Substrate-coating resist composition and method for producing resist pattern

Abstract

A resist composition for coating a substrate, comprising (A) a polymer having a specific structure and (B) a photoacid generator having a specific structure.

Description

[Technical field]

[0001] The present invention relates to a resist composition for coating a substrate and a method for producing a resist pattern. [Background technology]

[0002] In recent years, the need for high integration of LSIs has been increasing, and finer patterns are being demanded. To meet such needs, lithography processes using short-wavelength light such as KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet light (EUV; 13 nm), X-rays, electron beams, etc. are being put to practical use. To meet such demands for finer resist patterns, photosensitive resin compositions used as resists in fine processing are also required to have high resolution. Finer patterns can be formed by exposure to light with a short wavelength, but high dimensional accuracy is required.

[0003] In the lithography process, a resist pattern is formed by exposing and developing the resist. During exposure, a phenomenon is known in which the light incident on the resist and the light reflected from the substrate or the air interface interfere with each other in multiple ways, generating standing waves. The generation of standing waves reduces the pattern dimensional accuracy. In order to reduce the standing waves, there have been attempts to form an anti-reflective film on the upper and / or lower layers of the resist. The lower anti-reflective film can reduce the influence of reflection from the substrate, and therefore has a large effect of reducing standing waves. However, when the lower anti-reflective film is formed, a removal process is required, and therefore the lower anti-reflective film may not be suitable for some subsequent processing steps, and there is a demand for reducing standing waves without forming a lower anti-reflective film in order to simplify the manufacturing process.

[0004] It has been proposed that by incorporating an organic acid compound into lithography components such as resist, the migration speed of the acid generated by, for example, an acid generator can be suppressed, thereby reducing standing waves (Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2022 / 023230 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have found that there are one or more problems with resist compositions that require improvement, such as the following: when a lower anti-reflective coating is not formed, the effect of reducing standing waves in the resist pattern is low; the resist pattern width is non-uniform; the resist pattern has low rectangularity; the resist pattern has low resolution; the resist pattern has low heat resistance; and the production process is inefficient. [Means for solving the problem]

[0007] The present inventors have surprisingly found that standing waves can be reduced by increasing the diffusion of the acid of a photoacid generator contained in a resist composition. The present invention provides a substrate-coating resist composition comprising a polymer (A) and a photoacid generator (B), Polymer (A) comprises at least one repeating unit represented by formula (A-1) and (A-2), and optionally further comprises at least one repeating unit represented by formula (A-3) and (A-4); The resist composition contains a photoacid generator (B) represented by formula (B-1). [ka] Where: C y 11 and C y 21 are each independently aryl or heteroaryl having 5 or 6 ring atoms; R 11 , R 21 , R 41 and R45 are each independently C 1-5 alkyl, in which methylene may be replaced by oxy; 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 to 5; p41 is 0-4, p45 is 1-2, and p41+p45≦5; P 31 is C 4-20 Here, a part or all of the alkyl may form a ring, a part or all of the H in the alkyl may be substituted with a halogen, and a methylene in the alkyl may be substituted with an oxy or a carbonyl. B n+ Cation B n- Anion (B-1) Where: B n+ The cations are n-valent overall, B n- The anion as a whole has a valency of n, where n is 1 to 3; B n- The anion is an anion represented by formula (BA-1), [ka] Where: C y a is a hydrocarbon ring having 5 or 6 ring atoms, one of which may be replaced by nitrogen; L a1is C 1-5 is alkylene, R a2 is nitro or cyano R a3 is unsubstituted or fluorine-substituted, C 1-10 is alkyl, na1 is 0 or 1, na2 is a number from 0 to 3, na3 is a number between 0 and 3.

[0008] The method for producing a resist pattern according to the present invention comprises the following steps. (1) applying the composition directly onto a substrate; (2) heating the composition to form a resist layer; (3) exposing the resist layer; (4) post-exposure baking the resist layer; and (5) developing the resist layer.

[0009] A method for producing a device according to the present invention comprises the method described above. Effect of the Invention

[0010] According to the present invention, one or more of the following effects can be expected: Even when a lower anti-reflective coating is not formed, the effect of reducing standing waves in the resist pattern is high; the resist pattern has a uniform width; the resist pattern has high rectangularity; the resist pattern has high resolution; the resist pattern has high heat resistance; and the manufacturing process is highly efficient. [Brief description of the drawings]

[0011] [Figure 1] Figure 1 is a conceptual diagram showing the cross-sectional shape of a negative resist pattern when affected by standing waves. [Diagram 2] FIG. 2 is a conceptual diagram showing the cross-sectional shape of a negative resist pattern when not affected by standing waves. [Diagram 3] FIG. 1 is a conceptual diagram showing a cross-sectional shape of a trench pattern. [Figure 4] A conceptual diagram showing the cross-sectional shapes of trench patterns with different Wt / Wb. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The embodiment of the present invention will be described in detail below.

[0013] [Definition] In this specification, unless otherwise specifically stated, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "a" or "the" means "at least one." An element of a concept may be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of the elements as well as its use alone. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "C x-y ", "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown by structural formulas, the n or m in parentheses indicates the number of repeats. Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to a compound having that function (for example, in the case of a base generator, it is a compound that generates a base). There may be an embodiment in which the compound is dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, such a solvent is preferably contained in the composition according to the present invention as the solvent (C) or another component.

[0014] <Substrate-coating resist composition> The substrate coating resist composition of the present invention (hereinafter sometimes simply referred to as the composition) comprises a polymer (A) and a photoacid generator (B). In the present invention, the substrate-coating resist composition refers to a resist composition that coats a substrate without an underlying antireflective film. In the present invention, the substrate may be a single layer or a laminate, and may have a structure such as a groove formed thereon. The composition according to the present invention is preferably a substrate-coating chemically amplified resist composition, more preferably a substrate-coating chemically amplified KrF resist composition. The composition according to the present invention can be used as either a positive-type or a negative-type. In a preferred embodiment of the present invention, the composition according to the present invention is a substrate-coating chemically amplified positive-type KrF resist composition. In another preferred embodiment of the present invention, the composition according to the present invention is a substrate-coating chemically amplified negative-type KrF resist composition.

