Thick-film photoresist composition and method for manufacturing photoresist films using the same.

Abstract

The objective is to provide a thick-film photoresist composition capable of forming highly rectangular photoresist patterns. The solution is a thick-film photoresist composition comprising 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 photoresist composition used in the manufacture of semiconductor elements or semiconductor integrated circuits, and a method for manufacturing a photoresist film using the same. [Previous Technology]

[0002] In the manufacturing process of semiconductor devices, microfabrication using photoresist lithography is generally performed. The microfabrication steps include forming a thin photoresist 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 with active light such as ultraviolet light through the mask pattern, developing the exposed layer to obtain the photoresist pattern, using the obtained photoresist pattern as a protective film, and etching the substrate to form micro-protrusions corresponding to the above pattern.

[0003] Miniaturization of photoresist patterns is required. On the other hand, to cope with high-energy ion implantation, photoresist patterns with high aspect ratios are required. When forming thick-film photoresist patterns, the required properties of the composition or the process conditions are different from those of thin films. Therefore, when thick-film photoresist compositions are formed by simply adjusting the viscosity of the thin film photoresist composition, it is impossible to form the required shape, which presents unique difficulties. The purpose of Patent Document 1 is to obtain a composition that forms a pattern with a cross-sectional shape close to a rectangle even when it is a thick film, and to examine a composition containing a chemically amplified polymer and multiple acid generating agents. In order to have resistance to subsequent steps such as ion implantation or etching, the shape of the top of the photoresist pattern becomes important, and it is still required to form a photoresist composition with the desired shape.

[0004] For thin-film photoresist, the addition of organic acids is examined to improve development defects or the shape of the photoresist pattern. For example, Patent Document 2 examines the addition of maleic acid and the like to a thin-film photoresist composition with a film thickness of approximately 0.2 μm. Patent Document 3 examines the use of photoresist patterns to obtain well-shaped thick films for creating magnetic film patterns in magnetic memory media. [Prior Art Documents] [Patent Documents]

[0005] Patent Document 1: Japanese Patent Application Publication No. 2018-109701; Patent Document 2: Japanese Patent Application Publication No. 2006-106693; Patent Document 3: Japanese Patent Application Publication No. 2007-206425 [Summary of the Invention]

[0006] [The problem that the invention aims to solve]

[0007] The inventors of this invention, regarding thick-film photoresist compositions and their use, believe that there are still more than one problem requiring improvement. These problems include, for example, the following: Inability to form a thick-film photoresist film. Insufficient rectangularity of the photoresist pattern. Recessed shape at the top of the photoresist pattern walls. Poor shape near the top of the pattern. Problems such as pattern damage occurring during the post-development process. Using a thick-film photoresist pattern as a mask, the substrate is not processed according to the intended purpose due to pattern damage during substrate processing. High number of defects. Insufficient sensitivity obtained from thick-film photoresist films. Poor stability over time. Decreasing film thickness of the photoresist film. The photoresist film or photoresist pattern is not heat-resistant. Small exposure margin. The photoresist pattern peels off from the substrate. This invention was made based on the above-described technical background, providing a thick-film photoresist composition and a method for manufacturing a photoresist film using the same. [Means for Solving the Problems]

[0008] The thick film photoresist composition of the present invention comprises a polymer (A), a deprotecting agent (B), a C4-12 carboxylic acid compound (C), and a solvent (D), wherein the photoresist film formed by the thick film photoresist 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 carboxyl groups, and the solvent (D) is an organic solvent (D1).

[0009] Furthermore, the method for manufacturing the photoresist film of the present invention comprises the following steps: (1) applying the above-mentioned composition onto a substrate; (2) heating the above-mentioned composition to form a photoresist film with a thickness of 0.8 to 20 μm. [Effects of the Invention]

[0010] By using the thick-film photoresist composition of the present invention, one or more of the following effects are expected: A thick-film photoresist film is formed. A photoresist pattern with high rectangularity can be formed. The recessed shape at the top of the photoresist pattern walls can be reduced. The shape near the top of the pattern can be optimized. A photoresist pattern with high resistance can be obtained in post-development processes (e.g., etching). A substrate can be processed using the thick-film photoresist pattern as a mask. The number of defects can be reduced. Good sensitivity can be obtained even with a thick-film photoresist film. Good stability over time. The reduction in the thickness of the photoresist film can be suppressed. The photoresist film or photoresist pattern has high heat resistance. The exposure margin can be increased. The photoresist pattern can be prevented from peeling off from the substrate.

Implementation Method

[0012] [Form of the invention]

[0013] [Definitions] In this specification, unless otherwise specified, the definitions or examples set forth in the paragraph shall apply. The singular form includes the plural form, and "one" or "it" means "at least one". Certain conceptual elements can be expressed by a plurality, and when their quantity is stated (e.g., mass% or mol%), the quantity means the sum of those plurality. "And / or" includes all combinations of elements and also includes the use of elements. When "~" or "-" is used to indicate a numerical range, these include both endpoints and the unit is common. For example, 5 to 25 mol% means more than 5 mol% and less than 25 mol%. The descriptions of "Cx-y", "Cx~Cy", and "Cx" refer to the number of carbons in a molecule or substituent. For example, C1-6 alkyl means an alkyl chain having more than one and less than six carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has a plurality of repeating units, these repeating units are copolymerized. Such copolymerization can be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, the n or m, etc., listed in parentheses indicate the number of repeating units. Temperature units are in Celsius. For example, 20 degrees means 20 degrees Celsius. Additives refer to the compound itself that performs its function (e.g., if it is a base-generating agent, it is the compound that generates the base). The compound may also be dissolved or dispersed in a solvent and added to the composition. As one aspect of the invention, such a solvent is preferably included in the composition of the invention as solvent (D) or other components.

[0014] Hereinafter, embodiments of the present invention will be described in detail.

[0015] Thick-film photoresist composition The thick-film photoresist composition of the present invention (hereinafter also referred to as the composition) comprises a polymer (A), a deprotecting agent (B), a C4-12 carboxylic acid compound (C), and a solvent (D). The carboxylic acid compound (C) is an unsaturated hydrocarbon comprising 1, 2, or 3 carboxyl groups, and the solvent (D) comprises an organic solvent (D1). The term "thick-film photoresist composition" refers to a photoresist composition capable of forming a thick-film photoresist film. In the present invention, the thickness of the photoresist film formed by the thick-film photoresist composition is 0.8–20 μm (preferably 1–20 μm; more preferably 2–15 μm; even more preferably 7–15 μm; even more preferably 9–12 μm). The viscosity of the composition of the present invention is preferably 250–400 cP (more preferably 280–380 cP; even more preferably 300–350 cP). Here, the viscosity is measured using a capillary viscometer at 25°C. The composition of this invention is preferably a thick-film KrF chemically amplified photoresist composition or a thick-film positively amplified photoresist composition, more preferably a thick-film KrF positively amplified photoresist composition. Here, the term KrF used in the above-described suitable examples refers to the use of a KrF excimer laser when exposing the photoresist film formed from the photoresist composition.

