Resist composition, method for manufacturing resist film, and method for manufacturing device

Abstract

A resist composition, a method of manufacturing a resist film, and a method of manufacturing 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 Art

[0002] In recent years, the demand for high integration of LSI has been growing, and the miniaturization of patterns has become inevitable. In order to meet this demand, photolithography processes using KrF excimer laser (248nm), ArF excimer laser (193nm), extreme ultraviolet (EUV; 13nm), short-wavelength X-rays, electron beams, etc. have been put into practical use. In order to cope with the miniaturization of such resist patterns, and for photosensitive resin compositions used as resists in the miniaturization process, resin compositions with high resolution are required. Finer patterns can be formed by exposure with short-wavelength light, but high dimensional accuracy is required.

[0003] In the photolithography process, a resist pattern is formed by exposing and developing the resist. It is known that during exposure, incident light on the resist and reflected light from the substrate or air interface interfere with each other to produce a standing wave phenomenon. The generation of standing waves reduces the dimensional accuracy of the pattern. Attempts have been made to form an anti-reflective coating on the top and / or bottom layers of the resist to reduce the standing waves.

[0004] It has been proposed that, for example, an organic compound may be included in a photolithography component such as a resist to suppress the migration speed of an acid generated by an acid generator, thereby reducing standing waves (WO 2022 / 023230A).

[0005] Prior art literature

[0006] Patent Literature

[0007] [Patent Document 1] WO 2022 / 023230 A BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 1 is a conceptual diagram showing the cross-sectional shape of a resist pattern when not affected by a standing wave and when affected by a standing wave.

[0009] Figure 2 is a conceptual diagram showing a cross-sectional shape of a groove pattern. Summary of the invention

[0010] Problems to be solved by the present invention

[0011] The present inventors believe that the resist composition still has one or more problems that need to be improved. These problems are, for example, as described below.

[0012] The side wall of the resist pattern sways due to the standing wave; the width of the resist pattern is uneven; the rectangularity of the resist pattern is low; the sensitivity is low; and the resolution is low.

[0013] Means used to solve problems

[0014] The resist composition according to the present inventors contains a polymer (A), a photoacid generator (B) and an amide compound (D).

[0015] The amide compound (D) is represented by the formula (D-1).

[0016]

[0017] Among them, R d1 For straight chain C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR d4 R d5 ,

[0018] R d2 and R d3 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 alkyl,

[0019] R d4 and R d5 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 alkyl,

[0020] Among them, when R d1 When it is an alkyl group, R d1 Can be used with R d2 To form a ring, when R d1 For-NR d4 R d5 When R d4 or R d5 Can be used with R d2 Form a ring, and

[0021] When R d1 , R d2 , R d3 , R d4 and / or R d5 In the case of an alkyl group, the methylene group (-CH2-) in the alkyl group may be replaced by -NH-, -S- or -O-.

[0022] The method for manufacturing a resist film according to the present invention comprises the following steps:

[0023] (1) applying the above composition onto a substrate; and

[0024] (2) The composition is heated to form a resist film.

[0025] A method of manufacturing a device according to the present invention includes the above method.

[0026] Effects of the Invention

[0027] According to the present invention, one or more of the following effects can be expected.

[0028] The effect of reducing standing waves in the resist pattern is high; the width of the resist pattern is uniform; the rectangularity of the resist pattern is high; the resolution of the resist pattern is high; the heat resistance of the resist pattern is high; and the efficiency of the manufacturing process is high. DETAILED DESCRIPTION

[0029] The embodiments of the present invention are described in detail below.

[0030] [definition]

[0031] Unless otherwise stated in this specification, the definitions and examples described in this paragraph apply.

[0032] The singular form includes the plural form, and “a”, “an” or “it” means “at least one”. An element in a concept may be expressed using a plurality of species, and when describing an amount (for example, mass % or mol %), it refers to the total of the plurality of species.

[0033] "And / or" includes all combinations of elements and also includes individual use of the elements.

[0034] When "to / ~" or "-" is used to express a numerical range, both end points are included and the units are the same. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0035] Such as "C x-y ”, “C x -C y ” and “C x " indicates the number of carbon atoms in a molecule or substituent. For example, C 1-6 The alkyl group represents an alkyl chain having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl).

[0036] When a polymer has multiple repeating units, these repeating units are copolymerized. These copolymerizations are any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, n, m, etc. after the brackets represent the number of repetitions.

