Thick film chemically amplified positive resist composition and method for producing resist film using the same

Abstract

A thick-film chemically amplified positive resist composition is provided. The present invention relates to a composition comprising a specific alkali-soluble resin (A), a photoacid generator (B), and a specific solvent ( C). A thick-film chemically amplified positive resist composition comprising:

Description

[Technical Field]

[0001] The present invention relates to a thick-film chemically amplified positive 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 commonly 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 to accommodate high-energy ion implantation, etc. When forming a thick-film resist pattern, the performance and process conditions required of the composition differ from those required for a thin-film resist pattern, and therefore there is a particular difficulty in that the required shape cannot be formed simply by adjusting the viscosity of a thin-film resist composition to thicken the film.

[0004] Patent Document 1 discusses a positive resist composition for forming a thick-film resist using a mixed solvent containing propylene glycol monomethyl ether (PGME). It states that a high-boiling-point solvent is preferable as a solvent to be combined with PGME, but does not discuss resist films with a thickness of 11 μm or more. Patent Document 2 discusses a resist composition for forming a thick-film resist, which contains a solvent having a specific viscosity and saturated vapor pressure, with the aim of improving liquid transportability, but does not discuss resist films with a thickness of 11 μm or more. Patent Document 3 discusses the formation of a resist film with a thickness of 7 μm or more using a specific resin. Patent Document 4 discusses a resist that forms a thick film using a specific acid generator, but does not discuss a resist film with a thickness of 11 μm or more. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-248727 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-206673 [Patent Document 3] Japanese Patent Application Publication No. 2019-120765 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-206425 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have recognized that there are one or more problems that still need to be solved with respect to thick-film chemically amplified positive resist compositions and their use. These problems include, for example: Increasing the film thickness leads to larger depressions at the top of the resist pattern walls, a large number of defects, cracks in the resist pattern, low resistance to post-development processes, and the resist film or resist pattern being vulnerable to heat. [Means for solving the problem]

[0007] The thick-film chemically amplified positive resist composition according to the present invention comprises an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C). where The thickness of the resist film formed from the thick-film chemically amplified positive resist composition is 11.0 to 50.0 μm; The alkali-soluble resin (A) comprises at least one of the following repeating units: [ka] (where, R 11 , R 21 , R 41 and R 45 are each independently C 1-5 alkyl (wherein -CH2- in the alkyl may be replaced by -O-); R 12 , R 13 , R 14 , R 22 , R 23 , R 24 , R 32 , R 33 , R 34 , R 42 , R 43 and R 44 are each independently hydrogen, C 1-5 Alkyl, C 1-5 alkoxy, or -COOH; p11 is 0-4, p15 is 1-2, and p11+p15≦5; p21 is 0–5; p41 is 0-4, p45 is 1-2, and p41+p45≦5; P 31 is C 4-20 alkyl (wherein part or all of the alkyl may form a ring, and part or all of the H of the alkyl may be substituted with halogen); and The solvent (C) contains propylene glycol monomethyl ether (PGME) (C-1), and the content of PGME (C-1) is more than 50 mass % and 100 mass % or less based on the solvent (C).

[0008] The 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. [Effects of the Invention]

[0009] By using the thick-film chemically amplified positive resist composition according to the present invention, one or more of the following effects can be expected. A resist pattern with excellent shape can be formed even with a very thick resist film. The recessed shape at the top of the resist pattern wall can be suppressed. The number of defects can be reduced. A resist pattern with sufficient resistance in post-development processes (e.g., etching) can be obtained. Good sensitivity can be obtained even with a thick resist film. The resist film or resist pattern has sufficient heat resistance. Cracks can be suppressed with a thick resist film. [Brief explanation of the drawings]

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

[0011] [Definition] In this specification, unless otherwise specified, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "one" and "the" mean "at least one." An element of a concept can 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 elements as well as any single element. 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 1-6Alkyl refers to alkyl chains 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. This copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are represented by structural formulas, the n or m in parentheses indicates the repeating number. The temperature unit is Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to the compound itself that has that function (for example, in the case of a base generator, it refers to the compound itself that generates a base). The compound may be 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 of the present invention as the solvent (C) or another component.

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

[0013] Thick film chemically amplified positive resist composition The thick-film chemically amplified positive resist composition (hereinafter sometimes referred to as the composition) according to the present invention comprises an alkali-soluble resin (A), a photoacid generator (B) and a solvent (C). A thick-film resist composition is a resist composition that can form a thick resist film. In the present invention, the thickness of a resist film formed from the thick-film resist composition is 11.0 to 50 μm (preferably 11.0 to 20 μm; more preferably 11.0 to 18 μm; and even more preferably 12 to 18 μm). The solids concentration of the composition according to the present invention is preferably greater than 0% by mass and less than 80% by mass, more preferably 30 to 50% by mass, and even more preferably 35 to 45% by mass. The solids concentration is the concentration of all components excluding the solvent component, based on the composition. The viscosity is preferably 100 to 3,000 cP, more preferably 150 to 2,500 cP, and even more preferably 200 to 2,000 cP. The viscosity is measured at 25°C using a capillary viscometer. The composition according to the present invention is preferably a thick-film chemically amplified positive KrF resist composition. The term KrF used in the above preferred examples means that a KrF excimer laser is used to expose a resist film formed from the resist composition.

[0014] (A) Alkali-soluble resin The composition according to the present invention comprises an alkali-soluble resin (A) (hereinafter sometimes referred to as component (A), and the same applies to other components). Component (A) comprises at least one of the repeating units represented by the following formulae (A-1), (A-2), (A-3), and (A-4). Component (A) reacts with an acid to increase its solubility in an alkaline aqueous solution. Such an alkali-soluble resin 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 its solubility in an alkaline aqueous solution. Component (A) can be selected from those commonly used in lithography.

[0015] Formula (A-1) is as follows: [ka] where: R 11 are each independently C 1-5 It is alkyl (wherein methylene in the alkyl may be replaced by oxy); preferably methyl or ethyl; more preferably methyl. In the present invention, the expression "methylene in the alkyl may be replaced by oxy" means that oxy may be present between carbon atoms in the alkyl, and does not intend that the terminal carbon in the alkyl becomes oxy, that is, that it has alkoxy or hydroxy. R 12 , R 13, and R 14 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, or -COOH; preferably hydrogen or methyl; more preferably hydrogen. p11 is 0 to 4; preferably 0 or 1; and more preferably 0. p15 is 1 to 2; preferably 1. p11+p15≦5.