[0016] (A) Polymer The composition of this invention comprises polymer (A). The polymer (A) used in this invention is one whose solubility in an alkaline aqueous solution increases upon reaction with an acid. Such a polymer, for example, has acid groups protected by a protecting group; if an acid is added externally, the protecting group is removed, and the solubility in the alkaline aqueous solution increases. Such a polymer can be arbitrarily selected from those commonly used in lithography.

[0017] Polymer (A) is preferably a repeating unit comprising a group of repeating units selected from the group consisting of repeating units represented by formulas (P-1), (P-2), (P-3), and (P-4). In these formulas, Rp1, Rp3, Rp6, and Rp8 are each independently hydrogen or a C1-4 alkyl group (preferably hydrogen or methyl; more preferably hydrogen). Rp2 and Rp4 are each independently a straight-chain, branched, or cyclic C3-15 alkyl group (here, the alkyl group may be fluorinated, and the -CH2- in the alkyl group may be substituted with -O-). Here, the aforementioned "fluorinated alkyl group" means that the H present in the alkyl group is substituted with F. This means that all or part of the H present in the aforementioned fluorinated alkyl group is substituted with F, or may be completely substituted. In one embodiment of the invention, Rp2 and Rp4 are not fluorinated. Furthermore, in one embodiment of the invention, the -CH2- in the alkyl groups of Rp2 and Rp4 is not substituted with -O-. Rp2 is preferably methyl, isopropyl, tributyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl, or ethyladamantyl (Rp2 is more preferably branched or cyclic; particularly preferably tributyl, ethylcyclopentyl, ethylcyclohexyl, or ethyladamantyl; even more preferably tributyl). Rp4 is preferably C3-10 (more preferably C3-8; particularly preferably C3-5; even more preferably tributyl). T1 and T2 are each independently a single bond or a C1-12 linker (preferably a single bond). As the C1-12 linker of T1 or T2, each can be independently an enylalkyl group, -COO-Rt-, -O-Rt-, or a combination of any two or more of these, preferably -COO-Rt-. Rt is an alkyl or cycloalkyl group (preferably C1-5 alkyl; especially -CH2-, -(CH2)2-, or -(CH2)3-). Rp5, Rp7, and Rp9 are each independently a C1-5 alkyl group (here, the -CH2- in the alkyl group can be replaced by -O-), preferably methyl or tributyl, more preferably methyl. In one embodiment of the invention, the -CH2- in the alkyl group of Rp5, Rp7, and Rp9 can be replaced by -O-. x1 is 1 to 3 (preferably 1, 2, or 3; more preferably 1). x2, x3, and x5 are each independently 0 to 2 (preferably 0, 1, or 2; more preferably 0). x4 is 1 to 2 (preferably 0 or 1; more preferably 1).

[0018] Since these repeating units can be appropriately blended according to their purpose, their blending ratio is not particularly limited, but it is preferable to blend them in a manner that increases their solubility in an alkaline aqueous solution by means of acid. Based on all repeating units in the polymer, the ratio of repeating units in (P-1) and (P-2) is preferably 5 to 50 mol% (more preferably 10 to 40 mol%). In polymer (A), the number of repeating units of formulas (P-1), (P-2), (P-3) and (P-4) are respectively set as np1, np2, np3 and np4. np1 / (np1+np2+np3+np4) is preferably 0 to 60% (more preferably 1 to 60%; even more preferably 5 to 50%; even more preferably 10 to 30%). The ratio of np2 / (np1+np2+np3+np4) is preferably 0-60% (more preferably 0-50%; even more preferably 5-50%; and even more preferably 5-30%). In one embodiment of the invention, np2 / (np1+np2+np3+np4) = 0% is also suitable. The ratio of np3 / (np1+np2+np3+np4) is preferably 0-90% (more preferably 5-80%; even more preferably 30-80%; and even more preferably 50-70%). The ratio of np4 / (np1+np2+np3+np4) is preferably 0-60% (more preferably 1-50%; even more preferably 5-40%; and even more preferably 10-30%). Preferably, np1+np2 > 0%, that is, at least one of np1 and np2 is greater than 0%. More preferably, np1 is greater than 0%. np1, np2, np3, and np4 preferably satisfy the following formulas: 0%≦np1 / (np1+np2+np3+np4)≦60%, 0%≦np2 / (np1+np2+np3+np4)≦60%, 0%≦np3 / (np1+np2+np3+np4)≦90%, and 0%≦np4 / (np1+np2+np3+np4)≦60%, and np1+np2>0%. The polymer (A) may also contain repeating units other than those shown in formulas (P-1), (P-2), (P-3), and (P-4). Here, the total number of repeating units ntotal contained in polymer (A) preferably satisfies the following formula: 80% ≤ (np1+np2+np3+np4) / ntotal ≤ 100%. (np1+np2+np3+np4) / ntotal is more preferably 90-100% (especially 95-100%). (np1+np2+np3+np4) / ntotal = 100%, that is, excluding repeating units other than those shown in formulas (P-1), (P-2), (P-3) and (P-4), is also a preferred embodiment of the present invention.

[0019] Specific examples of polymer (A) are as follows.

[0020] The mass-average molecular weight (Mw) of polymer (A) is preferably 2,000 to 200,000 (more preferably 4,000 to 200,000; even more preferably 8,000 to 30,000). Here, the mass-average molecular weight is obtained by conversion of polystyrene by gel permeation chromatography.

[0021] The polymer (A) may be one or more. Based on the composition, the content of polymer (A) is preferably 20 to 45% by mass (more preferably 25 to 40% by mass; even more preferably 30 to 35% by mass).

[0022] (B) Deprotecting Agent The composition of this invention comprises a deprotecting agent (B). The deprotecting agent releases an acid upon exposure to light, which 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 acid groups protected by protecting groups, the acid removes the protecting groups. The deprotecting agent used in the composition of this invention can be selected from those already known.

[0023] (B) The deprotectant releases an acid with an acid dissociation constant pKa(H2O) preferably -20 to 1.4 (more preferably -16 to 1.4; even more preferably -16 to 1.2; even more preferably -16 to 1.1) by exposure.

[0024] The deprotectant (B) is preferably expressed as formula (B-1) or formula (B-2).

[0025] Formula (B-1) is as follows: Bn+ cation Bn- anion (B-1) Wherein, the Bn+ cation comprises at least one cation selected from the group of cations represented by formulas (BC1) to (BC3), and all of them are n-valent (here, n is 1 to 3), and the Bn- anion comprises at least one anion selected from the group of anions represented by formulas (BA1) to (BA4), and all of them are n-valent. The n-valent is preferably monovalent or divalent, more preferably monovalent.