[0037] The temperature unit is Celsius, for example 20 degrees means 20 degrees Celsius.

[0038] The additive refers to a compound having a function itself (for example, in the case of a base generator, it refers to a compound that generates a base itself). It can also be an embodiment in which the compound is dissolved or dispersed in a solvent and added to the composition. As an embodiment of the present invention, it is preferred that such a solvent is contained in the composition of the present invention as a solvent (F) or other components.

[0039] <Resist Composition>

[0040] The resist composition according to the present invention (hereinafter referred to as composition) contains a polymer (A), a photoacid generator (B), and an amide compound (D) having a specific structure.

[0041] The composition according to the present invention is preferably a chemically amplified resist composition, more preferably a chemically amplified KrF resist composition.

[0042] The composition according to the present invention can also be used for both positive and negative types. In a preferred embodiment of the present invention, the composition according to the present invention is a positive chemically amplified resist composition, more preferably a positive chemically amplified KrF resist composition.

[0043] Polymer (A)

[0044] 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.

[0045] Polymer (A) comprises at least one of the repeating units represented by formula (A-1) and formula (A-2), and preferably, further comprises at least one of the repeating units represented by formula (A-3) and formula (A-4). More preferably, polymer (A) comprises the repeating unit represented by formula (A-1), and further comprises at least one of the repeating units represented by formula (A-3) and formula (A-4). In a preferred embodiment, polymer (A) comprises the repeating units represented by formula (A-1), formula (A-2) and formula (A-3), and more preferably, polymer (A) is substantially composed of the repeating units represented by formula (A-1), formula (A-2) and formula (A-3).

[0046] Formula (A-1) is as follows:

[0047]

[0048] Among them, C y 11 Each is independently an aryl or heteroaryl group having 5 or 6 ring atoms, preferably benzene.

[0049] R 11 Each independently is C1-5 The alkyl group (wherein the methylene group in the alkyl group may be replaced by an oxy group) is preferably a methyl group or an ethyl group, and more preferably a methyl group. In the present invention, the expression "the methylene group in the alkyl group may be replaced by an oxy group" means that an oxy group may exist between carbon atoms in the alkyl group, and does not mean that the terminal carbon in the alkyl group becomes an oxy group, that is, it does not mean that an alkoxy group or a hydroxy group exists in the alkyl group.

[0050] R 12 , R 13 and R 14 are independently hydrogen, C 1-5 Alkyl, C 1-5 The alkoxy group or -COOH is preferably hydrogen or methyl, more preferably hydrogen.

[0051] p11 is 0 to 4, preferably 0 or 1, and more preferably 0.

[0052] p15 is 1 to 2, preferably 1. The condition is that p11+p15≤5 is satisfied.

[0053] The polymer (A) may contain a plurality of repeating units represented by the formula (A-1). For example, the polymer (A) may have a structural unit with p15=1 and a structural unit with p15=2 at a ratio of 1:1. In this case, p15=1.5 as a whole. The same shall apply to the numbers representing the polymers in the present invention unless otherwise specified.

[0054] Exemplary embodiments of formula (A-1) include the following:

[0055]

[0056] Formula (A-2) is as follows:

[0057]

[0058] Among them, C y 21 Each is independently an aryl or heteroaryl group having 5 or 6 ring atoms, preferably benzene.

[0059] R 21 Each independently is C 1-5 The alkyl group (wherein the methylene group in the alkyl group may be substituted by an oxy group) is preferably a methyl group, an ethyl group, a tert-butyl group or a tert-butoxy group, more preferably a methyl group or an ethyl group, and further preferably a methyl group.

[0060] R 22 , R 23 and R 24 are independently hydrogen, C 1-5 Alkyl, C 1-5 The alkoxy group or -COOH is preferably hydrogen or methyl, more preferably hydrogen.

[0061] p21 is 0 to 5, preferably 0, 1, 2, 3, 4 or 5, more preferably 0 or 1, further preferably 0.

[0062] Exemplary embodiments of formula (A-2) include the following:

[0063]

[0064] Formula (A-3) is as follows:

[0065]

[0066] Among them, R 32 , R 33 and R 34 are independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH; preferably hydrogen, methyl, ethyl, tert-butyl, methoxy, tert-butoxy or -COOH; more preferably hydrogen or methyl; further preferably hydrogen.