[0016] Specific examples of formula (A-1) include the following. [ka]

[0017] Equation (A-2) is as follows: [ka] where: R 21 are each independently C 1-5 It is alkyl (wherein methylene in the alkyl may be replaced by oxy); it is methyl, ethyl, t-butyl or t-butoxy; more preferably it is methyl or ethyl; more preferably it is methyl. R 22 , R 23 , and R 24 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH; preferably hydrogen or methyl; more preferably hydrogen. p21 is 0 to 5; preferably 0, 1, 2, 3, 4 or 5; more preferably 0 or 1; and even more preferably 0.

[0018] Specific examples of formula (A-2) include the following. [ka]

[0019] Equation (A-3) is as follows: [ka] where: R 32 , R 33 and R 34 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, or -COOH; preferably hydrogen, methyl, ethyl, t-butyl, methoxy, t-butoxy, or -COOH; more preferably hydrogen or methyl; and even more preferably hydrogen. P 31 is C 4-20 Here, part or all of the alkyl may form a ring, part or all of the H in the alkyl may be substituted with halogen, and methylene in the alkyl may be substituted with oxy or carbonyl. 31 The alkyl portion of P is preferably branched or cyclic. 31 C 4-20 When alkyl is substituted with halogen, it is preferable that all of the alkyl is substituted, and the halogen is preferably F or Cl; F is more preferable. 31 C 4-20 In a preferred embodiment of the present invention, H in the alkyl is not substituted with halogen. 31 is preferably methyl, isopropyl, t-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, adamantyl, methyladamantyl, or ethyladamantyl; more preferably t-butyl, ethylcyclopentyl, ethylcyclohexyl, or ethyladamantyl; even more preferably t-butyl, ethylcyclopentyl, or ethyladamantyl; and even more preferably t-butyl.

[0020] Specific examples of formula (A-3) include the following. [ka]

[0021] Equation (A-4) is as follows: [ka] where: R 41 are each independently C 1-5 It is alkyl (wherein methylene in the alkyl may be replaced by oxy); preferably, it is methyl, ethyl or t-butyl; more preferably, it is methyl. R 45 are each independently C 1-5 It is alkyl (wherein methylene in the alkyl may be replaced by oxy); preferably, it is methyl, t-butyl or -CH(CH3)-O-CH2CH3. R 42 , R 43 , and R 44 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, or -COOH; preferably hydrogen or methyl; more preferably hydrogen. p41 is 0 to 4; more preferably 0 or 1; and even more preferably 0. p45 is 1 to 2; more preferably 1. p41+p45≦5.

[0022] Specific examples of formula (A-4) include the following. [ka]

[0023] The alkali-soluble resin (A) can contain multiple repeating units represented by formula (A-1), (A-2), (A-3), or (A-4). For example, it can have a 1:1 ratio of structural units where p15=1 and structural units where p15=2. In this case, the overall value of p15=1.5. Unless otherwise specified, the same applies hereinafter to the numbers representing polymers in the present invention. In a preferred embodiment of the present invention, the alkali-soluble resin (A) contains two or more repeating units represented by formula (A-3), and more preferably contains two repeating units represented by formula (A-3).

[0024] These structural units are appropriately blended depending on the purpose, and 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. The number of repeating units n of the repeating units (A-1), (A-2), (A-3) and (A-4) in the alkali-soluble resin (A) A-1 , n A-2 , n A-3 and n A-4 This is explained below. n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 40 to 80%; more preferably 45 to 75%; even more preferably 50 to 70%; and even more preferably 55 to 65%. n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0 to 40%; more preferably 0 to 35%; even more preferably 5 to 35%; and even more preferably 15 to 25%. n A-3 / (n A-1 +n A-2 +n A-3 +n A-4) is preferably 0 to 40%; more preferably 10 to 40%; even more preferably 15 to 30%; and even more preferably 15 to 25%. n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0 to 40%; more preferably 0 to 30%; even more preferably 0 to 10%; and even more preferably 0 to 5%. A-4 is 0 in one preferred embodiment of the present invention. In one aspect of the present invention, n A-3 >0 and n A-4 =0.

[0025] The alkali-soluble resin (A) may contain further repeating units other than the repeating units represented by (A-1), (A-2), (A-3) and (A-4). The total number n of all repeating units contained in the alkali-soluble resin (A) total Then, (n A-1 +n A-2 +n A-3 +n A-4 ) / n total is preferably 80 to 100%, more preferably 90 to 100%, and even more preferably 95 to 100%. In one preferred embodiment of the alkali-soluble resin (A), the resin does not contain any additional repeating units.

[0026] Specific examples of the alkali-soluble resin (A) include the following. [ka]

[0027] The weight average molecular weight (hereinafter sometimes referred to as Mw) of the alkali-soluble resin (A) is 12,000 to 50,000, more preferably 12,000 to 40,000, even more preferably 12,000 to 30,000, and even more preferably 15,000 to 30,000. Without being bound by theory, it is believed that the presence of an alkali-soluble resin (A) with this Mw makes it possible to suppress cracking when forming a resist pattern from the composition of the present invention. In the present invention, Mw can be measured by gel permeation chromatography (GPC). In one preferred example, the GPC column is set at 40°C, the elution solvent is tetrahydrofuran at 0.6 mL / min, and monodisperse polystyrene is used as the standard.

[0028] For the purpose of explanation, the alkali-soluble resin (A) in the composition according to the present invention can be used in combination of two or more types as long as it is represented by the above formula. For example, a composition containing both of the following two types of alkali-soluble resin (A) is also one embodiment of the present invention. [ka] The same applies to the composition of the present invention in the following description unless otherwise specified. Component (A) is composed of one or two types of polymers, preferably one type of polymer, and variations in Mw distribution and polymerization are permitted.

[0029] The content of component (A) is preferably greater than 0 mass% and not more than 50 mass%, more preferably 15 to 50 mass%, more preferably 20 to 45 mass%, and even more preferably 30 to 40 mass%, based on the composition.