[0026] Formula (BC1) is as follows. In this formula, each Rb1 is independently a C1-6 alkyl, C1-6 alkoxy, C6-12 aryl, C6-12 arylthio, or C6-12 aryloxy (preferably methyl, ethyl, tributyl, methoxy, ethoxy, phenylthio, or phenoxy; more preferably tributyl, methoxy, ethoxy, phenylthio, or phenoxy). Each nb1 is independently 0, 1, 2, or 3. A suitable form is when all nb1 is 1 and all Rb1 are the same. A suitable form is when nb1 is 0. The specific examples of formula (BC1) are as follows.

[0028] Formula (BC2) is as follows. In the formula, each Rb2 is independently a C1-6 alkyl, C1-6 alkoxy, or C6-12 aryl (preferably Rb2 is an alkyl group having a C4-6 branched structure; more preferably, it is a tributyl or 1,1-dimethylpropyl; especially preferably, it is a tributyl). Each Rb2 may be the same or different, preferably the same. Each nb2 is independently 0, 1, 2, or 3, preferably 1. The specific examples of formula (BC2) are as follows.

[0030] Formula (BC3) is as follows. In this formula, each of Rb3 is independently a C1-6 alkyl, C1-6 alkoxy, or C6-12 aryl (preferably methyl, ethyl, methoxy, or ethoxy; more preferably methyl or methoxy). Each of Rb4 is independently a C1-6 alkyl (preferably methyl or ethyl; more preferably methyl). Each of nb3 is independently 0, 1, 2, or 3, more preferably 3. The specific examples of formula (BC3) are as follows.

[0032] The Bn+ cation is preferably selected from the group of cations represented by formula (BC1) or (BC2) because it achieves better results.

[0033] Formula (BA1) is as follows. In this formula, each Rb5 is independently a C1-6 fluoro-substituted alkyl or a C1-6 alkyl group. For example, -CF3 indicates that the hydrogen in the methyl (C1) group is replaced by fluorine. Preferably, all hydrogens present in the C1-6 fluoro-substituted alkyl group are replaced by fluorine. The alkyl portion of Rb5 is preferably methyl, ethyl, or tributyl (more preferably methyl). In a suitable form, Rb5 is preferably a fluoro-substituted alkyl group, more preferably -CF3. The specific examples of formula (BA1) are as follows.

[0034]

[0035] Formula (BA2) is as follows. In this formula, Rb6 is a C1-6 fluoro-substituted alkyl, C1-6 fluoro-substituted alkoxy, C6-12 fluoro-substituted aryl, C2-12 fluoro-substituted acetyl, or C6-12 fluoro-substituted alkoxyaryl (preferably C2-6 fluoro-substituted alkyl; more preferably C2-3 fluoro-substituted alkyl; even more preferably C3 fluoro-substituted alkyl). In the fluoro-substituted alkyl group of Rb6, it is preferable that all hydrogen atoms present in the alkyl moiety are replaced by fluorine. The alkyl moiety of Rb6 is preferably methyl, ethyl, propyl, butyl, or pentyl (more preferably propyl, butyl, or pentyl; especially preferably butyl). The alkyl moiety of Rb6 is preferably straight-chain. Specific examples of formula (BA2) are as follows: C4F9SO3-, C3F7SO3-

[0037] Formula (BA3) is as follows. In this formula, each Rb7 is independently a C1-6 fluoro-substituted alkyl, C1-6 fluoro-substituted alkoxy, C6-12 fluoro-substituted aryl, C2-12 fluoro-substituted acetyl, or C6-12 fluoro-substituted alkoxyaryl (preferably C2-6 fluoro-substituted alkyl). The alkyl portion of Rb7 is preferably methyl, ethyl, propyl, butyl, or pentyl (more preferably methyl, ethyl, or butyl; especially preferably butyl). The alkyl portion of Rb7 is preferably straight-chain. Here, two Rb7s can be bonded together to form a fluorinated heterocyclic structure. In this case, the heterocycle can be monocyclic or polycyclic, but preferably a monocyclic structure with 5 to 8 constituent members. The specific examples of formula (BA3) are as follows.

[0038]

[0039] Formula (BA4) is as follows. In this formula, Rb8 is hydrogen, C1-6 alkyl, C1-6 alkoxy, or hydroxyl (preferably hydrogen, methyl, ethyl, methoxy, or hydroxyl; more preferably hydrogen or hydroxyl). Lb is carbonyl, oxygen, or carbonyloxy (preferably carbonyl or carbonyloxy; more preferably carbonyl). Yb is individually hydrogen or fluorine, preferably at least one of which is fluorine. nb4 is an integer from 0 to 10, preferably 0. nb5 is an integer from 0 to 21, preferably 4, 5, or 6. The specific examples of formula (BA4) are as follows.

[0041] The Bn-anion is preferably selected from the group containing anions represented by formula (BA2) or (BA3) because it achieves better results. The composition of the present invention contains two deprotecting agents (B), each containing an anion represented by (BA2) and an anion represented by (BA3), which are also suitable as anionic forms.

[0042] Formula (B-2) is as follows. In the formula, Rb9 is a C1-5 fluoro-substituted alkyl group (preferably an alkyl group in which all hydrogens of C1-4 are substituted by fluorine; more preferably an alkyl group in which all hydrogens of C1 or C4 are substituted by fluorine). Rb10 are each independently a C3-10 alken or alkynyl group (here, CH3- in the alken and alkynyl groups can be replaced by phenyl groups, and -CH2- in the alken and alkynyl groups can be replaced by at least any one of -C(=O)-, -O-, or extended phenyl groups), a C2-10 thioalkyl group, a C5-10 saturated heterocycle (preferably a C3-12 alken or alkynyl group, a C3-5 thioalkyl group, a C5-6 saturated heterocycle; 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 tertiary butyl, and Ph means extended phenyl or phenyl. Furthermore, in this 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). nb6=1 is also a suitable form.

[0043] As a specific example of equation (B-2), the following can be given.

[0044] (B) The molecular weight of the deprotecting agent is preferably 400 to 2,500, more preferably 400 to 1,500.

[0045] The deprotecting agent (B) may be one or more types, and a combination of two types is also preferred. Based on the total mass of the polymer (A), 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). For clarity, when two deprotecting agents (B) are used in combination, the above content refers to the sum of the two deprotecting agents (B).

[0046] (C) Carboxylic Acid Compound The composition of the present invention comprises a carboxylic acid compound (C) containing C4-12 carbon atoms. The number of carbon atoms in the carboxylic acid compound (C) is counted including 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 1, 2, or 3 (preferably 1 or 2) carboxyl groups. The carboxylic acid compound (C) has double or triple bonds between carbon atoms, preferably 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) refers to the first part (pKa1), and if there is only one pKa, that one pKa is used.