[0067] P 31 C 4-20 Alkyl, part or all of the alkyl group may form a ring, part or all of the H in the alkyl group may be substituted by halogen, and the methylene group in the alkyl group may be replaced by an oxy group or a carbonyl group. 31 The alkyl portion of is preferably branched or cyclic. 31 C 4-20 When the alkyl group is substituted with halogen, it is preferably completely substituted, and the substituted halogen is preferably F or Cl, more preferably F. 31 C 4-20 It is a preferred embodiment of the present invention that H in the alkyl group is not substituted by halogen. 31 Preferred is methyl, isopropyl, tert-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, adamantyl, methyladamantyl or ethyladamantyl, more preferably tert-butyl, ethylcyclopentyl, ethylcyclohexyl or ethyladamantyl, further preferably tert-butyl, ethylcyclopentyl or ethyladamantyl, further more preferably tert-butyl.

[0068] Exemplary embodiments of formula (A-3) include the following:

[0069]

[0070] Formula (A-4) is as follows:

[0071]

[0072] Among them, R 41 Each independently is C1-5 The alkyl group (wherein the methylene group in the alkyl group may be replaced by an oxy group) is preferably a methyl group, an ethyl group or a tert-butyl group, and more preferably a methyl group.

[0073] R 45 Each independently is C 1-5 The alkyl group (wherein the methylene group in the alkyl group may be replaced by an oxy group) is preferably a methyl group, a tert-butyl group or -CH(CH3)-O-CH2CH3.

[0074] R 42 , R 43 and R 44 are independently hydrogen, C 1-5 Alkyl, C 1-5 The alkoxy group or -COOH is preferably hydrogen or methyl, more preferably hydrogen.

[0075] p41 is 0 to 4, more preferably 0 or 1, and further preferably 0.

[0076] p45 is 1 to 2, more preferably 1.

[0077] Satisfies p41+p45≤5.

[0078] Exemplary embodiments of formula (A-4) include the following:

[0079]

[0080] 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 This will be explained later.

[0081] 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%, further preferably 55 to 75%, and further preferably 55 to 65%.

[0082] 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%, further preferably 5 to 25%, and further preferably 15 to 25%.

[0083] n A-3 / (n A-1 +nA-2 +n A-3 +n A-4 ) is preferably 0 to 50%, more preferably 10 to 40%, further preferably 15 to 35%, and further preferably 15 to 25%.

[0084] 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%, further preferably 0 to 10%, and further preferably 0 to 5%. A-4 Being 0 is also a preferred embodiment of the present invention.

[0085] Preferred embodiments include the following: A-1 / (n A-1 +n A-2 +n A-3 +n A-4 ) = 40 to 80%, n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 ) = 0 to 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%.

[0086] The polymer (A) may further contain other repeating units in addition to the repeating units represented by the formulae (A-1), (A-2), (A-3) and (A-4). When the total number of all repeating units contained in the polymer (A) is designated as n total hour,

[0087] (n A-1 +n A-2 +n A-3 +n A-4 ) / n total It is preferably 80 to 100%, more preferably 90 to 100%, and further preferably 95 to 100%. It is also a preferred embodiment that polymer (A) contains no other repeating units.

[0088] When the composition according to the present invention is a positive resist composition, exemplary embodiments of the polymer (A) include the following:

[0089]

[0090] When the composition according to the present invention is a negative resist composition, exemplary embodiments of the polymer (A) include the following:

[0091]

[0092] The mass average molecular weight (hereinafter referred to as Mw) of the polymer (A) is 3,000 to 50,000, more preferably 4,000 to 20,000, further preferably 10,000 to 19,000, and further preferably 11,000 to 13,000. Without being bound by theory, it is believed that since the polymer (A) has such Mw, a resist pattern having good rectangularity or resolution can be formed from the composition of the present invention.

[0093] In the present invention, Mw can be measured by gel permeation chromatography (GPC). When measuring, a preferred example is: the GPC column temperature is 40° C., the elution solvent is tetrahydrofuran, the elution rate is 0.6 mL / min, and monodisperse polystyrene is used as the standard.

[0094] The content of the polymer (A) is preferably 10 to 60% by mass, more preferably 10 to 30% by mass, further preferably 12 to 18% by mass, based on the total mass of the composition.

[0095] The composition according to the present invention may contain a polymer other than the polymer (A), but an embodiment containing no polymer other than the polymer (A) is a preferred embodiment.

