Resist composition, method for producing a resist film, and method for producing a device

Abstract

A resist composition, a method for producing a resist film, and a method for producing a device are provided.

Description

[Technical Field]

[0001] The present invention relates to a resist composition, a method for producing a resist film, and a method for producing a device. [Background technology]

[0002] In recent years, the need for higher integration of LSIs has increased, resulting in a demand for finer patterns. To meet these needs, lithography processes using KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet (EUV; 13 nm), short-wavelength X-rays, electron beams, and the like have been put to practical use. To meet this demand for finer resist patterns, photosensitive resin compositions used as resists during fine processing are also required to have high resolution. Although finer patterns can be formed by exposure to short-wavelength light, high dimensional accuracy is required.

[0003] In the lithography process, a resist pattern is formed by exposing and developing the resist. During exposure, the light incident on the resist and the light reflected from the substrate or air interface interfere with each other, resulting in the generation of standing waves. The generation of standing waves reduces the dimensional accuracy of the pattern. To reduce standing waves, attempts have been made to form anti-reflective coatings on the top and / or bottom layers of the resist. For example, it has been proposed that adding an organic compound to lithography components such as resists can suppress the migration speed of the acid generated from an acid generator and reduce standing waves (WO 2022 / 023230). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2022 / 023230 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have found that resist compositions still have one or more problems that require improvement. These problems include, for example: The sidewalls of the resist pattern vibrate due to the effects of standing waves; the width of the resist pattern is non-uniform; the rectangularity of the resist pattern is poor; the sensitivity is low; and the resolution is low. [Means for solving the problem]

[0006] The resist composition according to the present invention contains a polymer (A), a photoacid generator (B), and an amide compound (D). The amide compound (D) is represented by the following formula (D-1). [ka] (In the formula, R d1 is a linear C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR d4 R d5 and R d2 and R d3 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 is alkyl, R d4 and R d5 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 is alkyl, R d1 is alkyl, R d1 is R d2 may form a ring with R d1 Ga-NR d4 R d5 If R d4 or R d5 is R d2 may form a ring with R d1 , R d2 , Rd3 , R d4 and / or R d5 When is alkyl, the methylene (-CH2-) in the alkyl may be replaced with -NH-, -S- or -O-).

[0007] The method for producing a resist film according to the present invention comprises: (1) applying the composition onto a substrate; (2) heating the composition to form a resist film.

[0008] Methods for manufacturing devices according to the present invention include the methods described above. [Effects of the Invention]

[0009] According to the present invention, one or more of the following effects can be expected. The resist pattern has a high effect of reducing standing waves; 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 explanation of the drawings]

[0010] [Figure 1] 1A and 1B are conceptual diagrams showing cross-sectional shapes of resist patterns when not affected by standing waves and when affected by standing waves. [Figure 2] FIG. 1 is a conceptual diagram showing a cross-sectional shape of a trench pattern. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail.

[0012] definition Unless otherwise specified herein, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "one" or "that" means "at least one." When elements of a concept can be expressed in plural, and an amount thereof (e.g., mass % or mole %) is given, it refers to the sum of the plural. "And / or" includes all combinations of elements as well as the use of elements alone. When a numerical range is indicated using "to" or "to-," both endpoints are included 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 carbon atoms in a molecule or substituent. For example, C 1-6 Alkyl 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 can be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When a polymer or resin is represented by a structural formula, the n, m, etc. next to the parentheses indicate the repeating number. Celsius is used as a temperature unit. For example, 20 degrees means 20 degrees Celsius. The additive refers to the compound itself having that function (for example, in the case of a base generator, the compound itself that generates a base). Alternatively, an embodiment is possible 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 solvent (F) or as a separate component.

[0013] <Resist composition> The resist composition according to the present invention (hereinafter referred to as the composition) contains a polymer (A), a photoacid generator (B), and an amide compound (D) having a specific structure. The composition according to the present invention is preferably a chemically amplified resist composition, and more preferably a chemically amplified KrF resist composition. The composition according to the present invention can be used for both positive and negative resists. In a preferred embodiment of the present invention, the composition according to the present invention is a positive chemically amplified resist composition, and more preferably a positive chemically amplified KrF resist composition.

[0014] Polymer (A) The composition according to the present invention contains a polymer (A) (hereinafter referred to as component (A), and the same applies to other components). The polymer (A) is preferably a polymer having a reactive group, and more preferably an alkali-soluble polymer.

[0015] Polymer (A) comprises at least one repeating unit represented by formula (A-1) and formula (A-2), and preferably further comprises at least one repeating unit represented by formula (A-3) and formula (A-4). More preferably, polymer (A) comprises a repeating unit represented by formula (A-1) and further comprises at least one repeating unit represented by (A-3) and (A-4). In a preferred embodiment, polymer (A) comprises repeating units represented by formula (A-1), (A-2) and (A-3), and more preferably consists essentially of repeating units represented by formula (A-1), (A-2) and (A-3).

[0016] Formula (A-1) is as follows: [ka] (In the formula, C y 11 are each independently an aryl or heteroaryl having 5 or 6 ring atoms, preferably benzene. R 11 are each independently C 1-5It is alkyl (methylene in the alkyl may be replaced with oxy), preferably methyl or ethyl, more preferably methyl. In the present invention, "methylene in the alkyl may be replaced with oxy" means that oxy can exist between carbon atoms in the alkyl, and this does not intend that the terminal carbon in the alkyl becomes oxy, i.e., has alkoxy or hydroxy. R 12 , R 13 and R 14 are each independently hydrogen, C 1-5 Alkyl, C 1-5 It is 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 is satisfied.

[0017] Polymer (A) may contain multiple repeating units represented by formula (A-1). For example, polymer (A) may have a structural unit where p15=1 and a structural unit where p15=2 in a ratio of 1:1. In this case, the overall p15 is 1.5. Unless otherwise specified, the same applies to the numbers representing polymers in the present invention.

[0018] Exemplary embodiments of formula (A-1) include the following: [ka]

[0019] Formula (A-2) is as follows: [ka] (In the formula, C y 21 are each independently an aryl or heteroaryl having 5 or 6 ring atoms, preferably benzene. R 21 are each independently C 1-5 It is alkyl (methylene in the alkyl may be replaced by oxy), preferably methyl, ethyl, t-butyl or t-butoxy, more preferably methyl or ethyl, and even more preferably methyl. R 22 , R 23 and R 24 are each independently hydrogen, C 1-5 Alkyl, C 1-5 It is alkoxy or —COOH, preferably hydrogen or methyl, more preferably hydrogen. p 21 is 0 to 5, preferably 0, 1, 2, 3, 4 or 5, more preferably 0 or 1, and even more preferably 0.