[0047] The composition of the present invention reduces the depression of the top shape of the photoresist pattern described later by including a carboxylic acid compound (C), and can achieve a highly rectangular shape. Although not bound by theory, it is believed that the unsaturated fatty acids contained in the carboxylic acid compound (C) are not easily decomposed by the heat during the formation or exposure of the photoresist film, and the pattern shape can be controlled by the high acidity (low pKa1). Although not bound by theory, it is believed that the carboxylic acid compound (C) quenches amines from the environment, and the acid (e.g. from the deprotecting agent (B)) can prevent the change in the base solubility of the polymer (A) from being hindered by amines from the environment. Although not bound by theory, it is believed that because the molecular weight of the carboxylic acid compound (C) is small, it tends to exist near the film surface due to the evaporation of the solvent during film formation and can quench environmental amines that tend to have a significant impact near the film surface.

[0048] In a preferred form, 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).

[0049] Formula (c-1) is as follows. In the formula, Ar11 is a C5-10 aromatic hydrocarbon ring, which can be monocyclic or polycyclic. Ar11 is preferably benzene or naphthalene (more preferably benzene). R11 is OH or NH2, preferably OH. n11 is 0 or 1 (preferably 1). n12 is 0, 1, or 2 (preferably 1).

[0050] Specific examples of aromatic carboxylic acids (C-1) include benzoic acid, 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, etc., with 2-hydroxybenzoic acid being preferred.

[0051] Equation (c-2) is as follows. In the equation, L21 is -C=C- or -C≡C-, preferably -C=C-. L22 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).

[0052] Specific examples of aliphatic carboxylic acids (C-2) include fumaric acid and maleic acid, with fumaric acid being preferred.

[0053] The molecular weight of the carboxylic acid compound (C) is preferably 80 to 200, and more preferably 90 to 140.

[0054] The carboxylic acid compound (C) may be one or more. Based on the polymer (A), the content of the carboxylic acid compound (C) is preferably 0.01 to 5% by mass (more preferably 0.03 to 4% by mass; even more preferably 0.10 to 2% by mass; even more preferably 0.12 to 1.00% by mass).

[0055] (D) Solvent The composition of the present invention comprises a solvent (D). Solvent (D) comprises an organic solvent (D1). Based on solvent (D), the content of organic solvent (D1) is preferably 80-100% by mass (more preferably 95-100% by mass; even more preferably 98-100% by mass; even more preferably 100% by mass).

[0056] The organic solvent (D1) is not particularly limited as long as it can dissolve all the incorporated components, and can be selected arbitrarily from those commonly used in lithography. Specifically, examples include 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 also referred to as PGME) and propylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMEA) and propylene glycol monoethyl ether acetate; lactates such as methyl lactate and ethyl lactate (hereinafter also referred to as EL); aromatic hydrocarbons such as toluene and xylene; acetamides such as N,N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone, etc. These can be used alone or in combination of two or more. As a suitable form, the solvent (D) comprises at least one selected from the group consisting of ethylene glycol monoalkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, lactates, aromatic hydrocarbons, amides and lactones as an organic solvent (D1).

[0057] Due to its relationship with other layers or films, a form in which the (D) solvent is substantially water-free is also acceptable. For example, the amount of water in the total (D) solvent is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and even more preferably 0.001% by mass or less. A form in which the (D) solvent is water-free (0% by mass) is also suitable.

[0058] Based on the composition, the content of solvent (D) is preferably 50 to 80% by mass (more preferably 55 to 75% by mass; even more preferably 60 to 70% by mass).

[0059] (E) Quenching Agent The composition of the present invention comprises a quenching agent (E). The quenching agent (E) has the effect of inhibiting the diffusion of acid from the deprotecting agent (B) generated in the exposure section, or inhibiting the deactivation of acid on the surface of the photoresist film caused by components such as amines contained in the air. Furthermore, the pH of the composition can be controlled by adjusting the amount of quenching agent (E). The quenching agent (E) has a different structure from the carboxylic acid compound (C). The quenching agent (E) is preferably an amine compound (E1) or a carboxylate (E2). When the quenching agent (E) is a carboxylate (E2), it releases acid upon irradiation by light, but the acid does not directly act on the polymer. This is different from the deprotecting agent (B) that directly acts on the polymer, as the released acid causes the protective groups of the polymer to detach.

[0060] As amine compounds (E1), examples include: (i) ammonia; (ii) primary aliphatic amines having 1 to 16 carbon atoms and their derivatives, such as methylamine, ethylamine, isopropylamine, tributylamine, cyclohexylamine, ethylenediamine, tetraethylamine, etc.; (iii) secondary aliphatic amines having 2 to 32 carbon atoms and their derivatives, such as dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, N,N-dimethylmethylenediamine, etc.; (iv) tertiary aliphatic amines having 3 to 48 carbon atoms and their derivatives, such as trimethylamine, triethylamine, dimethylethylamine, tricyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N',N'-pentamethyldiethyltriamine, 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 their derivatives, such as pyrrole, azole, thiazole, imidazole, 4-methylimidazolium, pyridine, methylpyridine, butylpyridine, etc. As an amine compound (E1), (iv) is the preferred form. In (iv), [2-(2-methoxyethoxy)ethyl] is the preferred form.

[0061] The molecular weight of the amine compound (E1) is preferably 17 to 500, more preferably 60 to 400. The base dissociation constant pKb(H2O) of the amine compound (E1) is preferably -12 to 5, more preferably 1 to 4.

[0062] The carboxylate (E2) is an acid that releases its acid dissociation constant pKa(H2O) upon exposure, preferably 1.5 to 8, more preferably 1.5 to 5. In a preferred form, the carboxylate (E2) is represented by formula (e-2). Cm+ cation Cm- anion Formula (e-2) Wherein, the Cm+ cation comprises at least one cation selected from the group comprising cations represented by formulas (EC1) and (EC2), and all are m-valent (here, m is 1 to 3), and the Cm- anion comprises at least one anion represented by formula (EA), all being m-valent. The m-valent is preferably monovalent or divalent, more preferably monovalent.

[0063] Formula (EC1) is as follows. In this formula, each Re1 is independently a C1-6 alkyl, C1-6 alkoxy, or C6-12 aryl (preferably methyl, ethyl, tributyl, methoxy, ethoxy, phenylthio, or phenoxy; more preferably tributyl, methoxy, ethoxy, phenylthio, or phenoxy; even more preferably tributyl or methoxy). Each ne1 is independently 0, 1, 2, or 3. A suitable form is when all ne1s are 1 and all Re1s are the same. A suitable form is when ne1 is 0. Specific examples of formula (EC1) are as follows.