[0015] Polymer (A) The composition according to the present invention comprises a polymer (A) (hereinafter, sometimes referred to as component (A), the same applies to other components). The polymer (A) comprises at least one of repeating units represented by formulae (A-1) and (A-2), and optionally further comprises at least one of repeating units represented by formulae (A-3) and (A-4). More preferably, the polymer (A) comprises a repeating unit represented by formula (A-1), and further comprises at least one of repeating units represented by formulae (A-3) and (A-4).

[0016] Formula (A-1) is as follows: [ka] Where: C y 11 are each independently aryl or heteroaryl having 5 or 6 ring atoms, preferably benzene. R 11 are each independently C 1-5 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 carbons 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, and preferably 1, provided that p11+p15≦5.

[0017] Polymer (A) can contain multiple repeating units represented by formula (A-1). For example, it can contain a 1:1 ratio of a structural unit with p15=1 and a structural unit with p15=2. In this case, p15=1.5 as a whole. Hereinafter, unless otherwise specified, the same applies to the numbers expressing polymers in the present invention.

[0018] Specific examples of formula (A-1) include the following. [ka]

[0019] Formula (A-2) is as follows. [ka] Where: C y 21 are each independently aryl or heteroaryl having 5 or 6 ring atoms, preferably benzene. R 21 are each independently C 1-5 It is alkyl (wherein methylene in the alkyl may be replaced by oxy), preferably methyl, ethyl, t-butyl or t-butoxy, more preferably methyl or ethyl, more preferably 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 an integer of 0 to 5, preferably 0, 1, 2, 3, 4 or 5, more preferably 0 or 1, and even more preferably 0.

[0020] Specific examples of formula (A-2) include the following. [ka]

[0021] Equation (A-3) is as follows. [ka] Where: R 32 , R 33 and R 34 are each independently hydrogen, C 1-5 Alkyl, C 1-5Alkoxy, 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 It is an alkyl. Here, a part or all of the alkyl may form a ring, a part or all of the H of the alkyl may be substituted with a halogen, and a methylene in the alkyl may be replaced with an oxy or carbonyl. Here, a part or all of the alkyl may form a ring, a part or all of the H of the alkyl may be substituted with a halogen, and a methylene in the alkyl may be replaced with an oxy or carbonyl. P 31 The alkyl portion of P is preferably branched or cyclic. 31 C 4-20 When the alkyl is substituted with a halogen, it is preferable that all of the alkyl groups are substituted, and the halogen group is preferably F or Cl, and more preferably F. 31 C 4-20 In a preferred embodiment of the present invention, H in the alkyl group is not substituted with a 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 still more preferably t-butyl.

[0022] Specific examples of formula (A-3) include the following. [ka]

[0023] 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 methyl, ethyl or t-butyl, more preferably methyl. R 45 are each independently C 1-5 Alkyl (wherein methylene in the alkyl may be replaced by oxy), preferably methyl, t-butyl or -CH(CH 3 )-O-CH 2 CH 3 It is. 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 an integer of 0 to 4, more preferably 0 or 1, and further preferably 0. p45 is 1 to 2, and more preferably 1. p41+p45≦5.

[0024] Specific examples of formula (A-4) include the following. [ka]

[0025] The number of repeating units n of the repeating units (A-1), (A-2), (A-3) and (A-4) in the polymer (A) A-1 , n A-2 , n A-3 and n A-4 The following explains this. n A-1 / (n A-1 +n A-2 +n A-3 +n A-4) is preferably 0 to 100%, more preferably 50 to 80%, even more preferably 55 to 75%, and still more preferably 55 to 65%. n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0 to 100%, more preferably 0 to 30%, even more preferably 5 to 25%, and still more preferably 15 to 25%. n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0 to 50%, more preferably 10 to 40%, even more preferably 15 to 35%, and still more preferably 15 to 25%. n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0 to 50%, more preferably 0 to 30%, even more preferably 0 to 10%, and even more preferably 0 to 5%. A-4 In a preferred embodiment of the present invention, n is 0. 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 ) = 10 to 50%, and n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 )=0 to 40% is a preferred embodiment.

[0026] The polymer (A) may contain additional repeating units other than the repeating units represented by (A-1), (A-2), (A-3) and (A-4). The total number of all repeating units contained in the polymer (A), n 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 further preferably 95 to 100%. In one suitable embodiment of the polymer (A), no further repeating unit is contained.

[0027] When the composition according to the present invention is a positive resist composition, specific examples of the polymer (A) include the following. [ka]

[0028] When the composition according to the present invention is a negative resist composition, specific examples of the polymer (A) include the following. [ka]

[0029] The mass average molecular weight (hereinafter sometimes referred to as Mw) of polymer (A) is 3,000 to 50,000, more preferably 4,000 to 20,000, even more preferably 10,000 to 19,000, and even more preferably 11,000 to 13,000. Without being bound by theory, it is believed that by having polymer (A) with this Mw, it becomes possible to form a resist pattern with good rectangularity or resolution 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.

[0030] The content of the polymer (A) is preferably from 10 to 40 mass %, more preferably from 12 to 38 mass %, and further preferably from 15 to 36 mass %, based on the total mass of the composition. The composition according to the present invention may contain a polymer other than the polymer (A), but a preferred embodiment is one in which the composition does not contain any polymer other than the polymer (A).

[0031] Photoacid generator (B) The composition according to the present invention comprises a photoacid generator (B) represented by formula (B-1). The composition according to the present invention has a standing wave reducing effect, and without being bound by theory, it is believed that this is due to the following reasons. The anion of the photoacid generator (B) is an anion represented by formula (BA-1) as described below, which contains a hydrocarbon ring having 5 or 6 ring atoms, and the polymer (A) comprises at least one of the repeating units represented by formulas (A-1) and (A-2), which contain an aryl or heteroaryl group. The anions of the photoacid generator (B) each have a ring structure as described above, and therefore have the same structure as the polymer (A). This lowers the energy barrier for the acid to thermally diffuse through the polymer, and does not impede the movement of protons. As a result, the diffusion distance of the acid becomes longer, which is thought to counteract the effects of standing waves on the sidewalls of the pattern, making the sidewalls of the pattern smooth.