[0020] Exemplary embodiments of formula (A-2) include: [ka]

[0021] Formula (A-3) is as follows: [ka] (In the formula, R 32 , R 33 and R 34 are each independently hydrogen or 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 It is an alkyl. 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 halogen, or a methylene in the alkyl may be substituted with oxy or carbonyl. P 31The alkyl portion of P is preferably branched or cyclic. 31 C in 4-20 When alkyl is substituted with halogen, it is preferred that all of them are substituted, and the substituted halogen is preferably F or Cl, more preferably F. 31 C in 4-20 It is a preferred embodiment of the present invention that the H of the alkyl is not substituted with any 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.

[0022] Exemplary embodiments of formula (A-3) include: [ka]

[0023] Formula (A-4) is as follows: [ka] (In the formula, R 41 are each independently C 1-5 It is alkyl (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 It is alkyl (methylene in the alkyl may be replaced by oxy), and is preferably methyl, t-butyl or -CH(CH3)-O-CH2CH3. R 42 , R 43 and R 44are each independently hydrogen, C 1-5 Alkyl, C 1-5 It is 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, and more preferably 1. p41+p45≦5 is satisfied.)

[0024] Exemplary embodiments of formula (A-4) include: [ka]

[0025] Next, the number of repeating units (A-1), (A-2), (A-3), and (A-4) in the polymer (A) is n A-1 , n A-2 , n A-3 and n A-4 This article explains: 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 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 100%, more preferably 0 to 30%, even more preferably 5 to 25%, 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 50%, more preferably 10 to 40%, even more preferably 15 to 35%, and even more preferably 15 to 25%. nA-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 is also a preferred embodiment of the present invention. Preferred embodiments include: 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 )=0~40%.

[0026] The polymer (A) may contain additional repeating units other than the repeating units represented by formulas (A-1), (A-2), (A-3) and (A-4). The total number of all repeating units contained in the polymer (A) is 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 even more preferably 95 to 100%. It is also a preferred embodiment that the polymer (A) does not contain any further repeating units.

[0027] When the composition according to the present invention is a positive resist composition, exemplary embodiments of the polymer (A) include the following: [ka]

[0028] When the composition according to the present invention is a negative resist composition, exemplary embodiments of the polymer (A) include the following: [ka]

[0029] The weight average molecular weight (hereinafter 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 wishing to be bound by theory, it is believed that when polymer (A) has 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). A preferred example of the measurement is to use a GPC column at 40°C, tetrahydrofuran as an elution solvent at 0.6 mL / min, and monodisperse polystyrene as a standard.

[0030] The content of the polymer (A) is preferably from 10 to 60 mass %, more preferably from 10 to 30 mass %, and even more preferably from 12 to 18 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 one preferred embodiment does not contain any polymer other than the polymer (A).

[0031] Photoacid generator (B) The composition according to the present invention contains a photoacid generator (B). The photoacid generator (B) releases an acid upon irradiation with light, and this acid acts on the polymer to increase the solubility of the polymer in an alkaline aqueous solution. For example, if the polymer 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.

[0032] Upon exposure, the photoacid generator (B) preferably releases an acid having an acid dissociation constant pKa(H2O) of -20 to 1.4, more preferably an acid having an acid dissociation constant pKa(H2O) of -16 to 1.4, even more preferably an acid having an acid dissociation constant pKa(H2O) of -16 to 1.2, and even more preferably an acid having an acid dissociation constant pKa(H2O) of -16 to 1.1.

[0033] The photoacid generator (B) is preferably represented by formula (B-1). B n+ Cation B n- Anion (B-1) (In the formula, B n+ The cations consist of at least one cation selected from the group consisting of cations represented by formulae (BC1) to (BC3), and have a valence of n (n is 1 to 3, preferably 1 or 2, more preferably 1) as a whole. B n- The anion is composed of at least one anion selected from the group consisting of anions represented by formulas (BA1) to (BA4), and has a valence of n as a whole.

[0034] Equation (BC1) is as follows: [ka] (In the formula, R b1 are each independently C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, C 6-12Aryloxy, nitro, sulfo, carboxy, hydroxy, amino, cyano, halogen, C 1-6 C with halogen-substituted alkyl or ester bond 2-8 is a hydrocarbon group, preferably C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio or C 6-12 Aryloxy, more preferably methyl, ethyl, t-butyl, methoxy, ethoxy, phenylthio or phenyloxy, and even more preferably t-butyl, methoxy, ethoxy, phenylthio or phenyloxy. Each nb1 is independently 0, 1, 2, or 3, and preferably 0 or 1. In a preferred embodiment, all nb1's are 0. In another preferred embodiment, all nb1 are 1 and all R b1 are identical.

[0035] Exemplary embodiments of formula (BC1) include: [ka]

[0036] Equation (BC2) is as follows: [ka] (In the formula, R b2 are each independently C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfo, carboxy, hydroxy, amino, halogen, C 1-6 C with halogen-substituted alkyl or ester bond 2-8 A hydrocarbon group, preferably C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 aryl, more preferably C 4-6It 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] Exemplary embodiments of formula (BC2) include: [ka]

[0038] Equation (BC3) is as follows: [ka] (In the formula, R b3 are each independently C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfo, carboxy, hydroxy, amino, halogen, C 1-6 C with halogen-substituted alkyl or ester bond 2-8 is a hydrocarbon group, preferably 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 alkyl, preferably methyl or ethyl, more preferably methyl, provided that two R b4 may be linked to each other to form a ring, but preferably do not form a ring. Each nb3 is independently 0, 1, 2 or 3, and more preferably 3.

[0039] Exemplary embodiments of formula (BC3) include: [ka]

[0040] B n+ The cation is preferably selected from the group consisting of cations represented by formula (BC1) or formula (BC2), and more preferably is a cation represented by formula (BC1).

[0041] Formula (BA1) is as follows: [ka] (In the formula, 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. 1-6 All of the hydrogen atoms in the fluorine-substituted alkyl group 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] Exemplary embodiments of formula (BA1) include: [ka]

[0043] Formula (BA2) is as follows: [ka] (In the formula, 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 6-12fluorine-substituted alkoxyaryl, preferably C 1-6 fluorine-substituted alkyl, more preferably C 2-6 Fluorine-substituted alkyl.)R b6 The alkyl moiety 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 R is preferably linear. b6 is preferably C 1-6 It is a fluorine-substituted alkyl.

[0044] Exemplary embodiments of formula (BA2) include: C4F9SO3 - and C3F7SO3 - .

[0045] Equation (BA3) is as follows: [ka] (In the formula, 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 straight-chain. In the formula, two R b7 may be bonded to each other to form a fluorine-substituted heterocyclic structure, in which case the heterocyclic ring may be monocyclic or polycyclic, but is preferably a monocyclic structure having 5 to 8 members.