[0030] (B) Photoacid generator The composition according to the present invention comprises a photoacid generator (B). Here, component (B) releases an acid upon irradiation with light. Preferably, the acid from component (B) acts on component (A) to increase the solubility of component (A) in an alkaline aqueous solution. For example, if component (A) has an acid group protected by a protecting group, the protecting group is removed by the acid. The component (B) used in the composition according to the present invention can be selected from conventionally known compounds.

[0031] Upon exposure, the component (B) 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, and even more preferably -16 to 1.1.

[0032] The component (B) is preferably represented by formula (B-1) or formula (B-2).

[0033] Formula (B-1) is as follows: B n+ Cation B n- Anion (B-1) where: B n+ The cation is a cation represented by formula (BC1), a cation represented by formula (BC2), or a cation represented by formula (BC3), and B n+ The cation as a whole has a valence of n, where n is 1 to 3, preferably 1 or 2, and more preferably 1; B n- The anion is an anion represented by formula (BA1), an anion represented by formula (BA2), an anion represented by formula (BA3), or an anion represented by formula (BA4), and B n- The anion as a whole has a valence of n.

[0034] Equation (BC1) is as follows: [ka] where: R b1 are each independently, C 1-6Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, or C 6-12 Aryloxy is 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 and all R b1 In another preferred embodiment, nb1 is 0.

[0035] Specific examples of formula (BC1) are as follows: [ka]

[0036] Equation (BC2) is as follows: [ka] where: R b2 are each independently, C 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 aryl, preferably C 4-6 It is preferably alkyl having a branched structure, more preferably t-butyl or 1,1-dimethylpropyl, and even more preferably t-butyl. Each nb2 is independently 0, 1, 2 or 3, and preferably 1.

[0037] A specific example of formula (BC2) is as follows: [ka]

[0038] Equation (BC3) is as follows: [ka] where: R b3 are each independently, C 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, C 1-6 It is alkyl, preferably methyl or ethyl, more preferably methyl. Each nb3 independently represents 0, 1, 2 or 3, and more preferably 3.

[0039] A specific example of formula (BC3) is as follows: [ka]

[0040] B n+ The cation is preferably selected from the group consisting of cations represented by formula (BC1) or (BC2) because it exerts a better effect.

[0041] Equation (BA1) is as follows: [ka] where R b5 are each independently, C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, 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 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.

[0042] Specific examples of formula (BA1) are as follows: [ka]

[0043] 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 C 2-6 fluorine-substituted alkyl, more preferably C 2-3 R is preferably a fluorine-substituted alkyl, and more preferably a C3 fluorine-substituted alkyl. b6 In the fluorine-substituted alkyl of the formula R, all of the 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, and even more preferably butyl. b6 The alkyl portion of is preferably straight chain. nb4 is 1 or 2, preferably 1. If nb4 is 2, R b6 becomes bivalent, and the above R b6 From this, the hydrogen or fluorine is single-bonded to the S atom.

[0044] Specific examples of formula (BA2) are as follows: CF3SO3 - , C4F9SO3 - , C3F7SO3 - [ka]

[0045] Equation (BA3) is as follows: [ka] where: R b7 are each independently, 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 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, and 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 ring or a polycyclic ring, but is preferably a monocyclic structure having 5 to 8 members.

[0046] Specific examples of formula (BA3) are as follows: [ka]

[0047] Equation (BA4) is as follows: [ka] where: R b8 is hydrogen, C 1-6 Alkyl, C 1-6 alkoxy, or hydroxy; Preferably it is 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. nb5 is an integer of 0 to 10, and is preferably 0. nb6 is an integer of 0 to 21, and is preferably 4, 5 or 6.

[0048] Specific examples of formula (BA4) are as follows: [ka]

[0049] Equation (B-2) is as follows: [ka] where: R b9 is C 1-5 fluorine-substituted alkyl, preferably C 1-4 and alkyl in which all hydrogen atoms at C1 or C4 are substituted with fluorine atoms. R b10 are each independently, C 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), C 2-10 Thioalkyl, C 5-10 saturated heterocyclic ring, preferably C 3-12 Alkenyl or alkynyl, C 3-5 Thioalkyl, C 5-6The saturated heterocycle is 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). nb7 is 0, 1 or 2, preferably 0 or 1, and more preferably 0. In one preferred embodiment, nb7=1.

[0050] Specific examples of formula (B-2) include the following. [ka]

[0051] The molecular weight of the photoacid generator (B) is preferably 400 to 2,500, and more preferably 400 to 1,500.

[0052] The component (B) may be one type or two or more types. The content of component (B) is preferably greater than 0 mass% and equal to or less than 20 mass%, more preferably 0.05 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.5 to 1.5 mass%, based on the total mass of component (A).

[0053] (C) Solvent The composition according to the present invention comprises (C) a solvent. The solvent (C) contains propylene glycol monomethyl ether (PGME) (C-1), and the content of PGME (C-1) is greater than 50 mass% and not more than 100 mass%, preferably 60 to 95 mass%, and more preferably 65 to 90 mass%, based on the solvent (C).

[0054] The solvent (C) preferably further comprises a solvent (C-2) other than the solvent (C-1). The solvent (C-2) is selected from the group consisting of an alcohol solvent (C-2-1) and a low-boiling point solvent (C-2-2). The alcohol solvent (C-2-1) is a compound in which the hydrogen atoms of a chain or alicyclic hydrocarbon are substituted with hydroxy, and the methylene may be replaced with oxy or carbonyl, and the hydrogen atom may be replaced with aryl. The content of the solvent (C-2) is 0% by mass or more and less than 50% by mass, preferably 5 to 45% by mass, and more preferably 10 to 35% by mass, based on the solvent (C).

[0055] Examples of the alcohol solvent (C-2-1) include methanol, ethanol, n-propanol, i-propanol (isopropyl alcohol, IPA), n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6 -Dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene The alkyl esters are selected from the group consisting of pyrene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, 4-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-2-pentanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 3-methyl-2-hexanol, 2-methyl-2-hexanol, ethyl lactate (EL), propyl lactate, n-butyl lactate, n-amyl lactate, butyric acid, methyl 2-hydroxyisobutyrate, methyl 2-hydroxybutyrate, methyl 3-hydroxybutyrate, methyl 4-hydroxybutyrate, ethyl 2-hydroxyisobutyrate, ethyl 2-hydroxybutyrate, ethyl 3-hydroxybutyrate, and ethyl 4-hydroxybutyrate, preferably IPA and / or EL.