[0032] Formula (B-1) is as follows. B n+ Cation B n- Anion (B-1) Where: B n+ The cations are n-valent overall, B n- The anion as a whole has a valency of n, where n is 1 to 3. B n- The anion is an anion represented by the formula (BA-1). [ka] Where: C y a is a hydrocarbon ring having 5 or 6 ring atoms, one of which may be replaced by nitrogen, preferably benzene, pyridine, pyrrole. L a1 is C 1-5 Alkylene, preferably C 1-3 It is preferably alkylene, and more preferably ethylene. R a2 is nitro or cyano, preferably nitro. R a3 is unsubstituted or fluorine-substituted, C 1-10 alkyl, preferably unsubstituted or fluorine-substituted, C 1-8 It is an alkyl. na1 is 0 or 1. na2 is a number of 0 to 3, and preferably 0 or 1. na3 is a number of 0 to 3, and preferably 0, 1 or 2.

[0033] Specific examples of the anion represented by formula (BA-1) include the following. [ka]

[0034] More preferably, B n- The anion is represented by formula (BA-1a). [ka] Where: Ra4 is nitro. R a5 is unsubstituted or fluorine-substituted, C 1-3 It is alkyl, preferably unsubstituted or fluorine-substituted methyl, more preferably methyl. na4 is 0 or 1. na5 is 0, 1 or 2.

[0035] B n+ The cation is not particularly limited as long as it is one that is commonly used as a cation for a photoacid generator, but is preferably selected from the group consisting of cations represented by formula (BC-1), cations represented by formula (BC-2), and cations represented by formula (BC-3), and is preferably the cation represented by formula (BC-1).

[0036] Equation (BC-1) is as follows. [ka] Where: R b1 are each independently 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, or C 6-12 Aryloxy, preferably methyl, ethyl, t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy, more preferably t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy. Each nb1 is independently 0, 1, 2 or 3, preferably 0 or 1, and more preferably 0.

[0037] Specific examples of formula (BC1) include the following. [ka]

[0038] Equation (BC-2) is as follows. [ka] Where: R b2 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 Aryl, preferably C 4-6 Each R in the formula is an alkyl having a branched structure. b2 may be the same or different, but it is more preferable that they are the same. b2 is 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.

[0039] Specific examples of formula (BC2) include the following. [ka]

[0040] Equation (BC-3) is as follows. [ka] Where: R b3 are each independently hydroxy, 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 1-6 alkyl, preferably methyl, ethyl, propyl, or butyl. b4 may be bonded to each other to form a ring structure, and in the case of ring formation, it is preferable to form a 5- or 6-membered alicyclic ring. Each nb3 is independently 0, 1, 2 or 3, preferably 1, 2 or 3, and more preferably 1 or 3. nb4 is 0 or 1, and is preferably 0.

[0041] Specific examples of formula (BC3) include the following. [ka]

[0042] The photoacid generator (B) may contain fluorine, but in consideration of the environmental impact, a form not containing fluorine is also preferred.

[0043] The photoacid generator (B) may be one or two or more types, but is preferably one or two types, and more preferably one type. The content of the photoacid generator (B) is preferably from 0.2 to 5 mass %, more preferably from 1 to 4 mass %, based on the total mass of the polymer (A).

[0044] Solvent (C) The composition according to the present invention may further include a solvent (C). The solvent (C) is not particularly limited as long as it can dissolve each of the components to be blended. The solvent (C) is preferably water, a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or any combination thereof. Specific examples of the solvent include water, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene, 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-Nonylalcohol, 2,6-Dimethylheptanol-4, n-Decanol, sec-U nonyl 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-ethylhexanediol All-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol,Acetophenone, Fenchone, Ethyl Ether, i-Propyl Ether, n-Butyl Ether (Di-n-Butyl Ether, DBE), n-Hexyl Ether, 2-Ethylhexyl Ether, Ethylene Oxide, 1,2-Propylene Oxide, Dioxolane, 4-Methyldioxolane, Dioxane, Dimethyldioxane, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Diethyl Ether, Ethylene Glycol Mono-n-Butyl Ether, Ethylene Glycol Mono-n-Hexyl Ether, Ethylene Glycol Monophenyl Ether, Ethylene Glycol Mono-2-Ethylbutyl Ether, Ethylene Glycol Dibutyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Diethyl Ether, Diethylene Glycol Mono-n-Butyl Ether, Diethylene Glycol Di-n-Butyl Ether, Diethylene Glycol Mono-n-Hexyl Ether, Ethoxytriglycol, Tetraethylene Glycol Di-n-Butyl Ether, Propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate (normal butyl acetate, nBA), i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate,Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, Examples of the solvent include n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more. The solvent (C) more preferably comprises propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl acetate, n-butyl ether, 2-heptanone, cyclohexanone, or any combination thereof, and even more preferably is propylene glycol monomethyl ether, ethyl lactate, or a mixture thereof. When two types are mixed, the mass ratio of the first solvent to the second solvent is preferably 95:5 to 5:95 (more preferably 90:10 to 10:90, and even more preferably 80:20 to 20:80). In relation to other layers or films, the solvent (C) may not substantially contain water. For example, the amount of water in the entire solvent (C) 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. In another preferred embodiment, the solvent (C) may not contain water (0% by mass).

[0045] The content of the solvent (C) is preferably 50 to 95 mass %, more preferably 60 to 93 mass %, and further preferably 70 to 90 mass %, based on the total mass of the composition. By increasing or decreasing the amount of the solvent in the entire composition, the film thickness after formation can be controlled.

[0046] Base Compound (D) The composition according to the present invention may further comprise a basic compound (D). The basic compound (D) has the effect of suppressing environmental impact. In addition to the above effects, the basic compound also has the effect of suppressing the inactivation of the acid on the membrane surface due to amine components contained in the air.