[0046] Exemplary embodiments of formula (BA3) include: [ka]

[0047] Formula (BA4) is as follows: [ka] (In the formula, R b8 is hydrogen, C 1-6 Alkyl, C 1-6 It is alkoxy or hydroxy, preferably hydrogen, methyl, ethyl, methoxy or hydroxy, more preferably hydrogen or hydroxy. L b is carbonyl, oxy or carbonyloxy, preferably carbonyl or carbonyloxy, more preferably carbonyl. Y b are each independently hydrogen or fluorine, and preferably at least one of them 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] Exemplary embodiments of formula (BA4) include: [ka]

[0049] The molecular weight of component (B) is preferably 400 to 2,500, and more preferably 400 to 1,500.

[0050] The component (B) may be one type or two or more types, but is preferably one type or two or more types, and more preferably one type. The content of component (B) is preferably 0.05 to 5 mass %, more preferably 0.1 to 5 mass %, and even more preferably 1 to 4 mass %, based on polymer (A).

[0051] Photoreactive quencher (C) The composition according to the present invention may further contain a photoreactive quencher (C). The photoreactive quencher (C) releases an acid upon irradiation with light, but the acid does not directly act on the polymer. In this respect, the photoreactive quencher differs from the photoacid generator (B), which directly acts on the polymer by removing the protecting group of the polymer with the released acid.

[0052] Component (C) functions as a quencher, suppressing the diffusion of acid resulting from the disappearance of component (B) generated in the exposed region. Without being bound by theory, this is thought to be due to the following mechanism: Upon exposure, acid is released from component (B), and when this acid diffuses into the unexposed region (unexposed region), salt exchange occurs with component (C). In other words, the anion of component (B) and the cation of component (C) form a salt. This suppresses the diffusion of acid. At this time, the anion of component (C) is released, but since it is a weak acid and cannot deprotect the polymer, it is thought that it does not affect the unexposed region.

[0053] The photoreactive quencher (C) releases an acid having an acid dissociation constant pKa(H2O) of preferably 1.5 to 8, more preferably 1.5 to 5, upon exposure to light.

[0054] Component (C) is preferably at least one selected from the group consisting of photoreactive quenchers represented by formula (C-1). C m+ Cation C m- Anion Formula (C-1) (In the formula, C m+ The cations consist of at least one cation selected from the group consisting of cations represented by formula (CC1) and formula (CC2), and have a valence of m (m is 1 to 3) as a whole. C m- The anion is composed of at least one anion represented by formula (CA) and has a valence of m as a whole. The valence of m is preferably monovalent or divalent, and more preferably monovalent.

[0055] Formula (CC1) is as follows: [ka] (In the formula, R c1 are each independently C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 It is aryl, preferably methyl, ethyl, t-butyl, methoxy, ethoxy, phenylthio or phenyloxy, more preferably t-butyl, methoxy, ethoxy, phenylthio or phenyloxy, and even more preferably t-butyl or methoxy. Each ncl is independently 0, 1, 2, or 3, and more preferably 0 or 1. In a preferred embodiment, all nc1's are 0. In another preferred embodiment, all ncl's are 1 and all R c1 are identical.

[0056] Exemplary embodiments of formula (CC1) include: [ka]

[0057] Formula (CC2) is as follows: [ka] (In the formula, R c2 are each independently C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 aryl, preferably C 4-6R is an alkyl having a branched structure c2 may be the same or different, and more preferably are the same. c2 is more preferably t-butyl or 1,1-dimethylpropyl, and even more preferably t-butyl. Each nc2 is independently 0, 1, 2 or 3, preferably 1.

[0058] Exemplary embodiments of formula (CC2) include: [ka]

[0059] Formula (CA) is as follows: [ka] (In the formula, X is C 1-20 Hydrocarbon or C 6-12 X may be linear, branched, or cyclic, but is preferably linear or cyclic. When X is linear, it is preferably C 1-4 (More preferably C 1-2 ) and has one double bond in the chain, but is preferably saturated. When X is cyclic, it may be an aromatic monocyclic ring or a saturated monocyclic or polycyclic ring, and if it is a monocyclic ring, it is preferably a 6-membered ring, and if it is a polycyclic ring, it is preferably an adamantane ring. X is preferably methyl, ethyl, propyl, butyl, ethane, phenyl, cyclohexane, or adamantane, more preferably methyl, phenyl, or cyclohexane, and even more preferably phenyl. R c3 are each independently hydroxy, carboxy, C 1-6 Alkyl or C 6-10 It is aryl, preferably hydroxy, methyl, ethyl, 1-propyl, 2-propyl, t-butyl or phenyl, more preferably hydroxy. nc3 is 1, 2 or 3, preferably 1 or 2, and more preferably 1. nc4 is 0, 1 or 2, preferably 0 or 1, and more preferably 1.

[0060] Exemplary embodiments of formula (CA) include: [ka]

[0061] The molecular weight of the photoreactive quencher (C) is preferably 300 to 1,400, more preferably 300 to 1,200. The content of the photoreactive quencher (C) is preferably 0.01 to 3 mass %, more preferably 0.05 to 1.5 mass %, and even more preferably 0.08 to 0.8 mass %, based on the total mass of the polymer (A).

[0062] Amide Compound (D) The composition according to the present invention comprises an amide compound (D). Component (D) is represented by formula (D) and does not include an anilide or an imide. In the present invention, the presence of the amide compound (D) significantly reduces the effects of standing waves. Without being bound by theory, it is believed that component (D) has an amide structure, which easily interacts with the acid generated from the photoacid generator (B), thereby reducing the rate of acid migration.

[0063] Formula (D-1) is as follows: [ka] (In the formula, R d1 is a linear C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR d4 R d5 and R d2 and R d3 are each independently hydrogen, straight chain C1-10 Alkyl or branched chain C 3-10 is alkyl, R d4 and R d5 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 is alkyl, R d1 is alkyl, R d1 is R d2 may form a ring with R d1 Ga-NR d4 R d5 If R d4 or R d5 is R d2 may form a ring with R d1 , R d2 , R d3 , R d4 and / or R d5 When is alkyl, the methylene (-CH2-) in the alkyl may be replaced with -NH-, -S- or -O-).

[0064] The amide compound (D) is preferably represented by formula (D-1a) or formula (D-1b), and is preferably represented by formula (D-1b).

[0065] Formula (D-1a) is as follows: [ka] (In the formula, R da1 is a linear C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 and preferably a linear C 2-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 and more preferably amino or methyl. R da2 and R da3 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C3-10 It is alkyl, preferably hydrogen or methyl. R da4 and R da5 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 It is alkyl, preferably hydrogen or methyl. R da1 , R da2 , R da3 , R da4 and / or R da5 When is alkyl, methylene in the alkyl may be replaced by -NH-, -S- or -O-.