[0065] Formula (EC2) is as follows. In the formula, each Re2 is independently a C1-6 alkyl, C1-6 alkoxy, or C6-12 aryl (preferably Re2 is an alkyl group having a C4-6 branched structure; more preferably, it is a tributyl or 1,1-dimethylpropyl; especially preferably, it is a tributyl). Each Re2 may be the same or different, but preferably the same. Each ne2 is independently 0, 1, 2, or 3, preferably 1. The specific examples of formula (EC2) are as follows.

[0067] Formula (EA) is as follows. In the formula, X is a C1-20 hydrocarbon group, which can be straight-chain, branched, or cyclic, but is preferably straight-chain or cyclic. When straight-chain, it is preferably C1-4 (more preferably C1-2), and preferably has one double bond or is saturated. When cyclic, it can be a monocyclic or saturated aromatic ring; when monocyclic, it is preferably a 6-membered ring; when polycyclic, it is preferably an adamantane ring. X is preferably methyl, ethyl, propyl, butyl, ethane, phenyl, cyclohexane, or adamantane (more preferably methyl, phenyl, or cyclohexane; especially phenyl). Re3 is independently OH, C1-6 alkyl, or C6-10 aryl (preferably OH, methyl, ethyl, 1-propyl, 2-propyl, tributyl, 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; even better is 1). Specific examples of formula (EA) are as follows.

[0069] The molecular weight of the carboxylate (E2) is preferably 300 to 1,400, and more preferably 300 to 1,200.

[0070] The quencher (E) may be one or more types. Based on the polymer (A), the content of the quencher (E) is preferably 0.001 to 5% by mass (more preferably 0.05 to 2% by mass; even more preferably 0.01 to 1% by mass).

[0071] (F) Surfactant The composition of the present invention includes a surfactant (F). The coating properties of the composition can be improved by means of the surfactant (F). Examples of surfactants (F) include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0072] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oil-based ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters, polyhydroxy fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers; alkynyl alcohols, alkynyl diols, polyethoxyl oxides of alkynyl alcohols, and polyethoxyl oxides of alkynyl alcohols; fluorinated surfactants such as Fluorad (trade name, Sumitomo 3M), MEGAFAC (trade name, DIC), and Surflon (trade name, Asahi Glass); and organosiloxane surfactants such as KF-53 (trade name, Shin-Etsu Chemical Industry). Examples of the aforementioned alkynyl alcohols include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyyn-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0073] Examples of anionic surfactants include ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkylbenzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfuric acid, and ammonium salts or organic amine salts of alkyl sulfuric acid.

[0074] Furthermore, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauryl propyl hydroxybenzene.

[0075] The surfactant (F) may be used alone or in combination of two or more. Based on the polymer (A), the content of surfactant (F) is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass.

[0076] (G) Additives The composition of the present invention may include additives (G) other than (A) to (F). Additive (G) is preferably selected from at least one of the group consisting of surface smoothers, plasticizers, pigments, contrast enhancers, acids, bases, free radical generators, substrate adhesion enhancers, and defoamers. Based on polymer (A), the content of additive (G) is preferably 0.01 to 10% by mass, more preferably 0.1 to 2% by mass. The absence of additive (G) (0% by mass) is also a suitable form of the composition of the present invention.

[0077] Method for manufacturing photoresist film The method for manufacturing photoresist film of the present invention comprises the following steps: (1) applying the composition of the present invention onto a substrate; (2) heating the aforementioned composition to form a photoresist film with a film thickness of 0.8 to 20 μm. Hereinafter, one aspect of the manufacturing method of the present invention will be described.

[0078] Step (1) Apply the composition of the present invention to a substrate (e.g., silicon / silicon dioxide coated substrate, silicon nitride substrate, silicon wafer substrate, glass substrate, and ITO substrate, etc.) by a suitable method. Here, in the present invention, "above" includes the case where it is formed directly above the substrate and the case where it is formed with other layers in between. For example, a planarization film or a photoresist underlayer film can be formed directly above the substrate, and the composition of the present invention can be applied directly above it. It is more suitable to apply the composition of the present invention directly above the substrate (without other layers in between). There are no particular limitations on the application method; for example, methods using a spinner or a coating machine can be used for coating.

[0079] Step (2) After the application of the composition, a photoresist film with a thickness of 0.8 to 20 μm is formed by heating. (2) Heating is performed, for example, by a heating plate. The heating temperature is preferably 100 to 250°C (more preferably 100 to 200°C; even more preferably 100 to 160°C). The temperature here refers to the heating environment, such as the heating surface temperature of the heating plate. The heating time is preferably 30 to 300 seconds (more preferably 60 to 240 seconds). Heating is preferably performed in an atmospheric or nitrogen atmosphere. The thickness of the photoresist film is selected according to the purpose, but when using the composition of the present invention, a more superior pattern can be formed when a thick coating film is formed. Therefore, the thickness of the photoresist film is preferably thick, 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).

[0080] Furthermore, a photoresist pattern can be manufactured by a method comprising the following steps: (3) exposing the aforementioned photoresist film; (4) developing the aforementioned photoresist film. For clarity, steps (1) and (2) are performed before step (3). The numbers in parentheses indicating steps indicate the order. The same applies thereafter.

[0081] Step (3) Expose the photoresist film through a specific mask. There is no particular limitation on the wavelength of the light used for exposure, but it is preferable to use light with a wavelength of 13.5–248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet light (wavelength 13.5 nm) can be used, with KrF excimer laser being preferred. These wavelengths are permissible within a range of ±1%. After exposure, post-exposure bake (PEB) may be performed as needed. The post-exposure bake temperature is preferably 80–150°C, more preferably 100–140°C, and the baking time is 0.3–5 minutes, preferably 0.5–2 minutes.

[0082] Step (4) The exposed photoresist film is developed using a developing solution. As a developing method, methods previously used for developing photoresist, such as liquid development, immersion development, and shaking immersion development, can be used. Furthermore, as a developing solution, an aqueous solution containing inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium silicate, organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, and triethylamine, and quaternary amines such as tetramethylammonium hydroxide (TMAH) can be used; preferably, a 2.38% by mass TMAH aqueous solution. A surfactant may also be added to the developing solution. The temperature of the developing solution is preferably 5–50°C, more preferably 25–40°C, and the developing time is preferably 10–300 seconds, more preferably 30–60 seconds. After development, washing or rinsing may be performed as needed. When using a positive photoresist composition, the exposed portion is removed by development, forming a photoresist pattern. This photoresist pattern can also be made finer by using shrinkage materials, for example.