[0047] The basic compound (D) is preferably ammonia, C 1-16 Primary aliphatic amines, C 2-32 Secondary aliphatic amines, C 3-48 Tertiary aliphatic amines, C 6-30 Aromatic amines of C 5-30 and derivatives thereof.

[0048] Specific examples of the basic compound (D) include ammonia, ethylamine, n-octylamine, ethylenediamine, triethylamine, triethanolamine, tripropylamine, tributylamine, triisopropanolamine, diethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0049] The molecular weight of the basic compound (D) is preferably 17-500, and more preferably 100-350.

[0050] The content of the basic compound (D) is preferably 0.005 to 2 mass%, more preferably 0.05 to 0.9 mass%, based on the total mass of the polymer (A). In consideration of the storage stability of the composition, it is also a suitable embodiment that does not contain the basic compound (D).

[0051] Surfactant (E) The composition according to the present invention may contain a surfactant (E). By containing a surfactant, the coating property can be improved. Examples of surfactants that can be used in the present invention include (I) anionic surfactants, (II) cationic surfactants, and (III) nonionic surfactants, and more specifically, (I) alkylsulfonates, alkylbenzenesulfonic acids, and alkylbenzenesulfonates, (II) laurylpyridinium chloride, and laurylmethylammonium chloride, and (III) polyoxyethylene octyl ethers, polyoxyethylene lauryl ethers, polyoxyethylene acetylenic glycol ethers, fluorine-containing surfactants (e.g., Fluorad (3M), Megafac (DIC), Sulfuron (Asahi Glass), and organic siloxane surfactants (e.g., KF-53, KP341 (Shin-Etsu Chemical)).

[0052] These surfactants can be used alone or in combination of two or more. The content of the surfactant (E) is preferably 0.005 to 1 mass %, more preferably 0.01 to 0.1 mass %, based on the total mass of the polymer (A).

[0053] Plasticizer (F) The composition according to the present invention may further contain a plasticizer (F). By adding a plasticizer, film cracking can be suppressed. Examples of the plasticizer (F) include an alkali-soluble vinyl polymer and an acid-dissociable group-containing vinyl polymer. More specifically, examples thereof 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 acid polyimide, polyacrylamide, polyacrylonitrile, polyvinyl phenol, novolac, and copolymers thereof, and more preferably polyvinyl ether, polyvinyl butyral, and polyether ester. The content of the plasticizer (F) is preferably 0 to 5 mass %, more preferably 0 to 3 mass %, based on the total mass of the polymer (A). In one preferred embodiment of the present invention, no plasticizer (F) is contained.

[0054] Crosslinker (G) The composition according to the present invention may further include a crosslinking agent (G). In the present invention, the crosslinking agent refers to a compound having a crosslinking function itself. The crosslinking agent is not particularly limited as long as it crosslinks the polymer (A) intramolecularly and / or intermolecularly.

[0055] Examples of the crosslinking agent include melamine compounds, guanamine compounds, glycoluril compounds or urea compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and compounds containing a double bond such as an alkenyl ether group. Compounds containing a hydroxyl group are also used as crosslinking agents. Examples of epoxy compounds include tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether. Examples of melamine compounds include hexamethylolmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, and mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, and mixtures thereof. Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, and mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, and mixtures thereof. Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 methylol groups of tetramethylol glycoluril are methoxymethylated, and mixtures thereof, compounds in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated, and mixtures thereof. Examples of urea compounds include tetramethylol urea, tetramethoxymethyl urea, compounds in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, and mixtures thereof, tetramethoxyethyl urea, and the like.Examples of compounds containing an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0056] Examples of crosslinking agents containing hydroxy groups include the following: [ka]

[0057] The crosslinking agent (G) can be used alone or in combination of two or more kinds. The content of the crosslinking agent (G) is preferably from 0 to 30% by mass, more preferably from 0 to 20% by mass, based on the total mass of the polymer (A). When the composition according to the present invention is a positive type, the content of the crosslinking agent (G) is preferably 0 to 5 mass %, more preferably 0 to 1.0 mass %, and further preferably 0 to 0.1 mass %, based on the total mass of the polymer (A). When the composition according to the present invention is a positive type, a preferred embodiment of the present invention is one in which the crosslinking agent (G) is not contained. When the composition according to the present invention is a negative type, the content of the crosslinking agent (G) is preferably 3 to 30 mass %, more preferably 5 to 20 mass %, and further preferably 5 to 12 mass %, based on the total mass of the polymer (A).

[0058] Additive (H) The composition according to the present invention may further contain an additive (H) other than the components (A) to (G). The additive (H) is preferably a polymer other than the polymer (A), a photoreactive quencher, a surface smoothing agent, a contrast enhancing agent, an acid, a dye, a radical generator, a substrate adhesion enhancing agent, an antifoaming agent, or any combination thereof. The content of the additive (H) (when there are multiple additives, the sum of the additives) is preferably 0 to 5 mass %, more preferably 0 to 3 mass %, and further preferably 0 to 1 mass %, based on the total mass of the polymer (A). In one preferred embodiment of the present invention, the composition according to the present invention does not contain the additive (H).

[0059] Sulfonyloxyimide Compounds (I) The composition according to the present invention may further contain a sulfonyloxyimide compound (I) represented by formula (I-1). [ka] Where: L i is an alkylene, arylene, or alkoxylene; R i is alkyl, aryl, halogen-substituted alkyl, or halogen-substituted aryl. The content of the sulfonyloxyimide compound (I) is preferably 0 to 0.5 mass%, more preferably 0 to 0.1 mass%, and further preferably 0 to 0.01 mass%, based on the total mass of the polymer (A). In one preferred embodiment of the present invention, no sulfonyloxyimide compound (I) is contained.