[0066] Exemplary embodiments of compounds represented by formula (D-1a) include urea, tetramethylurea, acetamide, dimethylacetamide, formamide, and N,N-dimethylformamide.

[0067] Formula (D-1b) is as follows: [ka] (In the formula, R db1 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 It is alkyl, preferably hydrogen, methyl or ethyl, and the methylene in the alkyl may be replaced by -NH-, -S- or -O-, but is preferably not replaced. L d is a linear or branched chain C 3-8 Alkylene, straight or branched chain C 3-5 Alkylene, more preferably linear C 3-5 It is alkylene, and methylene in the alkyl may be replaced by -NH-, -S- or -O-, preferably may or may not be replaced by -NH, more preferably is not replaced. In a preferred embodiment, the ring in (D-1b) is a 5- or 6-membered ring.

[0068] Exemplary embodiments of compounds represented by formula (D-1b) include ε-caprolactam, σ-valerolactam, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone.

[0069] Considering safety and environmental properties, component (D) is preferably selected from the group consisting of ε-caprolactam, σ-valerolactam, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone.

[0070] The molecular weight of component (D) is preferably 17-500, and more preferably 60-400.

[0071] The component (D) may be one type or two or more types, preferably one type or two or more types, and more preferably one type. The content of component (D) is preferably 0.01 to 7 mass %, more preferably 0.1 to 6 mass %, and even more preferably 0.7 to 3 mass %, based on the total mass of polymer (A).

[0072] Basic Compounds (E) The composition according to the present invention may further contain a basic compound (E), which is expected to have the effect of suppressing environmental impact and the effect of suppressing inactivation of the acid on the membrane surface by amine components contained in the air.

[0073] Component (E) 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 and C 5-30 heterocyclic amines.

[0074] Exemplary embodiments of component (E) 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.

[0075] The base dissociation constant pKb(H2O) of the basic compound (E) is preferably -12 to 5, more preferably 1 to 4.

[0076] The molecular weight of component (E) is preferably 17-500, and more preferably 100-350.

[0077] The component (E) may be one type or two or more types. The content of the component (E) is preferably 0.01 to 3 mass %, more preferably 0.05 to 1.5 mass %, and even more preferably 0.08 to 0.8 mass %, based on the polymer (A).

[0078] Solvent (F) The composition according to the present invention may further contain a solvent (F). In the present invention, component (D) is not included in component (F). Component (F) is not particularly limited as long as it can dissolve each of the components to be mixed. Component (F) is preferably water, a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or any combination thereof, more preferably propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, n-butyl acetate, n-butyl ether, 2-heptanone, cyclohexanone, or any combination thereof, and even more preferably PGME, PGMEA, or a mixture thereof. When two solvents 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 one embodiment of the present invention, component (F) is substantially free of water relative to other layers or films. The water content, based on the total mass of component (F), is preferably 0.1 mass% or less, more preferably 0.01 mass% or less, and even more preferably 0.001 mass% or less. In another preferred embodiment, component (F) is free of water (0 mass%).

[0079] The content of component (F) is preferably 30 to 90 mass %, more preferably 60 to 90 mass %, and even more preferably 75 to 85 mass %, based on the total mass of the composition.

[0080] Surfactant (G) The composition according to the present invention may contain a surfactant (G). When component (G) is contained, coating properties can be improved. Surfactants that can be used in the present invention include (I) anionic surfactants, (II) cationic surfactants, and (III) nonionic surfactants. More specifically, these include (I) alkyl sulfonates, alkyl benzene sulfonic acids, and alkyl benzene sulfonates, (II) lauryl pyridinium chloride and lauryl methyl ammonium chloride, and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene acetylene glycol ether, fluorine-based surfactants (e.g., Fluorad (3M), Megaface (DIC Corporation), Surflon (AGC Inc.)), and organosiloxane-based surfactants (e.g., KF-53 and KP341 (Shin-Etsu Chemical Co., Ltd.)).

[0081] These surfactants may be used alone or in combination of two or more kinds. The content of component (G) is preferably 0 to 20 mass %, more preferably 0.005 to 3 mass %, and even more preferably 0.01 to 1 mass %, based on the total mass of polymer (A).

[0082] Additive (H) The composition according to the present invention may further contain an additive (H) other than components (A) to (G), which is selected from at least one of the group consisting of a plasticizer, a dye, a contrast enhancer, an acid, and a substrate adhesion enhancer. The content of additive (H) (or the total content if multiple additives (H)) is preferably 0 to 20 mass %, more preferably 0 to 5 mass %, and even more preferably 0 to 1 mass %, based on the total mass of polymer (A). It is also a preferred embodiment of the present invention that the composition according to the present invention does not contain component (H).

[0083] The present invention also relates to use of the amide compound or composition represented by formula (D-1) according to the present invention for suppressing standing waves on the side surfaces of a resist pattern, improving the resolution, rectangularity, and / or heat resistance of the resist pattern.

[0084] <Method for producing a resist film> The method for producing a resist film according to the present invention comprises: (1) applying the composition directly onto a substrate; (2) heating the composition to form a resist film. The method for producing a resist pattern according to the present invention comprises: producing a resist film by the above method; (3) exposing the resist film; (4) developing the resist film. The numbers in parentheses indicate the order of the steps. For example, when describing steps (1), (2), and (3), the order of the steps is as described above.

[0085] The composition according to the present invention is applied above 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 an appropriate method. Here, in the present invention, "above" includes a case where a film is formed directly above the substrate, and a case where a film is formed above the substrate via another layer. For example, a planarizing film or a resist underlayer film may be formed directly above the substrate, and the composition according to the present invention can be applied directly above the planarizing film or the resist underlayer film. In the present invention, the effect is exhibited even without forming an underlayer antireflective film, so it is preferable to apply the composition according to the present invention directly above the substrate. The application method is not particularly limited, but examples include a coating method using a spinner or a coater.

[0086] After application of the composition, a resist film is formed by heating (pre-baking). The resist film is heated, for example, using a hot plate. The heating temperature is preferably 100 to 250°C, more preferably 80 to 200°C, and even more preferably 90 to 180°C. The heating time is preferably 60 to 300 seconds, more preferably 90 to 180 seconds. Heating is preferably carried out in an air or nitrogen gas atmosphere.

[0087] The thickness of the resist film varies depending on the exposure wavelength, but is preferably 0.01 to 5 μm, and more preferably 0.1 to 2.5 μm.

[0088] This resist film is exposed through a predetermined mask. The wavelength of light used for exposure is not particularly limited, but a light source of 248 nm±1% or 193 nm±1% is preferably used for exposure. After exposure, post-exposure baking can be performed as necessary. The post-exposure baking temperature is preferably 80 to 150°C, more preferably 100 to 140°C, and the heating time is preferably 60 to 300 seconds, more preferably 60 to 180 seconds. Heating is preferably performed in an air or nitrogen gas atmosphere.