[0056] The boiling point of the low-boiling point solvent (C-2-2) is preferably 80 to 130°C, more preferably 80 to 110°C, and even more preferably 80 to 100°C under 1 atmospheric pressure. The low-boiling point solvent (C-2-2) is, for example, selected from the group consisting of n-propanol, i-propanol (IPA), n-butanol, i-butanol, sec-butanol, t-butanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, ethylene glycol monomethyl ether, 2-methyl-2-pentanol, 3-methyl-2-butanol, 2-methyl-2-butanol, propylene glycol dimethyl ether, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone, and is preferably IPA and / or propylene glycol dimethyl ether.

[0057] The solvent (C) may further contain a solvent (C-3) other than the solvents (C-1) and (C-2). Examples of the solvent (C-3) include propylene glycol monomethyl ether acetate (PGMEA) and N-methylpyrrolidone. The content of solvent (C-3) is less than 50% by mass, preferably 0 to 35% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass, based on solvent (C). A preferred embodiment of the present invention is one in which no solvent (C-3) is contained.

[0058] It has been found that when forming a resist pattern, as the film thickness increases, hollows tend to form at the top of the resist pattern walls. According to the present invention, hollows can be suppressed. Without being bound by theory, this is thought to be due to the following. When attempting to form a resist film with a very large thickness of 11.0 to 50.0 μm, the solvent on the surface of the film evaporates and hardens first, acting as a lid, with the solvent remaining under the lid and resulting in areas where the density of the solid components of the film (e.g., alkali-soluble resin (A)) is reduced. The areas with reduced density are more susceptible to diffusion of acid from the photoacid generator (B), and acid is thought to diffuse from the exposed areas even into unexposed areas. For example, although outside the scope of the present invention, if a resist composition containing a large amount of a high-boiling-point solvent (such as PGMEA) and using a low-boiling-point solvent (such as PGME) as a secondary solvent is used to produce a resist film with a thickness of 11 to 50 μm, after applying this resist composition to a substrate and pre-baking, the low-boiling-point solvent will evaporate first, and then the upper part of the resist film will harden and act as a lid, leaving some of the high-boiling-point solvent behind. It is thought that the diffusion of acid into such areas of reduced density in the unexposed areas will cause those areas to dissolve significantly during development, resulting in a hollowed-out shape. Without being bound by theory, it is believed that the above phenomenon is less likely to occur when the composition of the present invention is used, since the main solvent is PGME, a low-boiling point solvent. Furthermore, when PGME is combined with a solvent selected from the group consisting of low-boiling point solvents (C-2-2), it is possible to prevent PGME from evaporating significantly before the other solvents, making it less likely that the solvent will remain in the resist film. When PGME is combined with an alcohol solvent (C-2-1), since both are alcohol-based, the azeotropic phenomenon promotes solvent evaporation, making it less likely that the solvent will remain in the film. Reducing the amount of solvent remaining in the film suppresses the diffusion of acid into unexposed areas, making them less likely to react with the developer, and thus suppressing gouging.

[0059] The content of the (C) solvent is preferably 20% by mass or more and less than 100% by mass, more preferably 50 to 79% by mass, and even more preferably 55 to 65% by mass, based on the composition.

[0060] (D) Basic compounds The composition according to the present invention may further contain (D) a basic compound. The component (D) is expected to have the effect of suppressing the diffusion of acid generated in exposed areas, and by adding a base to the composition, it is expected to have the effect of suppressing acid deactivation on the film surface due to amine components contained in the air. The component (D) is preferably ammonia, C 1-16 Primary aliphatic amine compounds, C 2-32 Secondary aliphatic amine compounds, C 3-48 Tertiary aliphatic amine compounds, C6-30 Aromatic amine compounds, or C 5-30 It is a heterocyclic amine compound. C 1-16 Examples of primary aliphatic amine compounds include methylamine, ethylamine, isopropylamine, tert-butylamine, cyclohexylamine, ethylenediamine, and tetraethylenediamine. C 2-32 Examples of secondary aliphatic amine compounds include dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, and N,N-dimethylmethylenediamine. C 3-48 Examples of tertiary aliphatic amine compounds include trimethylamine, triethylamine, dimethylethylamine, triisobutylamine, triethanolamine, tri-n-octylamine, tricyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, tris[2-(dimethylamino)ethyl]amine, and tris[2-(2-methoxyethoxy)ethyl]amine. C 6-30 Examples of aromatic amine compounds include aniline, benzylamine, naphthylamine, N-methylaniline, 2-methylaniline, 4-aminobenzoic acid, and phenylalanine. C 5-30 Examples of heterocyclic amine compounds include pyrrole, oxazole, thiazole, imidazole, 4-methylimidazole, pyridine, methylpyridine, butylpyridine, and 1,4-diazabicyclo[2.2.2]octane.

[0061] The molecular weight of the component (D) is preferably 17-500, and more preferably 60-400. The component (D) may be one type or two or more types. The content of the component (D) is preferably 0.01 to 3 mass %, more preferably 0.03 to 1 mass %, and even more preferably 0.05 to 0.5 mass %, based on the total mass of the component (A).

[0062] (E) Surfactant The composition according to the present invention may further comprise a surfactant (E). Component (E) can improve the applicability of the composition. Examples of component (E) include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0063] 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), MEGAFACE (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-hexyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0064] Examples of the anionic surfactant include ammonium salts or organic amine salts of alkyldiphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyldiphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkylbenzenesulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfate, and ammonium salts or organic amine salts of alkyl sulfate.

[0065] Further, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauric acid amidopropyl hydroxysulfone betaine.

[0066] The component (E) may be one type or two or more types. The content of the component (E) is preferably 0.0001 to 1 mass %, more preferably 0.001 to 1 mass %, and even more preferably 0.05 to 0.5 mass %, based on the component (A).

[0067] (F) Plasticizer The composition according to the present invention may further contain a plasticizer (F). By containing the component (F), film cracking during thick film formation can be suppressed. Examples of component (F) include alkali-soluble vinyl polymers and vinyl polymers containing an acid-dissociable group. More specific examples include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoate, polyvinyl ether, polyvinyl butyral, polyvinyl alcohol, polyether ester, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, maleic polyimide, polyacrylamide, polyacrylonitrile, polyvinyl phenol, novolak, and copolymers thereof, with polyvinyl ether, polyvinyl butyral, and polyether ester being more preferred.