[0060] Carboxylic Acid Ester (J) The composition according to the present invention may further comprise a carboxylic acid ester (J) represented by formula (J-1). [ka] Where: R j1 is C 1-10 Alkyl, or -OR j1' and R j2 -OR j2 ' and R j1 ' and R j2 ' are each independently 1-20 is a hydrocarbon, R j3 and R j4 are each independently H or C 1-10 is alkyl, R j1 and R j3 Or R j4 , or R j2 and R j3 Or R j4 may be bonded to form a saturated or unsaturated hydrocarbon ring, nj is 1 or 2, However, when nj=1, R j1 or R j1 ', and R j2 At least one of ' is C 3-20 It is a hydrocarbon. The content of the carboxylate ester (J) is preferably 0 to 2 mass%, more preferably 0 to 1 mass%, and further preferably 0 to 0.1 mass%, based on the total mass of the polymer (A). A preferred embodiment of the present invention is one in which no carboxylate ester (J) is contained (0%).

[0061] The present invention also relates to the use of the above composition for suppressing standing waves, improving resolution, improving rectangularity, and / or improving heat resistance.

[0062] <Method of manufacturing resist pattern> The method for producing a resist pattern according to the present invention comprises the following steps. (1) applying the composition directly onto a substrate; (2) heating the composition to form a resist layer; (3) exposing the resist layer; (4) post-exposure baking the resist layer; and (5) developing the resist layer. Here, the numbers in parentheses indicate the order of the steps. For example, if steps (1), (2), and (3) are listed, the order of the steps will be as above.

[0063] The composition according to the present invention is applied directly 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.) by a suitable method. Here, the present invention does not include the case where a lower anti-reflective film is formed on the substrate. The application method is not particularly limited, and examples thereof include coating methods using a spinner or coater.

[0064] After application of the composition, a resist layer is formed by heating (pre-baking). The formation of the resist layer is carried out, for example, by using a hot plate. The heating temperature is preferably 80 to 250°C, more preferably 80 to 200°C, and further preferably 90 to 180°C. The heating time is preferably 30 to 600 seconds, more preferably 30 to 300 seconds, and further preferably 60 to 180 seconds. Heating is preferably carried out in air or nitrogen gas atmosphere.

[0065] The thickness of the resist layer varies depending on the exposure wavelength, but is preferably 50 to 10,000 nm, more preferably 200 to 3,000 nm, and even more preferably 200 to 2,000 nm.

[0066] The resist layer is exposed through a predetermined mask. The wavelength of light used for exposure is not particularly limited, but it is preferable to expose with light having a wavelength of 13.5 to 365 nm. Specifically, i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), extreme ultraviolet light (wavelength 13.5 nm), etc. can be used, and KrF excimer laser is preferable. These wavelengths allow a range of ±1%. After exposure, post exposure bake can be performed as necessary. The temperature of post exposure bake is preferably 80 to 150°C, more preferably 100 to 140°C, and the heating time is 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0067] After exposure, development is carried out using a developer. The developer used is preferably a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH). 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 90 seconds. For example, a surfactant can be added to these developers. When a positive resist composition is used, the exposed areas are removed by development, and when a negative resist composition is used, the unexposed areas of the resist layer are removed by development, forming a resist pattern. This resist pattern can be made even finer by using, for example, a shrink material.

[0068] The resist pattern formed, whether positive or negative, has a reduced effect of standing waves and has smooth side portions. FIG. 1 is a schematic diagram of the cross-sectional shape of a negative resist pattern when it is affected by a standing wave. A resist pattern 1 is formed on a substrate 2. When a waveform shape with a large amplitude is formed in the cross section, a small difference in film thickness causes a large fluctuation in the resist top shape, resulting in poor dimensional accuracy, so it is preferable that such an amplitude is small. Here, the first point where the resist pattern is maximized from the contact point between the substrate and the resist pattern toward the upper side is called an antinode 3, and the point directly above that where the resist pattern is minimized is called a node 4. The distance between the antinode and the node in the direction parallel to the substrate is called an antinode distance 5. It is preferable that this antinode distance is small, and specifically, the antinode distance / target pattern width (hereinafter sometimes referred to as the standing wave index) is preferably less than 10%, and more preferably 5% or less. Here, the target pattern width may be the width of the top of the resist when it is assumed that there is no influence of the standing wave. By reducing the standing waves that appear in the resist pattern, it is possible to suppress pattern collapse caused by the formation of shapes different from the intended shape or notches, making it easier to stably form finer patterns. Figure 2 is a schematic diagram of the cross-sectional shape of a negative resist pattern when it is not affected by standing waves. In a negative resist, the polymer is insolubilized through the medium of acid generated by exposure, so light does not reach the bottom as easily, and less acid is generated than the top, making the bottom less likely to become insolubilized than the top. As a result, the formed pattern tends to have an inverted tapered shape. In Figure 2, there are no antinodes or nodes, and in this case, the standing wave index is considered to be 0.

[0069] Furthermore, the resist pattern formed has a high degree of rectangularity. 3 and 4 show schematic diagrams of a vertical cross section of a trench pattern 22 on a substrate 21. The width of the top of the pattern is Wt, and the width of the bottom of the pattern is Wb. This ratio Pr is defined as Pr=Wt / Wb. When a positive resist is used and the resist pattern is a trench pattern with a film thickness of 1.5 μm, a line width of 0.8 μm, and a space width of 0.2 μm, the ratio is preferably 0.7≦Pr≦1.2, and more preferably 0.8≦Pr≦1.1. Preferably, the resist pattern produced has an inverted tapered shape. This method can be suitably used in a lift-off process.

[0070] The method for producing a metal pattern according to the present invention comprises the steps of: The method comprises: producing a resist pattern by the method described above; (6a) forming a metal layer on the resist pattern; and (7a) removing the remaining resist pattern and the metal layer thereon. Steps (1) to (5) are followed by steps (6a) and (7a). The order of steps is as described above. The metal layer is formed by, for example, deposition or sputtering of a metal such as gold or copper (which may be a metal oxide or the like). Thereafter, the resist pattern is removed together with the metal layer formed thereon using a stripping solution to form a metal pattern. The stripping solution is not particularly limited as long as it is used as a resist stripping solution, but for example, N-methylpyrrolidone (NMP), acetone, and an alkaline solution are used. When the resist according to the present invention is a negative type, it tends to have an inverse tapered shape as described above. When it is inverse tapered, the metal on the resist pattern and the metal formed in the part where the resist pattern is not formed are separated from each other, so that it can be easily stripped. The thickness of the metal pattern formed is preferably 10 to 70,000 nm. The thickness of the metal pattern is preferably 5 to 70% of the resist film thickness, more preferably 10 to 70%, and further preferably 25 to 50%.