[0089] After exposure, the resist layer is developed using a developer. The developer used is preferably a 2.38% by 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. A surfactant, for example, can also be added to these developers. When a positive resist composition is used, the resist layer in the exposed region is removed by development, and when a negative resist composition is used, the resist layer in the unexposed region is removed by development, thereby forming a resist pattern. Furthermore, the resist pattern can be made even finer by using, for example, a shrinking agent.

[0090] In both positive and negative resist patterns, the effects of standing waves are reduced and the pattern sides have a smooth shape. 1 is a schematic diagram of the cross-sectional shapes of a resist pattern 2 not affected by standing waves and a resist pattern 3 affected by standing waves on a substrate 1. When a resist pattern is affected by standing waves, if a waveform with a large amplitude is formed in the cross section, even a slight difference in film thickness will cause a large fluctuation in the resist top shape and deteriorate dimensional accuracy, so it is preferable that such amplitude be small. If the widths of the resist pattern at the points where the thickness of the resist pattern is minimum and maximum from the point where the substrate and resist pattern contact each other upward are Wi and Wo, respectively, and the ratio Sw is Wi / Wo, then when Sw is 1, the resist pattern is rectangular, and the closer Sw is to 1, the more the effect of standing waves is suppressed, which is preferable.

[0091] The method for producing a processed substrate according to the present invention comprises: producing a resist pattern by the above method; (5) performing processing using the resist pattern as a mask, In step (5), the underlying film of the resist pattern or the substrate, more preferably the substrate, is processed.

[0092] Thereafter, if necessary, the substrate is further processed to form a device. This further processing can be performed using known methods. A method for producing a device according to the present invention includes any of the methods described above, and preferably further includes the step of forming wiring on the processed substrate. Examples of devices include semiconductor devices, liquid crystal display devices, organic electroluminescence display devices, plasma display devices, solar cell devices, etc., with semiconductor devices being preferred.

[0093] The composite according to the present invention is obtained as an intermediate in the production stage of a processed substrate, and comprises at least a substrate and a resist pattern formed above the substrate, and the resist pattern contains at least a polymer A' derived from a polymer (A) having a reactive group, and an amide compound (D). The resist pattern further contains a photoacid generator (B) and / or a quencher (C).

[0094] Preferred embodiments are listed below. [Embodiment 1] A resist composition comprising a polymer (A), a photoacid generator (B), and an amide compound (D): The amide compound (D) is a composition represented by the following formula (D-1): [ka] (In the formula, R d1 is a linear C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR d4 R d5 and R d2 and R d3 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 is alkyl, R d4 and R d5 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 is alkyl, R d1 is alkyl, R d1 is R d2 may form a ring with R d1 Ga-NR d4 R d5 If R d4 or R d5 is R d2 may form a ring with R d1 , R d2 , R d3 , R d4and / or R d5 When is alkyl, methylene (-CH2-) in the alkyl may be replaced by -NH-, -S- or -O-), The content of the amide compound (D) is preferably from 0.01 to 7 mass %, more preferably from 0.1 to 6 mass %, based on the total mass of the polymer (A).

[0095] [Embodiment 2] The composition of embodiment 1, wherein the amide compound (D) is represented by formula (D-1a) or formula (D-1b): [ka] (In the formula, R da1 is a linear C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 and preferably a linear C 2-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 and R da2 and R da3 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 is alkyl, R da4 and R da5 are each independently hydrogen, straight chain C 1-10 Alkyl or branched chain C 3-10 is alkyl, R da1 , R da2 , R da3 , R da4 and / or R da5 When is alkyl, methylene in the alkyl may be replaced by -NH-, -S- or -O-), [ka] (In the formula, R db1 are each independently hydrogen, straight chain C 1-10Alkyl or branched chain C 3-10 alkyl, wherein methylene in the alkyl may be replaced by -NH-, -S- or -O-; L d is a linear or branched chain C 3-8 alkylene, and a methylene in the alkylene may be replaced by -NH-, -S- or -O-. Preferably, the amide compound (D) is selected from the group consisting of urea, tetramethylurea, acetamide, dimethylacetamide, formamide, N,N-dimethylformamide, ε-caprolactam, σ-valerolactam, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

[0096] [Embodiment 3] The composition of embodiment 2, wherein the amide compound (D) is represented by formula (D-1b): Preferably, the amide compound (D) is selected from the group consisting of ε-caprolactam, σ-valerolactam, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

[0097] [Embodiment 4] Polymer (A) comprises at least one repeating unit represented by formula (A-1) and formula (A-2), and optionally further comprises at least one repeating unit represented by formula (A-3) and formula (A-4): [ka] [In the formula, C y 11 and C y 21 are each independently an aryl or heteroaryl having 5 or 6 ring atoms, preferably an aryl having 5 or 6 ring atoms; R 11 , R 21 , R 41 and R 45 are each independently C 1-5alkyl (wherein methylene 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 to 5, p41 is 0 to 4, p45 is 1 to 2, and p41+p45≦5; P 31 is C 4-20 alkyl (wherein some or all of the alkyls may form a ring, some or all of the H in the alkyl may be substituted with halogen, and methylene in the alkyl may be substituted with -O- or carbonyl), and the composition according to at least one of any of embodiments 1 to 3; Preferably, in the composition according to embodiment 1 or 2, the number of repeating units (A-1), (A-2), (A-3) and (A-4) in the polymer (A) is n 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 +nA-4 )=0~50%, or n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 )=0~50%; Preferably, n is the total number of all repeating units contained in the polymer (A). total But the following formula: (n A-1 +n A-2 +n A-3 +n A-4 ) / n total = 80 to 100% fulfilled, or Preferably, the polymer (A) has a mass average molecular weight Mw of 3,000 to 50,000.

[0098] [Embodiment 5] The composition of at least one of embodiments 1 to 4, wherein the photoacid generator (B) is represented by formula (B-1): B n+ Cation B n- Anion Formula (B-1) [ka] [In the formula, B n+ The cation is a cation represented by formula (BC1) (In the formula, R b1 are each independently C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, C 6-12 Aryloxy, nitro, sulfo, carboxy, hydroxy, amino, cyano, halogen, C 1-6 C with halogen-substituted alkyl or ester bond 2-8 is a hydrocarbon group, nb1 are each independently 0, 1, 2 or 3; Cation represented by formula (BC2) [ka] (In the formula, R b2 are each independently C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfo, carboxy, hydroxy, amino, halogen, C 1-6 C with halogen-substituted alkyl or ester bond 2-8 is a hydrocarbon group, nb2 are each independently 0, 1, 2, or 3, and Cation represented by formula (BC3) [ka] (In the formula, R b3 are each independently C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfo, carboxy, hydroxy, amino, halogen, C 1-6 C with halogen-substituted alkyl or ester bond 2-8 is a hydrocarbon group, R b4 are each independently C 1-6 alkyl, provided that two R b4 may be linked to each other to form a ring, nb3 each independently represents 0, 1, 2, or 3; The total is n-valent (n is 1 to 3), B n- The anion is an anion represented by formula (BA1) [ka] (In the formula, R b5 are each independently C 1-6 Fluorine-substituted alkyl or C 1-6 alkyl), An anion represented by formula (BA2) [ka] (In the formula, 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), An anion represented by formula (BA3) [ka] (In the formula, 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, and two R b7 may be bonded to each other to form a fluorine-substituted heterocyclic structure), and An anion represented by formula (BA4) [ka] (In the formula, 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, nb4 is an integer from 0 to 10, nb5 is an integer of 0 to 21), The total is n-valent.