[0068] The composition provided by the present invention can achieve good physical properties even when the component (F) is present in a film thickness of at least 11 to 50 μm. The content of the component (F) is preferably 0 to 3 mass %, more preferably 0 to 1 mass %, based on the composition. A preferred embodiment of the present invention is one in which the composition is substantially free of the component (F). Another preferred embodiment of the present invention is one in which the composition is free of the component (F) (0.0 mass %). Without being bound by theory, it is believed that a low content of the component (F) can improve the etching resistance and heat resistance of the resist film, and / or improve the shape of the resist pattern. An improvement in the shape of the resist pattern more preferably means an improvement in the shape of the pattern top.

[0069] (G) Additives The composition according to the present invention may contain an additive (G) other than (A) to (F). Component (G) is selected from the group consisting of a surface smoothing agent, a photoreaction quencher, a dye, a contrast enhancer, an acid, a radical generator, a substrate adhesion enhancer, and an antifoaming agent. The content of component (G) (or the sum of the contents when multiple components are present) is preferably 0.01 to 10 mass %, more preferably 0.1 to 2 mass %, based on component (A). A preferred embodiment of the present invention is one in which no component (G) is present (0 mass %).

[0070] The photoreactive quencher can be used to suppress inactivation of the acid on the resist film surface by components such as amines contained in the air, and is different from the photoacid generator (B). In a preferred embodiment of the present invention, the acid that acts directly on the alkali-soluble resin (A) is not a photoreactive quencher but an acid released from the photoacid generator (B). The photoreactive quencher releases an acid upon exposure to light, and the acid preferably has an acid dissociation constant pKa(H2O) of 1.5 to 8 (more preferably 1.5 to 5). The photoreactive quencher is composed of a cation and an anion, and specific examples of the cation and anion include the following. [ka]

[0071] Resist film manufacturing method 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 above a substrate; (2) Heating the composition to form a resist film. The compound comprises: An embodiment of the manufacturing method according to the present invention will be described below.

[0072] Process (1) The composition according to the present invention is applied by an appropriate method onto a substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, etc.). Here, in the present invention, "above" includes cases where the composition is formed directly onto the substrate and cases where the composition is formed via another layer. For example, a planarizing film or a resist underlayer film may be formed directly onto the substrate, and the composition according to the present invention may be applied directly onto that. A more preferred embodiment is to apply the composition according to the present invention directly onto the substrate (without via another layer). The application method is not particularly limited, and examples include coating methods using a spinner or coater.

[0073] Process (2) After application of the composition, the composition is heated (pre-baked) to form a resist film. The heating in (2) is carried out, for example, by using a hot 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 atmosphere, for example, the temperature of the heating surface of a hot plate. The heating time is preferably 30 to 300 seconds (more preferably 60 to 240 seconds). The heating is preferably carried out in air or a 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 11.0 to 50.0 μm, more preferably 11.0 to 20.0 μm, even more preferably 11.0 to 18.0 μm, and even more preferably 12.0 to 18.0 μm.

[0074] 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). For clarity, steps (1) and (2) are performed before step (3). The numbers in parentheses indicating the steps indicate the order. The same applies hereinafter.

[0075] Process (3) The resist film is exposed through a predetermined mask. The wavelength of the light used for exposure is not particularly limited, but exposure with light having a wavelength of 13.5 to 248 nm is preferred. Specifically, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or extreme ultraviolet light (wavelength 13.5 nm) can be used, with a KrF excimer laser being preferred. These wavelengths allow for a ±1% range. After exposure, a post-exposure bake (PEB) can be performed as needed. The post-exposure bake temperature is preferably 80 to 150°C, more preferably 100 to 140°C, and the bake time is 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0076] Process (4) The exposed resist film is developed using a developer. Development methods such as paddle development, immersion development, and swing immersion development, which are conventional methods used in developing photoresists, can be used. The developer is 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), preferably a 2.38% by 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 a rinsing treatment can be performed as needed. When a positive resist composition is used, the exposed portions are removed by development, forming a resist pattern. This resist pattern can be further refined by using, for example, a shrink material.

[0077] When a thick resist pattern is formed using a chemically amplified resist, particularly when the aspect ratio is high, hollows may occur at the top of the walls of the resist pattern (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 on the side surface of the resist pattern to the substrate (hereinafter sometimes referred to as the recess width) is less than 1,200 nm, more preferably 0 to less than 800 nm, and even more preferably 0 to less than 500 nm. In the present invention, recession can be suppressed. Suppressing recessed portions is advantageous in that it can strengthen the resistance of the pattern in subsequent processes.

[0078] In addition, the following process (5) Processing using the resist pattern as a mask A processed substrate can be produced by a method comprising:

[0079] Process (5) The formed resist pattern is preferably used to process an underlayer film or a substrate (more preferably a substrate). Specifically, various underlying substrates can be processed using the resist pattern as a mask by dry etching, wet etching, ion implantation, metal plating, or the like. A more preferred embodiment is to etch a substrate by dry etching using the resist pattern of the present invention as a mask. The resist pattern of the present invention can be thickened, so it 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 the resist pattern, the SOC film may be processed using the BARC pattern, and the substrate may be processed using the SOC pattern.

[0080] Thereafter, if necessary, the substrate is further processed, preferably by forming wiring on the processed substrate, to manufacture a device. These processes can be performed using 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 referred to as a device. Examples of devices include semiconductor devices, liquid crystal display elements, organic EL display elements, plasma display elements, and solar cell elements, with semiconductor devices being preferred. [Example]

[0081] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0082] Preparation of Resist Composition 101 PGME and PGMEA were mixed in a mass ratio of 70:30 (=PGME:PGMEA) to obtain a mixed solvent. To this mixed solvent (62.0 mass%), alkali-soluble resin A1 (36.99 mass%), photoacid generator B1 (0.91 mass%), base compound D1 (0.04 mass%), and surfactant E1 (0.06 mass%) were added to obtain a mixed solution. The values ​​in parentheses indicate the content of each component relative to the total mass of the composition. The solid component concentration was 38.0 mass%. The mass ratio of these components was A1:B1:D1:E1 = 100:2.47:0.10:0.15. In the following examples, components other than the solvent are referred to as solid components, and the concentration of the sum of the components other than the solvent in the entire composition is referred to as the solid component concentration. The mixture is stirred at room temperature for 30 minutes to obtain a solution. Complete dissolution of each component is confirmed visually. The obtained solution is filtered through a 0.05 μm filter to obtain resist composition 101. A1: p-hydroxystyrene / styrene / t-butyl acrylate copolymer (Mw=27,000, random copolymer) [ka] B1: The following compound (Sumitomo Pharma Food & Chemical, ZK-0518) [ka] D1: Tris[2-(2-methoxyethoxy)ethyl]amine E1: MEGAFACE R-2011 (DIC)