[0071] The method for producing a patterned substrate according to the present invention includes the steps of: Producing a resist pattern by the method described above; (6b) Etching using the resist pattern as a mask; (7b) processing the substrate. The etching may be either dry etching or wet etching, and may be performed multiple times. Steps (1) to (5) are followed by steps (6b) and (7b).

[0072] The method for producing a patterned substrate according to the present invention includes the steps of: Producing a resist pattern by the method described above; (6c) etching the resist pattern; (7c) etching the substrate. Steps (1) to (5) are followed by steps (6c) and (7c) in the order described above. wherein the combination of steps (6c) and (7c) is repeated at least twice; and the substrate comprises a plurality of Si-containing layers stacked together, at least one Si-containing layer being electrically conductive and at least one Si-containing layer being electrically insulating. Preferably, conductive Si-containing layers and electrically insulating Si-containing layers are laminated alternately. Here, the thickness of the resist layer formed in (2) is preferably 0.5 to 200 μm.

[0073] The resist pattern according to the present invention can also be used for ion implantation. Therefore, the method for producing a processed substrate according to the present invention comprises the following steps. Producing a resist pattern by the method described above; and performing ion implantation using the resist pattern as a mask; or The resist pattern is used as a mask to process a layer below the resist pattern, forming a lower layer pattern, and then ion implantation is performed using the lower layer pattern as a mask. Ion implantation can be performed by a known method using a known ion implantation device. In the manufacture of semiconductor elements, liquid crystal display elements, and the like, an impurity diffusion layer is formed on the surface of a substrate. The formation of the impurity diffusion layer is usually performed in two stages: introduction of impurities and diffusion. One of the introduction methods is ion implantation, in which impurities such as phosphorus and boron are ionized in a vacuum, accelerated by a high electric field, and implanted into the surface of the support. As the ion acceleration energy during ion implantation, an energy load of 10 to 200 keV is generally applied to the resist pattern, which may destroy the resist pattern. The resist pattern formed by the present invention is a thick film, has high rectangularity, and has high heat resistance, and therefore can be suitably used for ion implantation applications in which ions are implanted at high energy. The ion source (impurity element) may be ions of boron, phosphorus, arsenic, argon, etc. The thin film on the substrate may be silicon, silicon dioxide, silicon nitride, aluminum, etc.

[0074] Thereafter, the substrate is further processed as necessary to form a device. This further processing can be performed by a known method. The method for producing a device according to the present invention includes any of the above methods, and preferably further includes a step of forming wiring on the processed substrate. Examples of the device include a semiconductor device, a liquid crystal display device, an organic electroluminescence display device, a plasma display device, and a solar cell device, and preferably a semiconductor device.

[0075] [Example] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0076] <Preparation of the composition of Example 1> PGME and EL are mixed in a mass ratio of 70:30 to obtain a mixed solvent. 100 parts by mass of polymer 1, 1.50 parts by mass of photoacid generator 1, 0.3 parts by mass of base compound 1, and 0.06 parts by mass of surfactant 1 are added to the mixed solvent so that the solid content concentration is 18.0% by mass. The solid content concentration means the concentration of all components other than the solvent (including the mixed solvent) contained in the composition in the entire composition. This is stirred at room temperature for 30 minutes. It is visually confirmed that the added materials are dissolved. This is filtered through a 0.05 μm filter. In this way, the composition of Example 1 is obtained. Polymer 1: Hydroxystyrene:styrene:t-butyl acrylate copolymer, molar ratio 6:2:2, Mw 12,000. The above ratios indicate the composition ratio of each repeating unit. The same applies below. [ka] Photoacid generator 1 [ka] Base compound 1: Tris[2-(2-methoxyethoxy)ethyl]amine Surfactant 1: MEGAFACE R-40, DIC

[0077] <Preparation of Compositions of Examples 2 to 5 and Comparative Example 1> Except for changing the components of the photoacid generator (B) as shown in Table 1, the compositions of Examples 2 to 5 and the composition of Comparative Example 1 are obtained in the same manner as in "Preparation of the composition of Example 1." [Table 1] In the table, Photoacid generator 2 [ka] Photoacid generator 3 [ka] Photoacid generator 4 [ka] Photoacid generator 5 [ka] Photoacid generator 6 [ka]

[0078] <Formation of Resist Pattern> Using a coater developer Mark8 (Tokyo Electron), each composition is dropped onto an 8-inch Si wafer and spin-coated. The wafer is heated at 140°C for 90 seconds using a hot plate under atmospheric conditions to form a resist layer. The thickness of the resist layer at this point is measured using an optical interference film thickness measuring device M-1210 (SCREEN) to be 1.5 μm. The resist layer is exposed using a KrF stepper FPA3000-EX5 (Canon). The exposed wafer is heated (PEB) at 120°C for 90 seconds using a hot plate under atmospheric conditions. The resist layer is then paddle developed with a 2.38% by mass TMAH aqueous solution for 60 seconds, washed with water, and spin-dried at 1,000 rpm. This forms a trench pattern with a line width of 0.8 μm and a space width of 0.2 μm. The line width and space width are measured at the bottom of the pattern. This pattern shape is shown typically in Figure 3. The optimum exposure dose is defined as the exposure dose that forms a trench pattern with a line width of 0.8 μm and a space width of 0.2 μm.