[0099] [Embodiment 6] The composition according to at least one of embodiments 1 to 5, further comprising a photoreaction quencher (C) and / or a basic compound (E): Preferably, the photoreaction quencher (C) is at least one selected from the group consisting of photoreaction quenchers represented by formula (C-1), and the basic compound (E) 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, and C 5-30 at least one compound selected from the group consisting of heterocyclic amine compounds, C m+ Cation C m- Anion Formula (C-1) [In the formula, C m+ The cation is a cation represented by formula (CC1) [ka] (In the formula, R c1 are each independently C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 is aryl, each nc1 is independently 0, 1, 2, or 3; and Cation represented by formula (CC2) [ka] (In the formula, R c2 are each independently C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 is aryl, each nc2 is independently 0, 1, 2, or 3; Overall, the number is m (m is 1 to 3), C m- The anion has the formula (CA) [ka] (In the formula, X is C 1-20 Hydrocarbon or C 6-12 is aryl, R c3 are each independently hydroxy, carboxy, C 1-6 Alkyl or C 6-10 is aryl, nc3 is 1, 2 or 3, nc4 is 0, 1 or 2), Overall, it is m-valent.

[0100] [Embodiment 7] The composition according to at least one of embodiments 1 to 6, wherein the photoacid generator (B) releases an acid having an acid dissociation constant pKa(H2O) of -20 to 1.4 upon exposure, preferably the photoreactive quencher (C) releases a weak acid having an acid dissociation constant pKa(H2O) of 1.5 to 8 upon exposure, preferably the basic compound (E) has a base dissociation constant pKb(H2O) of -12 to 5.

[0101] [Embodiment 8] The composition according to at least one of embodiments 1 to 7, wherein the molecular weight of the photoacid generator (B) is 400 to 2,500 (preferably 400 to 1,500), the molecular weight of the photoreactive quencher (C) is 300 to 1,400 (preferably 300 to 1,200), the molecular weight of the amide compound (D) is 17 to 500 (preferably 60 to 400), and / or the molecular weight of the basic compound (E) is 17 to 500 (preferably 100 to 350).

[0102] [Embodiment 9] 9. The composition of at least one of embodiments 1 to 8, further comprising a solvent (F), wherein preferably the solvent (F) is water, a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or any combination thereof.

[0103] [Embodiment 10] The content of polymer (A) is 10 to 60% by mass based on the total mass of the composition, and / or the content of the photoacid generator (B) is 0.05 to 5% by mass based on the total mass of the polymer (A); Preferably, the content of the photoreactive quencher is 0.01 to 3 mass% based on the total mass of the polymer (A), Preferably, the content of the basic compound (E) is 0.01 to 3 mass% based on the total mass of the polymer (A), The composition according to at least one of embodiments 1 to 9, wherein the content of the solvent (F) is preferably 30 to 90% by weight, based on the total weight of the composition.

[0104] [Embodiment 11] Further comprising a surfactant (G), Preferably, the composition further comprises an additive (H), wherein the additive (H) is selected from at least one of the group consisting of a plasticizer, a dye, a contrast enhancer, an acid, and a substrate adhesion enhancer; Preferably, the content of the surfactant (G) is 0 to 20% by mass based on the total mass of the polymer (A), The composition according to at least one of embodiments 1 to 10, wherein the content of additive (H) is preferably 0 to 20% by weight, based on the total weight of polymer (A).

[0105] [Embodiment 12] The composition according to at least one of embodiments 1 to 11, which is a positive chemically amplified resist composition.

[0106] [Embodiment 13] Use of the composition according to at least one of embodiments 1 to 12 or the amide compound represented by formula (D-1) for suppressing standing waves on the side surfaces of a resist pattern, improving the resolution, rectangularity, and / or heat resistance of the resist pattern.

[0107] [Embodiment 14] A method for producing a resist film, comprising: (1) applying the composition according to at least one of embodiments 1 to 12 above a substrate; (2) heating the composition to form a resist film; Preferably, the heating in (2) is carried out at 100 to 250°C and / or for 60 to 300 seconds, Preferably, the heating in (2) is carried out in an air or nitrogen gas atmosphere, or A method in which a resist film having a thickness of preferably 0.01 to 5 μm, more preferably 0.1 to 2.5 μm, is formed.

[0108] [Embodiment 15] A method for producing a resist pattern, comprising: producing a resist film by the above method; (3) a step of exposing the resist film, preferably using a light source of 248 nm±1% or 193 nm±1% for exposure; (4) developing the resist film.

[0109] [Embodiment 16] 16. The method of embodiment 15, further comprising performing a post-exposure bake between (3) and (4).

[0110] [Embodiment 17] 1. A method for producing a processed substrate, comprising: producing a resist pattern by the method according to embodiment 15 or 16; (5) performing processing using the resist pattern as a mask, Preferably, (5) is a method in which processing is performed on the underlayer film or the substrate (more preferably the substrate).

[0111] [Embodiment 18] A method for manufacturing a device, comprising the method according to at least one of embodiments 15 to 17.

[0112] [Embodiment 19] A composite comprising at least a substrate and a resist pattern formed on the substrate, wherein the resist pattern comprises at least a polymer A' derived from a polymer (A) having a reactive group and an amide compound (D); Preferably, the resist pattern further comprises a photoacid generator (B) and / or a quencher (C).

[0113] The present invention will be described below with reference to various examples, but the embodiments of the present invention are not limited to these examples.