[0083] When using chemically amplified photoresist to form thick-film photoresist patterns, especially when the aspect ratio is high, a recess occurs at the top of the photoresist pattern wall (details of the recessed portion are illustrated using diagrams in the embodiments). In a preferred embodiment, the distance between the perpendicular line from the top endpoint of the photoresist pattern to the substrate and the perpendicular line from the most recessed point on the side of the aforementioned photoresist pattern to the substrate (hereinafter also referred to as the intrusion width) is 50 nm or less (more preferably 0–45 nm; even more preferably 0–20 nm; even more preferably 0–1 nm). In this invention, this recess can be suppressed, and a pattern with high rectangularity can be formed. Since the recessed portion can be suppressed, the toughness of the pattern can be increased in subsequent steps, which is advantageous.

[0084] Furthermore, the substrate can be manufactured by a method comprising the following steps: (5) processing the photoresist pattern as a mask. As one aspect of the present invention, it is preferable that no metal (e.g., plating) is used between the patterns (grooves) of the photoresist pattern. That is, it is preferable that no metal (e.g., plating) is filled between the photoresist patterns.

[0085] The photoresist pattern formed in step (5) is preferably used for processing a lower film or substrate (more preferably a substrate). Specifically, using the photoresist pattern as a mask, various substrates can be processed using dry etching, wet etching, ion implantation, or metal plating. Using the photoresist pattern of the present invention as a mask and etching the substrate using dry etching is a preferred method. Since the photoresist pattern of the present invention can achieve a thick film, it can also be used for substrate processing using ion implantation. When processing a lower film using the photoresist pattern, the processing can be performed in stages. For example, the BARC layer can be processed using the photoresist pattern, the SOC film can be processed using the BARC pattern, and the substrate can be processed using the SOC pattern.

[0086] Then, the substrate is further processed as needed, preferably by forming wiring on the processed substrate, to manufacture a device. Such processing can be performed using well-known methods. As needed, the substrate is diced into wafers, connected to lead frames, and encapsulated in resin. In this invention, this encapsulated device is referred to as a device. Examples of devices include semiconductor elements, liquid crystal display elements, organic EL display elements, plasma display elements, and solar cell elements, preferably semiconductor elements.

[0087] By using the thick-film photoresist composition of the present invention, the pattern shape of the formed photoresist pattern can be controlled. Therefore, as another perspective, the present invention provides the following methods: A method for forming a photoresist pattern using the thick-film photoresist composition of the present invention and controlling the pattern shape. A method for forming a photoresist pattern using the thick-film photoresist composition of the present invention and controlling the penetration width of the photoresist pattern (preferably a method of reduction). A method for forming a photoresist pattern using the thick-film photoresist composition of the present invention and controlling the penetration width of the photoresist pattern to below 50 nm. The details of the thick-film photoresist composition in the above methods are as described above. Furthermore, the details of the manufacturing methods of the photoresist film, photoresist pattern, processing substrate, and apparatus are as described above. [Examples]

[0088] The present invention will be illustrated by way of example, as follows. However, the nature of the present invention is not limited to these examples.

[0089] Preparation of Composition 1: PGME and PGMEA were mixed at a mass ratio of 70:30 (=PGME:PGMEA) to obtain a mixed solvent. To this mixed solvent (66.0 parts by mass), polymer A1 (33.451 parts by mass), deprotecting agent B1 (0.067 parts by mass), deprotecting 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) were added. The mixture was stirred at room temperature for 30 minutes to obtain a solution. Visual inspection confirmed that all components were completely dissolved. The resulting solution was filtered through a 0.05 μm filter to obtain Composition 1. • Polymer A1: p-hydroxystyrene / styrene / tert-butyl acrylate copolymer (Mw=20,000, random copolymerization) • Deprotectant B1: The following compound (Gokyo Food & Chemical) • Deprotectant B2: The following compound (Gokyo Food & Chemical) • Carboxylic acid compound C1: 2-hydroxybenzoic acid • Quencher E1: Tris-[2-(2-methoxyethoxy)ethyl]amine • Surfactant F1: MEGAFAC R-2011 (DIC)

[0090] The formulations of compositions 2-5 and comparative compositions 1-5 were prepared in the same manner as composition 1, except that the carboxylic acid compound C1 was set to the compound listed in Table 1, and the amount of the compound added was changed in the same way as in composition 1, so that the molar ratio with respect to polymer A1 was the same. In Table 1, the pKa1 of each carboxylic acid compound is listed in parentheses adjacent to it, and the evaluation at the top of the pattern is a record of the measured value and an evaluation based on the criteria described later. [Table 1] Carboxylic acid compounds (pKa1) Evaluation of the top of the patterned wall Composition 1 2-Hydroxybenzoic acid (2.97) Less than 1nm A Composition 2 Benzoic acid (4.20) 12nm B Composition 3 3-Hydroxybenzoic acid (3.84) 40nm B Composition 4 4-Hydroxybenzoic acid (4.54) 10nm B Composition 5 Fumaric acid (3.03) Less than 1nm A Comparative composition 1 Oxalic acid (1.25) 206nm C Comparative composition 2 Malonic acid (2.83) 161nm C Comparative composition 3 Succinic acid (4.20) 76nm C Comparative composition 4 Glutaric acid (4.32) 52nm C Comparative composition 5 Citric acid (3.09%) 73nm C

[0091] In the example of forming the photoresist pattern, the above-modified composition was dropped onto an 8-inch Si wafer using a Mark 8 coating and developing machine (Tokyo Electron) and spin-coated. The wafer was heated at 140°C for 90 seconds under atmospheric conditions using a heated plate to form a photoresist film. The thickness of the photoresist film at this time point was measured to be 10.5 μm using an M-1210 (SCREEN) optical interferometric film thickness measuring device. The photoresist film was exposed using a KrF stepper FPA3000-EX5 (CANON). The exposed wafer was heated at 110°C (PEB) for 90 seconds under atmospheric conditions using a heated plate. Then, the photoresist film was developed with a 2.38% (w / w) TMAH aqueous solution for 60 seconds, washed with DIW, and spin-dried at 1,000 rpm. This formed a trench pattern with a linewidth of 15 μm, a gap width of 3 μm, and a top width of 9 μm. The linewidth and gap width are measured values ​​at the bottom of the pattern. Figure 1 schematically shows the shape of the pattern. A photoresist pattern 12 is formed on the substrate 11, and the linewidth 13, gap width 14, and top width 15 are as shown in Figure 1. A magnified schematic diagram of the top 16 of the pattern wall is shown in Figure 2. The exposure energy (mJ / cm2) used to obtain the pattern of this shape is taken as the sensitivity. When using composition 1, the sensitivity is 108 (mJ / cm2). The sensitivity of compositions 2 to 5 is recorded in Table 2. The sensitivity mentioned here refers to the sensitivity of the initial composition described later.

