ６ is C １－６ fluorine-substituted alkyl, C １－６ fluorine-substituted alkoxy, C ６－１２ fluorine-substituted aryl, C ２－１２ fluorine-substituted acyl, or C ６－１２ fluorine-substituted alkoxyaryl). The anion represented by formula (BA3): 【Chemical Formula 9】 (Here, each R ｂ７ is independently a C １－６ fluorine-substituted alkyl, C １－６ fluorine-substituted alkoxy, C ６－１２ fluorine-substituted aryl, C ２－１２ fluorine-substituted acyl, or C ６－１２ fluorine-substituted alkoxyaryl, and where two R ｂ７ may be bonded to each other to form a fluorine-substituted heterocyclic structure), and The anion represented by formula (BA4): 【Chemical Formula 10】 (Here R ｂ８ is hydrogen, C １－６ alkyl, C １－６ alkoxy, or hydroxy, and L ｂ is carbonyl, oxy or carbonyloxy, Y ｂ each independently is hydrogen or fluorine, nb4 is an integer from 0 to 10, and nb5 is an integer from 0 to 21) Consisting of at least one anion selected from the group consisting of; and having an overall n-valence) 【Chemical 11】 (Here R ｂ９ is a C １－５ fluorine-substituted alkyl, and R ｂ１０ is, independently of each other, C ３－１０ alkenyl or alkynyl (wherein CH in alkenyl and alkynyl ３ - may be substituted by phenyl, and -CH in alkenyl and alkynyl ２ - may be replaced by at least one of -C(=O)-, -O- or phenylene), C ２－１０ thioalkyl, C ５－１０ is a saturated heterocyclic ring, nb6 is 0, 1, or 2)

8. The composition according to claim 1, further comprising a surfactant (F).

9. The content of the polymer (A) is 20 to 45% by mass based on the composition, The content of the carboxylic acid compound (C) is 0.01 to 5% by mass based on the polymer (A), the composition according to claim 1.

10. The composition according to claim 1, which is a thick film chemically amplified resist composition.

11. A method for manufacturing a resist film, comprising the following steps. (1) Applying the composition according to at least one of claims 1 to 10 above the substrate; (2) Heating the composition to form a resist film with a film thickness of 0.8 to 20 μm.

12. A method for manufacturing a resist pattern, comprising the following steps. Forming a resist film by the method according to claim 11; (3) Exposing the resist film; (4) Developing the resist film.

13. The method for manufacturing a resist pattern according to claim 12, wherein the distance between the perpendicular line from the endpoint at the top of the resist pattern to the substrate and the perpendicular line from the most concave point on the side surface of the resist pattern to the substrate is 50 nm or less.

14. A method for manufacturing a processed substrate, comprising the following steps. Forming a resist pattern by the method according to claim 12; (5) Processing using the resist pattern as a mask.

15. A method for manufacturing a device, comprising the method according to claim 11.

Images