[0114] <Preparation of the composition of Example 101> PGME and EL were mixed in a mass ratio of 70:30 to obtain a mixed solvent. 100 parts by mass of polymer 1, 3.3 parts by mass of photoacid generator 1, 0.19 parts by mass of photoreaction quencher 1, 0.19 parts by mass of basic compound 1, 0.06 parts by mass of surfactant 1, and 0.5 parts by mass of ε-caprolactam as component (D) were added to the mixed solvent to obtain a solids concentration of 17% by mass. The solids concentration refers to the concentration of all components contained in the composition other than the solvent (mixed solvent, etc.) in the entire composition. The resulting mixture was stirred at room temperature for 30 hours. Dissolution of the added components was confirmed visually. The resulting mixture was filtered through a 0.05 μm filter. This yielded the composition of Example 1. Polymer 1: Hydroxystyrene:styrene:t-butyl acrylate copolymer, molar ratio 6:2:2, Mw: 12,000, The above ratios indicate the constituent ratios of each repeating unit. The same applies hereinafter. [ka] Photoacid generator 1 [ka] Photoreactive quencher 1 [ka] Basic compound 1: Tris[2-(2-methoxyethoxy)ethyl]amine Surfactant 1: KF-53 (Shin-Etsu Chemical Co., Ltd.).

[0115] <Preparation of Compositions of Examples 102 to 107 and Comparative Examples 101 to 108> The compositions of Examples 102 to 107 and Comparative Examples 101 to 108 were obtained in the same manner as in "Preparation of composition of Example 101," except that the ε-caprolactam of Example 1 was changed to the compounds and blending amounts shown in Tables 1 and 2. The numerical values ​​of the compositions in the tables are in parts by mass. [Table 1] [Table 2]

[0116] <Formation of resist pattern> Using a coater developer Mark 8 (Tokyo Electron Ltd.), each composition was dropped onto an 8-inch Si wafer and spin-coated. The wafer was then heated at 130°C for 140 seconds using a hot plate under atmospheric conditions to form a resist film. The thickness of the resist film at this stage was measured using an optical interference film thickness measuring device M-1210 (SCREEN) to find it to be 1.5 μm. This resist layer was exposed using a KrF stepper FPA3000-EX5 (Canon). The exposed wafer was then heated (PEB) at 120°C for 90 seconds using a hot plate under atmospheric conditions. The resist layer was then puddle-developed with a 2.38% by weight TMAH aqueous solution for 60 seconds, rinsed with water, and spin-dried at 1000 rpm. This resulted in a trench pattern with a line width of 0.36 μm and a space width of 0.18 μm. The line width and space width were measured at the bottom of the pattern. 2 is a schematic diagram of this pattern shape, in which a resist pattern 5 is formed on a substrate 4. The exposure dose at which a trench pattern having a line width of 0.36 μm and a space width of 0.18 μm is formed is defined as the optimum exposure dose, and the following evaluation is performed using this optimum exposure dose. In Comparative Example 102, no resist pattern was formed.

[0117] <Evaluation of cross-sectional shape> A cross section of the substrate formed in "Formation of Resist Pattern" is made, and its longitudinal section is observed with a scanning electron microscope (SEM). The widths of the resist pattern at the minimum and maximum thicknesses of the resist pattern, measured upward from the point where the substrate and resist pattern contact each other, are designated Wi and Wo, respectively. These Wi and Wo are measured, and the ratio Sw = Wi / Wo is calculated. The Sw value is evaluated according to the following criteria: The results are shown in Tables 1 and 2. A: Sw is greater than 0.95. B: Sw is greater than 0.9 and equal to or less than 0.95. C: Sw is greater than 0.8 and equal to or less than 0.9. D:Sw is 0.8 or less.

[0118] <Resolution evaluation> The resist pattern is formed in the same manner as in "Formation of Resist Pattern," but using a mask pattern with a space size of 0.50 to 0.08 μm, exposure is carried out at the optimum exposure dose described in "Formation of Resist Pattern." The minimum dimension at which the resist pattern can be formed is defined as the resolution (nm), and this resolution is evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2. [Explanation of symbols]

[0119] 1. Substrate 2. Resist patterns unaffected by standing waves 3. Resist patterns affected by standing waves 4. Substrate 5. Resist pattern

Claims

1. A resist composition comprising a polymer (A), a photoacid generator (B), and an amide compound (D): The amide compound (D) has a composition represented by the following formula (D-1): 【Chemical 1】 (In the formula, R ｄ１ is a linear C １－１０ Alkyl, branched chain C ３－１０ Alkyl or -NR ｄ４ R ｄ５ and R ｄ２ and R ｄ３ are each independently hydrogen, straight chain C １－１０ Alkyl or branched chain C ３－１０ is alkyl, R ｄ４ and R ｄ５ are each independently hydrogen, straight chain C １－１０ Alkyl or branched chain C ３－１０ is alkyl, R ｄ１ is alkyl, R ｄ１ is R ｄ２ may form a ring with R ｄ１ Ga-NR ｄ４ R ｄ５ If R ｄ４ or R ｄ５ is R ｄ２ may form a ring with R ｄ１ , R ｄ２ , R ｄ３ , R ｄ４ and / or R ｄ５ is alkyl, methylene (—CH ２ -) may be replaced by -NH-, -S- or -O-), Preferably, the content of the amide compound (D) is 0.01 to 7% by mass based on the total mass of the polymer (A).

2. The composition according to claim 1, wherein the amide compound (D) is represented by formula (D-1a) or formula (D-1b): 【Chemistry 2】 (In the formula, R ｄａ１ is a linear C １－１０ Alkyl, branched chain C ３－１０ Alkyl or -NR ｄａ４ R ｄａ５ and preferably a linear C ２－１０ Alkyl, branched chain C ３－１０ Alkyl or -NR ｄａ４ R ｄａ５ and R ｄａ２ and R ｄａ３ are each independently hydrogen, straight chain C １－１０ Alkyl or branched chain C ３－１０ is alkyl, R ｄａ４ and R ｄａ５ are each independently hydrogen, straight chain C １－１０ Alkyl or branched chain C ３－１０ is alkyl, R ｄａ１ , R ｄａ２ , R ｄａ３ , R ｄａ４ and / or R ｄａ５ When is alkyl, methylene in the alkyl may be replaced by -NH-, -S- or -O-), 【Chemistry 3】 (In the formula, R ｄｂ１ are each independently hydrogen, straight chain C １－１０ Alkyl or branched chain C ３－１０ alkyl, wherein methylene in the alkyl may be replaced by —NH—, —S— or —O—; L ｄ is a linear or branched chain C ３－８ alkylene, wherein a methylene in the alkylene may be replaced by -NH-, -S- or -O-.