[0092] Evaluation of the top of the pattern wall: A section of the sample made in the example of photoresist pattern formation was observed using a scanning electron microscope (SEM) to examine the vertical cross-section of the pattern. The degree of indentation (intrusion width) from the top of the pattern on the inner side was evaluated. Specifically, Figure 2 is used for explanation. Figure 2 schematically shows the top of the wall 21. A line was drawn perpendicular to the substrate from the endpoint of the top of the pattern, and another line was drawn perpendicular to the substrate from the most indented point on the side of the pattern. The distance between each line was taken as the intrusion width. The evaluation criteria are as follows: A: Intrusion width less than 1 nm B: Intrusion width 1 to 50 nm C: Intrusion width greater than 50 nm The evaluation results are recorded in Table 1.

[0093] Evaluation of stability over time: Immediately after modulation of each component, similar to the photoresist pattern formation example described above, a groove pattern with a linewidth of 15 μm, a gap width of 3 μm, and a top width of 9 μm was formed, and the sensitivity was measured. This was taken as the sensitivity of the initial composition. Each component was stored at 40°C for 30 days. Using these, similar to the photoresist pattern formation example, a groove pattern with a linewidth of 15 μm, a gap width of 3 μm, and a top width of 9 μm was formed, and the sensitivity was measured. This was taken as the sensitivity of the composition over time. The stability over time was evaluated by calculating (sensitivity of the composition over time) / (sensitivity of the initial composition). The evaluation criteria are as follows: Stable: Sensitivity change less than 10% Unstable: Sensitivity change greater than 10% The evaluation results are recorded in Table 2.

[0094] Film loss evaluation was performed using a Mark 8 coating and developing machine. The composition was dropped onto an 8-inch Si wafer and spin-coated. The wafer was heated at 140°C for 90 seconds under atmospheric conditions using a heated plate to form a photoresist film. The thickness of the photoresist film at this time point was measured using an M-1210 and taken as the initial film thickness. The above photoresist film formation was then performed, and the photoresist film was exposed using a KrF stepper FPA3000-EX5. The wafer was heated at 110°C for 90 seconds under atmospheric conditions using a heated plate using PEB. The photoresist film was developed for 60 seconds using a 2.38% (w / w) TMAH aqueous solution. This formed a trench pattern with a linewidth of 15 μm and a gap width of 3 μm. The wafer was then spin-dried at 1,000 rpm. The thickness of the photoresist film at this time point was measured using an M-1210 and taken as the post-exposure film thickness. If the ratio of post-exposure film thickness to initial film thickness is less than 99%, it is evaluated as having no film loss; if the ratio is greater than or equal to 99%, it is evaluated as having film loss. The evaluation results are recorded in Table 2.

[0095] Evaluation of Exposure Margin (EL): Using a composition without carboxylic acid compound (C) as a control, a groove pattern with a line width of 15 μm, a gap width of 3 μm, and a top width of 9 μm was formed, similar to the photoresist pattern formation example described above. The sensitivity was measured (this sensitivity is referred to as the reference sensitivity). Using the composition containing carboxylic acid compound (C) listed in Table 2, a groove pattern was formed in a manner similar to the photoresist pattern formation example described above, with a gap width of ±2% (i.e., 2.94 to 3.06 μm). The sensitivity was measured, and the change in sensitivity was calculated. EL = Change in sensitivity / Reference sensitivity × 100. The EL of each composition was calculated. The results are shown in Table 2.

[0096] In addition to forming a trench pattern with a linewidth of 15 μm and a gap width of 20 μm, the photoresist pattern was formed in the same manner as in the photoresist pattern formation example described above. The interface between the Si wafer and the photoresist wall was observed using a CD-SEM at a magnification of 50K. If peeling was observed, it was evaluated as present; otherwise, it was evaluated as absent. The evaluation results are recorded in Table 2. [Table 2] Carboxylic acid compounds Sensitivity mJ / cm 2 Stability over time Membrane Loss Reduction EL Peeling Composition 1 2-Hydroxybenzoic acid 108 stable none 33 none Composition 2 benzoic acid 108 stable none 30 none Composition 3 3-Hydroxybenzoic acid 117 stable none 28 none Composition 4 4-Hydroxybenzoic acid 133 stable none 26 none Composition 5 fumaric acid 105 stable none 30 none

[0097] Preparation of Composition 21: PGME and PGMEA were mixed at a mass ratio of 70:30 (=PGME:PGMEA) to obtain a mixed solvent. For this mixed solvent (66.0 parts by mass), polymer A1 (33.447 parts by mass), deprotectant B1 (0.067 parts by mass), deprotectant B2 (0.375 parts by mass), quencher E1 (0.01 parts by mass), and surfactant F1 (0.051 parts by mass) were added. 0.015% by mass of carboxylic acid compound C1 (2-hydroxybenzoic acid) was added relative to polymer A1, and the mixture was stirred at room temperature for 30 minutes to obtain a solution. The complete dissolution of all components was visually confirmed. The resulting solution was filtered through a 0.05 μm filter to obtain composition 21.

[0098] The formulations 22-26 were prepared in the same manner as those for formulation 21, except that the amount of carboxylic acid compound C1 added was changed as shown in Table 3. [Table 3] Added amount (relative to the mass of polymer A) Sensitivity mJ / cm 2 Evaluation of the top of the patterned wall Composition 21 0.015 105 16nm B Composition 22 0.038 100 16nm B Composition 23 0.100 97 16nm B Composition 24 0.150 102 Less than 1nm A Composition 25 0.200 106 Less than 1nm A Composition 26 0.600 138 Less than 1nm A

[0099] The formation of the photoresist pattern and the evaluation of the top of the pattern wall were performed in the same manner as described above, forming a groove pattern with a line width of 15 μm and a gap width of 3 μm. The sensitivity of each is recorded in Table 3. The evaluation of the top of the pattern wall was performed in the same manner, and the evaluation results are recorded in Table 3.

[0100] The formulation 31 was prepared in the same manner as the formulation 21, except that the carboxylic acid compound C1 was replaced with fumaric acid and the amount added was changed to 0.0126% by mass relative to polymer A1. Furthermore, 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 was approximately the same as that in their respective formulations.

[0101] The formulations 32-36 were prepared in the same manner as those for formulation 31, except that the amount of fumaric acid added was changed as shown in Table 4. [Table 4] Added amount (relative to the mass of polymer A) Sensitivity mJ / cm 2 Evaluation of the top of the patterned wall Composition 31 0.0126 104 15nm B Composition 32 0.032 94 Less than 1nm A Composition 33 0.084 98 Less than 1nm A Composition 34 0.126 99 Less than 1nm A Composition 35 0.168 101 Less than 1nm A Composition 36 0.504 112 Less than 1nm A

[0102] The formation of the photoresist pattern and the evaluation of the top of the pattern wall were performed in the same manner as described above, forming a groove pattern with a line width of 15 μm and a gap width of 3 μm. The sensitivity of each is recorded in Table 4. Similarly, the evaluation of the top of the pattern wall was also performed, and the evaluation results are recorded in Table 4. [Simplified Explanation of the Diagram]

[0011] Figure 1 is a conceptual diagram showing the cross-sectional shape of the photoresist pattern. Figure 2 is a conceptual diagram showing the top of the wall of the photoresist pattern.