[0083] Example of resist film formation An 8-inch silicon wafer is subjected to HMDS treatment at 90°C for 60 seconds. The prepared resist composition is spin-coated onto the 8-inch silicon wafer using a coater developer Mark8 (Tokyo Electron). The speed is changed from 1,000 to 3,500 rpm depending on the desired film thickness. The resist film is then baked on a hot plate at 140°C for 180 seconds to obtain a resist film. The film thickness of the obtained resist film is measured using an optical interference film thickness measuring device (M-1210, Dainippon Screen). Following the above procedure, resist composition 101 (solid component concentration: 38.0% by mass) was spin-coated at 1,000 rpm to form a resist film with a thickness of 15.0 μm. In the following examples, depending on the target film thickness, the solid component concentration is adjusted (the mass ratio of each solid component remains the same) or the rotation speed of the spin coating is adjusted. When forming a resist film having a thickness of 8 to 15 μm, composition 101 having a solid component concentration of 38.0 mass % is used as is. The rotation speed of the spin coating is 1,000 rpm for a film thickness of 15 μm and 3,500 rpm for a film thickness of 8 μm. By gradually increasing the rotation speed, the obtained film thickness can be gradually reduced. To form a resist film with a thickness of 4 to 7 μm, the same solvent is added to composition 101 to adjust the solid content to 32.0 mass %. The rotation speed for spin coating is 1,000 rpm for a film thickness of 7 μm, and the desired film thickness is obtained by gradually increasing the rotation speed. To form a resist film with a thickness of 2 to 3 μm, the same solvent is added to composition 101 to adjust the solid content to 19.0 mass %. The rotation speed for spin coating is 1,000 rpm for a film thickness of 3 μm, and the desired film thickness is obtained by gradually increasing the rotation speed. When forming a resist film with a thickness of 1 μm, the same solvent is added to composition 101 to adjust the solid content to 14.0 mass %. The rotation speed for spin coating is 1,000 rpm. The same applies to the change in film thickness, solid component concentration, and rotation speed when using a composition in which the solid component and solvent are changed from composition 101.

[0084] Example of resist pattern formation Using a KrF stepper (FPA3000-EX5, Canon), a 15 μm thick resist film obtained in the resist film formation example described above is exposed to light. Then, PEB is performed on a hot plate at 110°C for 180 seconds. This film is developed for 60 seconds in a 2.38% TMAH aqueous solution (AZ300MIF, Merck Electronics), forming a trench pattern with a line:space ratio of 3:1 and a space width of 5 μm. The cross-sectional shape of the resulting pattern is confirmed using a scanning electron microscope (S9200, Hitachi). When composition 101 (solid component concentration 38.0 mass %) is used to form a resist film with a thickness of 15 μm as in the above resist pattern formation example, a resist pattern with a top width of the pattern wall of 7 μm is obtained. When forming a resist pattern from a resist film having a thickness other than the above, exposure is carried out under the same conditions as for the 15 μm thick resist film. The pattern shape that is formed will be explained using Figure 1. In Figure 1(a), a resist pattern 12 is formed on a substrate 11, with a line width 13, space width 14, and top width 15 of 15 μm, 5 μm, and 7 μm, respectively. The pattern wall top 16 is the edge of the top, and this part can sometimes become hollowed out. The resist film thickness in Figure 1(a) is 15 μm. Figure 1(b) is a schematic diagram of the resist pattern when the film thickness is set to 5 μm without changing the slope. In the evaluation where the film thickness is changed, a pattern is produced without changing the slope as shown here.

[0085] Pattern wall top evaluation 1 A study is conducted to change the solvent. Composition 101 (solid component concentration 38.0 mass%) is used to form a resist film with a thickness of 15 μm as in the resist film formation example, and a resist pattern is formed as in the resist pattern formation example. A section of this sample is prepared and observed with an SEM. The degree to which the pattern is hollowed out inward from the top (digging-in width) is evaluated. A specific explanation will be given using Figure 2. Figure 2 schematically shows the wall top 21 of Figure 1. A line is drawn perpendicular to the substrate from the edge of the top of the pattern. A line is drawn perpendicular to the substrate from the most hollowed point on the side of the pattern. The distance between each line is the embedding width. The result is Example 101. The evaluation criteria are as follows: A: The bite width is less than 500 nm B: Biting width is 500nm or more and less than 800nm C: Biting width is 800nm ​​or more and less than 1,200nm D: The distance of the gouge is 1,200 nm or more The evaluation results are shown in Table 1. [Table 1] PGME: Propylene glycol monomethyl ether (boiling point 119°C) PGMEA: Propylene glycol 1-monomethyl ether 2-acetate (boiling point 146°C) IPA: Isopropyl alcohol (boiling point 83°C) EL: Ethyl lactate (boiling point 154°C) MMPOM: Propylene glycol dimethyl ether (boiling point 97°C)

[0086] The compositions shown in Table 1 were prepared in the same manner as in the preparation example of resist composition 101, except that the solvent was changed as shown in Table 1. The solid component and the solid component concentration of 38.0 mass% were not changed. A resist film with a thickness of 15 μm was formed using these as described in the resist film formation example, and a resist pattern was then formed as described in the resist pattern formation example. Slices of these samples were prepared and observed with an SEM. The evaluation of composition 102 corresponds to Example 102. The same applies hereinafter. The evaluation results are shown in Table 1.