3. The composition according to claim 2, wherein the amide compound (D) is represented by formula (D-1b):

4. The polymer (A) contains at least one repeating unit represented by formula (A-1) and formula (A-2), and optionally further contains at least one repeating unit represented by formula (A-3) and formula (A-4): 【Chemistry 4】 [In the formula, C ｙ １１ and C ｙ ２１ are each independently an aryl or heteroaryl having 5 or 6 ring atoms, preferably an aryl having 5 or 6 ring atoms; R １１ , R ２１ , R ４１ and R ４５ are each independently C １－５ alkyl (wherein methylene 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 to 5, p41 is 0 to 4, p45 is 1 to 2, and p41+p45≦5; P ３１ is C ４－２０ The composition according to any one of claims 1 to 3, which is alkyl (part or all of the alkyl may form a ring, part or all of H in the alkyl may be substituted with halogen, and methylene in the alkyl may be substituted with -O- or carbonyl). Preferably, the composition according to claim 1 or 2, wherein the number of repeating units (A-1), (A-2), (A-3) and (A-4) in the polymer (A) is n 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 to 50% or n Ａ－４ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) = 0 to 50%, Preferably, the total number of all repeating units contained in the polymer (A) is n ｔｏｔａｌ is expressed by the following formula: (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) / n ｔｏｔａｌ = 80 to 100% is met, or Preferably, the polymer (A) has a mass average molecular weight Mw of 3,000 to 50,000.

5. The composition according to any one of claims 1 to 4, wherein the photoacid generator (B) is represented by formula (B-1): B ｎ＋ Cation B ｎ－ Anion Formula (B-1) [In the formula, B ｎ＋ The cation is a cation represented by formula (BC1) 【Chemistry 5】 (In the formula, R ｂ１ are each independently C １－６ Alkyl, C １－６ Alkoxy, C ６－１２ Aryl, C ６－１２ Arylthio, C ６－１２ Aryloxy, nitro, sulfo, carboxy, hydroxy, amino, cyano, halogen, C １－６ C having halogen-substituted alkyl or ester bond ２－８ is a hydrocarbon group, nb1 are each independently 0, 1, 2 or 3; A cation represented by formula (BC2) 【Chemistry 6】 (In the formula, R ｂ２ are each independently C １－６ Alkyl, C １－６ Alkoxy, C ６－１２ Aryl, nitro, sulfo, carboxy, hydroxy, amino, halogen, C １－６ C having halogen-substituted alkyl or ester bond ２－８ is a hydrocarbon group, nb2 are each independently 0, 1, 2, or 3, and Cation represented by formula (BC3) 【Chemistry 7】 (In the formula, R ｂ３ are each independently C １－６ Alkyl, C １－６ Alkoxy, C ６－１２ Aryl, nitro, sulfo, carboxy, hydroxy, amino, halogen, C １－６ C having halogen-substituted alkyl or ester bond ２－８ is a hydrocarbon group, R ｂ４ are each independently C １－６ alkyl, provided that two R ｂ４ may be linked to each other to form a ring, nb3 each independently represents 0, 1, 2, or 3; The total valency is n (n is 1 to 3), B ｎ－ The anion is an anion represented by formula (BA1) 【Chemistry 8】 (In the formula, R ｂ５ are each independently C １－６ Fluorine-substituted alkyl or C １－６ alkyl), An anion represented by formula (BA2) 【Chemistry 9】 (In the formula, 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), An anion represented by formula (BA3) 【Chemistry 10】 (In the formula, 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, and two R ｂ７ may be bonded to each other to form a fluorine-substituted heterocyclic structure), and An anion represented by formula (BA4) 【Chemistry 11】 (In the formula, 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, nb4 is an integer from 0 to 10, nb5 is an integer from 0 to 21), The total is n-valent.

6. The composition according to any one of claims 1 to 5, further comprising a photoreaction quencher (C) and / or a basic compound (E): Preferably, the photoreaction quencher (C) is at least one selected from the group consisting of photoreaction quenchers represented by formula (C-1), and the basic compound (E) 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, and C ５－３０ at least one compound selected from the group consisting of heterocyclic amine compounds, C ｍ＋ Cation C ｍ－ Anion Formula (C-1) [In the formula, C ｍ＋ The cation is a cation represented by formula (CC1): 【Chemistry 12】 (In the formula, R ｃ１ are each independently C １－６ Alkyl, C １－６ Alkoxy or C ６－１２ is aryl, ncl is independently 0, 1, 2, or 3; and Cation represented by formula (CC2) 【Chemistry 13】 (In the formula, R ｃ２ are each independently C １－６ Alkyl, C １－６ Alkoxy or C ６－１２ is aryl, Each n c2 is independently 0, 1, 2, or 3; The total is m-valent (m is 1 to 3), C ｍ－ The anion has the formula (CA) 【Chemistry 14】 (In the formula, X is C １－２０ Hydrocarbon or C ６－１２ is aryl, R ｃ３ are each independently hydroxy, carboxy, C １－６ Alkyl or C ６－１０ is aryl, nc3 is 1, 2 or 3; nc4 is 0, 1 or 2), The total is m-valent.

7. The photoacid generator (B) exhibits an acid dissociation constant pKa (H ２ Preferably, the photoreactive quencher (C) releases an acid having an acid dissociation constant pKa (H ２ The base dissociation constant pKb(H) of the basic compound (E) is preferably 1.5 to 8. ２ The composition of any one of claims 1 to 6, wherein O) is -12 to 5.

8. The composition according to any one of claims 1 to 7, wherein the molecular weight of the photoacid generator (B) is 400 to 2,500 (preferably 400 to 1,500), the molecular weight of the photoreactive quencher (C) is 300 to 1,400 (preferably 300 to 1,200), the molecular weight of the amide compound (D) is 17 to 500 (preferably 60 to 400), and / or the molecular weight of the basic compound (E) is 17 to 500 (preferably 100 to 350).

9. The composition according to any one of claims 1 to 8, which is a positive chemically amplified resist composition.

10. A method for producing a resist film, comprising: (1) applying the composition according to any one of claims 1 to 9 above a substrate; (2) heating the composition to form a resist film; Preferably, the heating in (2) is carried out at 100 to 250°C and / or for 60 to 300 seconds; Preferably, the heating in (2) is carried out in an air or nitrogen gas atmosphere, or Preferably, a resist film having a thickness of 0.01 to 5 μm, more preferably 0.1 to 2.5 μm, is formed.

11. A method for producing a resist pattern, comprising: producing a resist film by the method according to claim 10; (3) a step of exposing the resist film, preferably using a light source of 248 nm±1% or 193 nm±1% for exposure; (4) developing the resist film.

12. The method of claim 11 further comprising performing a post-exposure bake between (3) and (4).

13. 1. A method for producing a processed substrate, comprising: A step of producing a resist pattern by the method according to claim 11 or 12; (5) performing processing using the resist pattern as a mask, Preferably, the method (5) involves processing the underlayer film or the substrate (more preferably the substrate).

14. A method for manufacturing a device comprising the method of claim 13.

15. A composite comprising at least a substrate and a resist pattern formed on the substrate, wherein the resist pattern comprises at least a polymer A' derived from a polymer (A) having a reactive group and an amide compound (D); Preferably, the resist pattern further comprises a photoacid generator (B) and / or a quencher (C).

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