Claims

1. A thick-film photoresist composition comprising a polymer (A), a deprotecting agent (B), a C4-12 carboxylic acid compound (C), and a solvent (D); wherein, The photoresist film system formed by the thick-film photoresist composition has a film thickness of 0.8–20 μm. The C4-12 carboxylic acid compound (C) is an unsaturated hydrocarbon containing 1, 2, or 3 carboxyl groups. The solvent (D) is composed of an organic solvent (D1). Based on this composition, the content of polymer (A) is 20–45% by mass; based on polymer (A), the content of C4-12 carboxylic acid compound (C) is 0.12–5% by mass; based on polymer (A), the content of deprotecting agent (B) is 0.05–10% by mass.

2. The composition of claim 1, wherein the carboxylic acid compound (C) of C4-12 is an aromatic carboxylic acid (C-1) represented by formula (c-1) or an aliphatic carboxylic acid (C-2) represented by formula (c-2); (wherein, Ar11 is benzene or naphthalene, R11 is OH or NH2, n11 is 0 or 1, and n12 is 1 or 2); (wherein, L21 is -C=C- or -C≡C-, L22 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 of claim 1 or 2 further comprises a quenching agent (E).

4. The composition of claim 1 or 2, wherein the pKa1(H2O) of the C4-12 carboxylic acid compound (C) is 3.03 to 6.

00.

5. The composition of claim 1 or 2, wherein the solvent (D) is selected from the group consisting of ethylene glycol monoalkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, lactates, aromatic hydrocarbons, amides and lactones.

6. The composition of claim 1 or 2, wherein the polymer (A) comprises repeating units selected from the group consisting of repeating units represented by formulas (P-1), (P-2), (P-3) and (P-4); (wherein, Rp1, Rp3, Rp6 and Rp8 are each independently hydrogen or C1-4 alkyl, Rp2 and Rp4 are each independently linear, branched or cyclic C3-15 alkyl, wherein the alkyl may be substituted with fluorine, and -CH2- in the alkyl may be substituted with -O-, T1 and T2 are each independently single bond or C1-12 linking group, Rp5, Rp7 and Rp9 are each independently C1-5 alkyl, wherein -CH2- in the alkyl may be substituted with -O-, x1 is 1 to 3, x2, x3 and x5 are each independently 0 to 2, and x4 is 1 to 2).

7. The composition of claim 1 or 2, wherein the deprotecting agent (B) is represented by formula (B-1) or formula (B-2); Bn+ cation Bn'- anion (B-1) (wherein, the Bn+ cation comprises at least one cation selected from the group comprising cations shown in (BC1), (BC2) and (BC3), and all are n-valent, where n is 1 to 3; the cation shown in formula (BC1): (wherein, Rb1 is each independently C1-6 alkyl, C1-6 alkoxy, C6-12 aryl, C6-12 arylthio or C6-12 aryloxy, and nb1 is each independently 0, 1, 2 or 3), the cation shown in formula (BC2): (wherein, Rb2 is each independently C1-6 alkyl, C1-6 alkoxy or C6-12 aryl, and nb2 is each independently 0, 1, 2 or 3), the cation shown in formula (BC3): (wherein, Rb3 are each independently C1-6 alkyl, C1-6 alkoxy, or C6-12 aryl; Rb4 are each independently C1-6 alkyl; and nb3 are each independently 0, 1, 2, or 3. The Bn'-anion comprises at least one anion selected from the group of anions shown in (BA1), (BA2), (BA3), and (BA4), and all are n' valence, where n' valence is 1 or 2. Anion shown in formula (BA1): (where Rb5 are each independently C1-6 fluorosubstituted alkyl or C1-6 alkyl). Anion shown in formula (BA2): (where Rb6 is C1-6 fluorosubstituted alkyl, C1-6 fluorosubstituted alkoxy, C6-12 fluorosubstituted aryl, C2-12 fluorosubstituted acetyl, or C6-12 fluorosubstituted alkoxyaryl). Anion shown in formula (BA3): (In the formula, each Rb7 is independently a C1-6 fluoro-substituted alkyl, C1-6 fluoro-substituted alkoxy, C6-12 fluoro-substituted aryl, C2-12 fluoro-substituted acetyl, or C6-12 fluoro-substituted alkoxyaryl. Here, two Rb7s can bond together to form a fluorinated heterocyclic structure.) The anion represented by formula (BA4): (In the formula, Rb8 is hydrogen, C1-6 alkyl, C1-6 alkoxy, or hydroxyl; Lb is carbonyl, oxy, or carbonyloxy; Yb is independently hydrogen or fluorine; nb4 is an integer from 0 to 10; and nb5 is an integer from 0 to 21.) (In the formula, Rb9 is a C1-5 fluoro-substituted alkyl.) Rb10 is independently a C3-10 alkenyl or alkynyl, C2-10 thioalkyl, or C5-10 saturated heterocycle. Here, CH3- in the alkenyl and alkynyl groups can be substituted with phenyl groups, and -CH2- in the alkenyl and alkynyl groups can be substituted with at least any one of -C(=O)-, -O-, or phenyl groups. nb6 is 0, 1, or 2.

8. The composition of claim 1 or 2 further comprises a surfactant (F).

9. As in claim 1 or 2, wherein, based on the composition, the content of solvent (D) is 50 to 80% by mass; the content of organic solvent (D1) is 80 to 100% by mass based on solvent (D); the content of quencher (E) is 0.001 to 5% by mass based on polymer (A); the content of surfactant (F) is 0.01 to 5% by mass based on polymer (A); or the content of additive (G) is 0.01 to 10% by mass based on polymer (A).

10. The composition of claim 1 or 2 is a thick-film chemically amplified photoresist composition.

11. A method for manufacturing a photoresist film, comprising the following steps: (1) applying a composition of at least any one of claims 1 to 10 onto a substrate; (2) heating the composition to form a photoresist film with a thickness of 0.8 to 20 μm.

12. A method for manufacturing a photoresist pattern, comprising the following steps: (3) forming a photoresist film by the method of claim 11; (4) exposing the photoresist film; and (5) developing the photoresist film.

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

14. A method for manufacturing a substrate comprising the following steps: (5) forming a photoresist pattern by means of claim 12 or 13; and (6) processing the photoresist pattern as a mask.

15. A method of manufacturing an apparatus comprising the method of at least any one of claims 11 to 14.

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