[0087] Pattern wall top evaluation 2 A study was conducted to change the solvent mixing ratio and resist film thickness. Each solvent was prepared by mixing PGME and PGMEA in the ratios shown in Table 2. Similar to composition 101, each composition was obtained by adding the solvent so that the mass ratio was A1:B1:D1:E1 = 100:2.47:0.10:0.15. The solid component concentration and rotation speed were changed as described in the resist film formation example, and a resist film with a thickness of 5 to 15 μm was obtained. Resist patterns were formed as described in the resist pattern formation example. Sections of these samples were prepared and observed using an SEM. The bite width (nm) was evaluated in the same manner as in Evaluation of Pattern Wall Top 1. The results are shown in Table 2. [Table 2]

[0088] Crack Evaluation A study was conducted to change the polymer Mw and film thickness. A resin identical to Resin A1 was prepared, except for the Mw listed in Table 3. PGME and PGMEA were mixed in a mass ratio of 70:30 (=PGME:PGMEA) to obtain a solvent. Similar to composition 101, the solvent was added so that the mass ratio of A1:B1:D1:E1 was 100:2.47:0.10:0.15. The solid component concentration and rotation speed were changed as described in the resist film formation example to obtain the desired film thickness. A resist pattern was then formed using these materials in the same manner as in the resist pattern formation example described above. The wafer on which the resist pattern was formed was visually observed and the evaluation criteria were as follows: A: No cracks found. B: Cracks are found. [Table 3]

[0089] Preparation of resist composition 201 Composition 201 (solid content: 38.0% by mass) is obtained by carrying out the same procedure as in the preparation example of composition 101, except that 100% PGME is used as the solvent.

[0090] heat resistance The procedure is carried out in the same manner as in the resist film formation example, and a resist film having a thickness of 15 μm is formed from composition 201. This is then treated in the same manner as in the resist pattern formation example to obtain a resist pattern. Samples were then prepared by additional baking at different temperatures. The additional baking time was standardized to 60 seconds. Sections of these resist patterns were observed with an SEM. No changes were observed in the resist pattern when the additional baking was at 100°C. Similarly, no changes were observed in the resist pattern when the additional baking was at 120°C or 140°C. However, a change in the shape of the resist pattern was observed when the additional baking was at 160°C. A change in the shape of the resist pattern was also observed when the additional baking was at 180°C, which is thought to be due to partial liquefaction of the top of the pattern.

[0091] Preparation of resist composition 301 PGME and PGMEA are mixed in a mass ratio of 70:30 (=PGME:PGMEA) to obtain a mixed solvent. The alkali-soluble resin A2 is used. The alkali-soluble resin A2, photoacid generator B1, base compound D1, surfactant E1, and plasticizer F1 are added to a solvent in a mass ratio of A1:B1:D1:E1:F1 = 100:2.47:0.10:0.15:20 to obtain a mixed solution with a solid concentration of 38.0 mass%. The mixed solution is stirred at room temperature for 30 minutes to obtain a solution. Complete dissolution of each component is confirmed visually. The resulting solution is filtered through a 0.05 μm filter to obtain resist composition 301. A2: p-hydroxystyrene / styrene / t-butyl acrylate copolymer (Mw=18,000, random copolymer) [ka] Formula 1 [ka] (x+z):y=60:40, block copolymer, Mw 3,600

[0092] Etching resistance The procedure is carried out in the same manner as in the resist film formation example, and a resist film having a thickness of 15 μm is formed from each of composition 201 and composition 301. These are then subjected to the procedure in the resist pattern formation example to obtain a resist pattern. The etching equipment used is NE-5000N (ULVAC). For O2 etching, the chamber pressure is set to 10 Pa, power to 500 W, bias to 100 W, gas flow rates are O2 (30 sccm), N2 (5 sccm), and He (266 sccm), and each film on the wafer is dry etched for 30 seconds. In CF4 etching, the chamber pressure is set to 10 Pa, power to 500 W, bias to 100 W, gas flow rates are CF4 (45 sccm) and He (266 sccm), and each film on the wafer is dry etched for 30 seconds. The film thickness is measured using an optical interference film thickness measuring device (M-1210, Dainippon Screen). The film thickness is measured before and after etching, and the difference between the former and the latter is calculated to calculate the etching rate per unit time. The etching rates of O2 etching and CF4 etching for composition 301 are set to 100%, while the O2 etching rate for composition 201 is 75% and the CF4 etching rate is 82%. Comparing composition 201 and composition 301, it can be seen that the resist film formed from composition 201 has improved etching resistance. [Explanation of symbols]

[0093] 11. Circuit board 12. Resist pattern 13. Line Width 14.Space width 15.Top width 16. Pattern wall top 21. Wall top 22.Bite width

Claims

1. A thick-film chemically amplified positive resist composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C): where: The thickness of the resist film formed from the thick-film chemically amplified positive resist composition is 11.0 to 50.0 μm; The alkali-soluble resin (A) contains at least one of the following repeating units: 【Chemistry 1】 (where, R １１ , R ２１ , R ４１ and R ４５ are each independently C １－５ Alkyl (wherein —CH ２ - may be replaced by -O-; R １２ , R １３ , R １４ , R ２２ , R ２３ , R ２４ , R ３２ , R ３３ , R ３４ , R ４２ , R ４３ and R ４４ are each independently hydrogen, C １－５ Alkyl, C １－５ alkoxy, or —COOH; p11 is 0 to 4, p15 is 1 to 2, and p11 + p15 ≦ 5; p21 is 0-5; p41 is 0 to 4, p45 is 1 to 2, and p41 + p45 ≦ 5; P ３１ is C ４－２０ alkyl (wherein part or all of the alkyl may form a ring, and part or all of the H of the alkyl may be substituted with halogen); and The solvent (C) contains propylene glycol monomethyl ether (PGME) (C-1), and the content of PGME (C-1) is more than 50 mass % and 100 mass % or less based on the solvent (C).

2. The composition of claim 1, wherein the solvent (C) further comprises a solvent (C-2): where: The solvent (C-2) is selected from the group consisting of alcohol solvents (C-2-1) and low boiling point solvents (C-2-2).

3. 3. The composition according to claim 1, wherein the alkali-soluble resin (A) has a mass average molecular weight of 12,000 to 50,000.

4. The number of repeating units n of the repeating units (A-1), (A-2), (A-3), and (A-4) in the alkali-soluble resin (A) Ａ－１ , n Ａ－２ , n Ａ－３ , and n Ａ－４ but, n Ａ－１ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ )=40~80%、 n Ａ－２ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ )=0~40%、 n Ａ－３ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) = 0 to 40%, or n Ａ－４ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ )=0~40% The composition according to at least one of claims 1 to 3, which is: Optionally, the total number n of all repeating units contained in the alkali-soluble resin (A) ｔｏｔａｌ Then, (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) / n ｔｏｔａｌ =80~100% Meet the following.