[0079] <Evaluation of rectangularity> Cut the substrate formed in "Formation of resist pattern" and observe the vertical cross section with a scanning electron microscope (SEM). Evaluate according to the following criteria, with the width Wt of the top of the resist pattern, Wb of the bottom of the resist pattern, and the ratio Pr = Wt / Wb. The evaluation results are shown in Table 1. A: 0.8≦Pr≦1.2 B: 0.7≦Pr<0.8 C:Pr>1.2 or Pr<0.7

[0080] <Evaluation of standing waves> The distance between antinodes of the standing wave of the resist pattern formed in the above "Evaluation of rectangularity" is evaluated according to the following criteria. The evaluation results are shown in Table 1. A: Internode distance is less than 10 nm B: Abdominal internode distance is 10 nm or more and less than 50 nm C: Abdominal internode distance is 50 nm or more

[0081] <Resolution evaluation> A resist pattern is formed in the same manner as in "Formation of a resist pattern", except that a mask pattern with a space size of 0.25 to 0.16 μm is used and exposure is performed at the optimum exposure dose described in "Formation of a resist pattern". The minimum dimension that can be formed is taken as the resolution (nm) and is evaluated according to the following criteria. The evaluation results are shown in Table 1. A: Resolution is 180nm or less B: Resolution is greater than 180 nm and less than 200 nm C: Resolution is 200nm or more

[0082] <Evaluation of heat resistance> A substrate on which a resist pattern has been formed by the method described in "Formation of a resist pattern" is heated on a hot plate at 150°C for 60 seconds. The change in the shape of the top of the resist pattern is then observed on a vertical cross section using an SEM and evaluated according to the following criteria. The evaluation results are shown in Table 1. A: No change in shape B: Changes of less than 50 nm C: Change of 50 nm or more

[0083] <Reference example: Formation of resist pattern with bottom anti-reflective film> As a reference example, a case where a bottom anti-reflective coating is formed under the resist layer is evaluated. Since the present invention is a composition that is directly coated on the substrate, the case where a bottom anti-reflective coating is formed on the substrate is outside the scope of the present invention. A bottom anti-reflective coating composition AZ KrF-17B (Merck Electronics) is applied onto an 8-inch Si wafer and baked at 180°C for 60 seconds to form a bottom anti-reflective coating (BARC) with a thickness of 45 nm. The composition of Example 1 or the composition of Comparative Example 1 is dropped onto this BARC and spin-coated. Thereafter, the same operations as those in "Formation of a resist pattern" above are carried out. Similarly to the above, when rectangularity, standing waves, resolution, and heat resistance were evaluated, the rectangularity of both compositions was rated B, while the others were rated A. In these cases, the presence of BARC requires a removal process, making them unsuitable for the implant process or lift-off process. [Explanation of symbols]

[0084] 1. Substrate 2. Resist pattern affected by standing waves 3. Belly 4. Section 5. Abdominal Internode Distance 11. Substrate 12. Resist pattern not affected by standing waves 21. Substrate 22. Trench Pattern

Claims

1. A substrate coating resist composition comprising a polymer (A) and a photoacid generator (B), Polymer (A) comprises at least one of the repeating units represented by formulas (A-1) and (A-2), and optionally further comprises at least one of the repeating units represented by formulas (A-3) and (A-4), and A resist composition in which the photoacid generator (B) is represented by formula (B-1). 【Chemistry 1】 (Here, C ｙ １１ and C ｙ ２１ Each of these is an aryl or heteroaryl compound having five or six ring atoms, R １１ 、 R ２１ 、 R ４１ and R ４５ are each independently C １－５ alkyl (wherein the methylene in the alkyl may be replaced by oxy); 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 These are, independently, hydrogen and C １－５ Alkyl, C １－５ It is an alkoxy or -COOH group; p11 is between 0 and 4, p15 is between 1 and 2, and p11 + p15 ≤ 5. p21 is 0-5, p41 is between 0 and 4, p45 is between 1 and 2, and p41 + p45 ≤ 5; P ３１ is C ４－２０ It is an alkyl group (where some or all of the alkyl group may form a ring, some or all of the H atoms of the alkyl group may be substituted with halogens, and the methylene group in the alkyl group may be replaced by an oxy or carbonyl group) B ｎ＋ Cation B ｎ－ Anion (B-1) (Here, B ｎ＋ The cation as a whole is n-valent, B ｎ－ An anion has an overall valence of n, where n is between 1 and 3. B ｎ－ Anions are anions represented by formula (BA-1), 【Chemistry 2】 Here, C ｙ ａ This is a hydrocarbon ring having five or six ring atoms, one of which may be replaced by nitrogen. L ａ１ C １－５ It is alkylene, R ａ２ It is nitro or cyano, R ａ３ C is either unsubstituted or fluorine-substituted. １－１０ It is alkyl, na1 is either 0 or 1. na2 is a number between 0 and 3. (na3 is a number between 0 and 3.)

2. B ｎ＋ The composition according to claim 1, wherein the cation is selected from the group consisting of a cation represented by formula (BC-1), a cation represented by formula (BC-2), and a cation represented by formula (BC-3): Preferably, the photoacid generator (B) consists of one or two types. 【Transformation 3】 (Here, R ｂ１ Each of them independently, C １－６ Alkyl, C １－６ Alkoxy, C ６－１２ Ariel, C ６－１２ Arylthio, or C ６－１２ It is an aryloxy, (nb1 is independently 0, 1, 2, or 3.) 【Chemistry 4】 (Here, R ｂ２ Each of them independently, C １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ It is Ariel, (nb2 is independently 0, 1, 2, or 3.) 【Transformation 5】 (Here, R ｂ３ These are, independently, hydroxyl and C. １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ It is Ariel, R ｂ４ Each of them independently, C １－６ It is alkyl, but with two R's ｂ４ They may be bonded to each other to form a ring structure. nb3 is independently 0, 1, 2, or 3. nb4 is either 0 or 1.

3. The number of repeating units n in polymer (A) is (A-1), (A-2), (A-3), and (A-4). 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 )=0~100%、 n Ａ－２ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ )=0~100%、 n Ａ－３ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) = 0-50%, or n Ａ－４ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ The composition according to claim 1 or 2, wherein the concentration is 0 to 50%: Preferably, the total number of repeating units in polymer (A) n ｔｏｔａｌ So, (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) / n ｔｏｔａｌ = Meets 80-100%, or Preferably, the mass-average molecular weight Mw of polymer (A) is 3,000 to 50,000.

4. The composition according to claim 1 or 2, further comprising solvent (C): Preferably, the solvent (C) comprises propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl acetate, n-butyl ether, 2-heptanone, cyclohexanone, or any combination thereof. Preferably, the solvent (C) content is 50 to 90% by mass based on the total mass of the composition.