5. The composition according to claim 1 , wherein the photoacid generator (B) is represented by formula (B-1) or formula (B-2): B ｎ＋ Cation B ｎ－ Anion (B-1) where: B ｎ＋ The cation is a cation represented by formula (BC1), a cation represented by formula (BC2), or a cation represented by formula (BC3), and B ｎ＋ the cation as a whole is n-valent, n being 1 to 3; B ｎ－ The anion is an anion represented by formula (BA1), an anion represented by formula (BA2), an anion represented by formula (BA3), or an anion represented by formula (BA4), and B ｎ－ The anion as a whole has a valency of n. 【Chemistry 2】 (where, R ｂ１ are each independently C １－６ Alkyl, C １－６ Alkoxy, C ６－１２ Aryl, C ６－１２ arylthio, or C ６－１２ is aryloxy, nb1 is independently 0, 1, 2 or 3. 【Transformation 3】 (where, R ｂ２ are each independently C １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ is aryl, nb2 is independently 0, 1, 2 or 3. 【Chemistry 4】 (where, R ｂ３ are each independently C １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ is aryl, R ｂ４ are each independently C １－６ is alkyl, nb3 is independently 0, 1, 2 or 3. 【Transformation 5】 (where R ｂ５ are each independently C １－６ Fluorine-substituted alkyl, C １－６ fluorine-substituted alkoxy, or C １－６ alkyl) 【Transformation 6】 (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, and nb4 is 1 or 2. 【Transformation 7】 (where, R ｂ７ are each independently 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, wherein two R ｂ７ may be bonded to each other to form a fluorine-substituted heterocyclic structure) 【Transformation 8】 (where, R ｂ８ is hydrogen, C １－６ Alkyl, C １－６ alkoxy, or hydroxy; L ｂ is carbonyl, oxy or carbonyloxy, Y ｂ are each independently hydrogen or fluorine, nb5 is an integer from 0 to 10, and nb6 is an integer from 0 to 21. 【Chemistry 9】 where: R ｂ９ is C １－５ is a fluorine-substituted alkyl; R ｂ１０ are each independently C ３－１０ Alkenyl or alkynyl (wherein CH in alkenyl and alkynyl) ３ - may be substituted by phenyl, -CH in alkenyl and alkynyl ２ - may be replaced by at least one of -C(=O)-, -O-, and phenylene), C ２－１０ Thioalkyl, C ５－１０ is a saturated heterocyclic ring, nb7 is 0, 1 or 2.

6. The composition according to at least one of claims 1 to 5, further comprising a basic compound (D): Optionally, the basic compound (D) is ammonia, C １－１６ Primary aliphatic amine compounds, C ２－３２ Secondary aliphatic amine compounds, C ３－４８ Tertiary aliphatic amine compounds, C ６－３０ Aromatic amine compounds, or C ５－３０ It is a heterocyclic amine compound.

7. The composition according to at least one of claims 1 to 6, further comprising a surfactant (E): optionally further comprising a plasticizer (F); or Optionally, the composition further comprises an additive (G), which is at least one selected from the group consisting of a surface smoothing agent, a photoreaction quencher, a dye, a contrast enhancing agent, an acid, a radical generator, a substrate adhesion enhancing agent, and an antifoaming agent.

8. the content of the alkali-soluble resin (A) is greater than 0 mass% and not more than 50 mass% based on the composition; The content of the photoacid generator (B) is more than 0 mass% and 20 mass% or less based on the alkali-soluble resin (A), and The composition according to at least one of claims 1 to 7, wherein the content of the solvent (C) is 20 mass% or more and less than 100 mass% based on the composition: optionally, the content of the basic compound (D) is 0.01 to 3 mass% based on the alkali-soluble resin (A); optionally, the content of the surfactant (E) is 0.0001 to 1% by mass based on the alkali-soluble resin (A); Optionally, the content of plasticizer (F) is 0 to 3% by weight based on the composition; or Optionally, the content of the additive (G) is 0.01 to 10% by mass based on the alkali-soluble resin (A).

9. The alcohol solvent (C-2-1) is methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol 4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, 4-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-2-pentanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 3-methyl-2-hexanol, 2-methyl-2-hexanol, ethyl lactate, propyl lactate, n-butyl lactate, n-amyl lactate, butyric acid, methyl 2-hydroxyisobutyrate, methyl 2-hydroxybutyrate, methyl 3-hydroxybutyrate, methyl 4-hydroxybutyrate, ethyl 2-hydroxyisobutyrate, ethyl 2-hydroxybutyrate, ethyl 3-hydroxybutyrate and ethyl 4-hydroxybutyrate; and The composition according to at least one of claims 1 to 8, wherein the low-boiling point solvent (C-2-2) has a boiling point of 80 to 130°C under 1 atmosphere: Optionally, the low boiling point solvent (C-2-2) is selected from the group consisting of n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, ethylene glycol monomethyl ether, 2-methyl-2-pentanol, 3-methyl-2-butanol, 2-methyl-2-butanol, propylene glycol dimethyl ether, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone.

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

11. A method for producing a resist film, comprising the following steps: (1) applying the composition according to at least one of claims 1 to 10 above a substrate; and (2) Heating the composition to form a resist film: optionally, the resist film has a thickness of 11.0 μm to 20 μm; Optionally, the heating in (2) is carried out for 100 to 250°C and / or 30 to 300 seconds; or Optionally, the heating in (2) is carried out in air or nitrogen gas atmosphere.

12. A method for producing a resist pattern, comprising the steps of: A resist film is formed by the method according to claim 11. (3) exposing the resist film; and (4) The resist film is developed.

13. 13. The method for producing a resist pattern according to claim 12, wherein the distance between a perpendicular line from an end point of the top of the resist pattern to the substrate and a perpendicular line from the most recessed point on the side surface of the resist pattern to the substrate is less than 1,200 nm.

14. A method for producing a processed substrate comprising the steps of: A resist pattern is formed by the method according to claim 12 or 13. (5) Processing using the resist pattern as a mask: Optionally, (5) processes the underlayer film or substrate.

15. A method for manufacturing a device, comprising the method according to at least one of claims 11 to 14. Optionally, further comprising forming wiring on the processed substrate; or Optionally, the device is a semiconductor device.

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