5. The composition according to claim 1 or 2, further comprising a basic compound (D): Preferably, the base compound (D) is ammonia, C １－１６ a primary aliphatic amine compound, C ２－３２ a secondary aliphatic amine compound, C ３－４８ a tertiary aliphatic amine compound, C ６－３０ an aromatic amine compound, C ５－３０ a heterocyclic amine compound, or any combination thereof, or Preferably, the content of the basic compound (D) is 0.01 to 5% by mass, based on the total mass of the polymer (A).

6. The composition according to claim 1 or 2, further comprising a surfactant (E): Preferably, the content of surfactant (E) is 0.005 to 1% by mass, based on the total mass of polymer (A).

7. The composition according to claim 1 or 2, further comprising a plasticizer (F): Preferably, the content of the plasticizer (F) is 0 to 0.5% by mass, based on the total mass of the polymer (A). Preferably, the composition further comprises a crosslinking agent (G), or Preferably, the crosslinking agent (G) content is 0 to 30% by mass, based on the total mass of polymer (A).

8. The composition according to claim 1 or 2, further comprising additive (H): Preferably, additive (H) is a polymer other than polymer (A), a photoreaction quencher, a surface smoothing agent, a contrast enhancer, an acid, a dye, a radical generator, a substrate adhesion enhancer, an antifoaming agent, or any combination thereof. Preferably, the content of additive (H) is 0 to 5% based on the total mass of polymer (A).

9. The composition according to claim 1 or 2, further comprising a sulfonyloxyimide compound (I) represented by formula (I-1): Preferably, the content of sulfonyl oxyimide compound (I) is 0 to 0.5% by mass, based on the total mass of polymer (A). 【Transformation 6】 (Here, L ｉ These are alkylenes, arylenes, or alkoxylenes. R ｉ (These are alkyl, aryl, halogen-substituted alkyl, and halogen-substituted aryl elements.)

10. The composition according to claim 1 or 2, further comprising a carboxylic acid ester (J) represented by formula (J-1). Preferably, the content of the carboxylic acid ester (J) is 0 to 2% by mass, based on the total mass of the polymer (A). 【Transformation 7】 (Here, R ｊ１ C １－１０ Alkyl, or -OR ｊ１ 'and, R ｊ２ is -OR ｊ２ ', and R ｊ１ 'and R ｊ２ 'Each is independently, C １－２０ It is a hydrocarbon, R ｊ３ and R ｊ４ These are, independently, H or C １－１０ It is alkyl, R ｊ１ and R ｊ３ Or R ｊ４ , or R ｊ２ and R ｊ３ Or R ｊ４ They may bond together to form saturated or unsaturated hydrocarbon rings. nj is either 1 or 2. However, when nj = 1, R ｊ１ or R ｊ１ ', and R ｊ２ At least one of ' is C ３－２０ (It is a hydrocarbon.)

11. The composition according to claim 1 or 2, wherein the content of polymer (A) is 10 to 40% by mass based on the total mass of the composition, or the content of photoacid generator (B) is 0.2 to 5% by mass based on the total mass of polymer (A).

12. The composition according to claim 1 or 2, which is a substrate coating chemically amplified resist composition: Preferably, the substrate coating resist composition is a substrate coating chemically amplified KrF resist composition, and preferably, the substrate coating resist composition is a substrate coating chemically amplified positive KrF resist composition, or Preferably, the substrate coating resist composition is a substrate coating chemically amplified negative KrF resist composition.

13. Use of the composition according to claim 1 or 2 for suppressing standing waves, improving resolution, improving rectangularity, and / or improving heat resistance.

14. A method for manufacturing a resist pattern, comprising the following steps: (1) Applying the composition according to claim 1 or 2 directly onto the substrate; (2) Heating the composition to form a resist layer; (3) Exposing the resist layer; (4) Heating the resist layer after exposure; and (5) Developing the resist layer: Preferably, light with a wavelength of 13.5 to 365 nm is used for exposure in (3). Preferably, the thickness of the resist layer formed in (2) is 50 to 10,000 nm, or Preferably, the resist pattern produced is in the shape of an inverted taper.

15. When the resist pattern is a trench pattern with a film thickness of 1.5 μm, a line width of 0.8 μm, and a space width of 0.2 μm, The method according to claim 14, wherein the width Wt of the trench pattern top and the width Wb of the trench pattern bottom satisfy 0.7 ≤ Wt / Wb ≤ 1.

2.

16. A method for manufacturing a metal pattern comprising the following steps: To manufacture a resist pattern by the method described in claim 14; (6a) Forming a metal layer on a resist pattern; and (7a) Remove the remaining resist patterns and the metal layer on top of them: Preferably, the film thickness of the metal pattern is 10 to 7,000 nm.

17. A method for manufacturing a patterned substrate comprising the following steps: To manufacture a resist pattern by the method described in claim 14; (6b) Etching using a resist pattern as a mask; and (7b) Processing the circuit board.

18. A method for manufacturing a patterned substrate comprising the following steps: A resist pattern is formed by the method according to claim 14. (6c) Etching the resist pattern; and (7c) Etching the substrate: Here, the combination of steps (6c) and (7c) is repeated at least twice; and the substrate consists of multiple Si-containing layers stacked on top of each other, with at least one Si-containing layer being conductive and at least one Si-containing layer being electrically insulating: Preferably, conductive Si-containing layers and electrically insulating Si-containing layers are alternately laminated; or Preferably, the resist layer formed in (2) has a thickness of 0.5 to 200 μm.

19. A method for manufacturing a processed substrate, comprising the following steps: Manufacturing a resist pattern by the method of claim 14; and Perform ion implantation using the aforementioned resist pattern as a mask, or Using the aforementioned resist pattern as a mask, the layer beneath the resist pattern is processed to form a lower layer pattern, and ion implantation is performed using the lower layer pattern as a mask.

20. A method for manufacturing a device comprising the method of claim 14: Preferably, the process further includes the step of forming wiring on the processed substrate; or Preferably, the device is a semiconductor device.

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