[0096] Photoacid generator (B)

[0097] The composition of the present invention contains a photoacid generator (B). The photoacid generator (B) releases an acid by light irradiation, and the acid acts on the polymer to increase the solubility of the polymer in an alkaline aqueous solution. For example, when the polymer has an acid group protected by a protecting group, the protecting group is eliminated by the acid. The component (B) used in the composition of the present invention can be selected from conventionally known components.

[0098] The photoacid generator (B) preferably releases an acid having an acid dissociation constant pKa (H2O) of -20 to 1.4 upon exposure, more preferably -16 to 1.4, further preferably -16 to 1.2, and further preferably -16 to 1.1.

[0099] The photoacid generator (B) is preferably represented by formula (B-1).

[0100] B n+ Cation B n-Anionic formula (B-1)

[0101] Among them, B n+ The cation is composed of at least one cation selected from the group consisting of cations represented by formula (BC1) to formula (BC3), and is n-valent as a whole (wherein n is 1 to 3, preferably 1 or 2, and more preferably 1).

[0102] B n- The anion is composed of at least one anion selected from the group consisting of anions represented by Formula (BA1) to Formula (BA4), and has a valence of n as a whole.

[0103] Formula (BC1) is as follows:

[0104]

[0105] Among them, R b1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, C 6-12 Aryloxy, nitro, sulfonyl, carboxyl, hydroxyl, amino, cyano, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbyl, preferably C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio or C 6-12 The aryloxy group is more preferably a methyl group, an ethyl group, a tert-butyl group, a methoxy group, an ethoxy group, a phenylthio group or a phenoxy group, and further preferably a tert-butyl group, a methoxy group, an ethoxy group, a phenylthio group or a phenoxy group.

[0106] nb1 is each independently 0, 1, 2 or 3, preferably 0 or 1.

[0107] In a preferred embodiment, all nb1 are zero.

[0108] In another preferred embodiment, all nb1 are 1, and all R b1 are the same.

[0109] Exemplary embodiments of Formula (BC1) include the following:

[0110]

[0111] Formula (BC2) is as follows:

[0112]

[0113] Among them, Rb2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfonyl, carboxyl, hydroxyl, amino, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbyl, preferably C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, more preferably having C 4-6 The branched alkyl group is more preferably a tert-butyl group or a 1,1-dimethylpropyl group, and further preferably a tert-butyl group.

[0114] nb2 are each independently 0, 1, 2 or 3, preferably 1.

[0115] Exemplary embodiments of Formula (BC2) include the following:

[0116]

[0117] Formula (BC3) is as follows:

[0118]

[0119] Among them, R b3 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfonyl, carboxyl, hydroxyl, amino, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbyl, preferably C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 The aryl group is preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and more preferably a methyl group or a methoxy group.

[0120] R b4 Each independently is C 1-6 Alkyl, preferably methyl or ethyl, more preferably methyl; provided that both R b4 They may be linked to each other to form a ring, but preferably do not form a ring.

[0121] nb3 is each independently 0, 1, 2 or 3, more preferably 3.

[0122] Exemplary embodiments of Formula (BC3) include the following:

[0123]

[0124] B n+The cation is preferably selected from the group consisting of cations represented by formula (BC1) or formula (BC2), and is more preferably a cation represented by formula (BC1).

[0125] Formula (BA1) is as follows:

[0126]

[0127] Among them, R b5 Each independently is 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 fluorine. 1-6 All hydrogen atoms present in the fluorine-substituted alkyl group are replaced by fluorine atoms. b5 The alkyl portion of is preferably methyl, ethyl or tert-butyl (more preferably methyl). b5 It is preferably a fluorine-substituted alkyl group, and more preferably -CF3.

[0128] Exemplary embodiments of Formula (BA1) include the following:

[0129]

[0130] Formula (BA2) is as follows:

[0131]

[0132] Among them, R b6 C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorinated acyl or C 6-12 Fluorine-substituted alkoxyaryl, preferably C 1-6 Fluorine-substituted alkyl, more preferably C 2-6 Fluorine-substituted alkyl. b6 The alkyl portion of R is preferably methyl, ethyl, propyl, butyl or pentyl, more preferably propyl, butyl or pentyl, further preferably butyl. b6 The alkyl portion of R is preferably linear. b6 Preferably C 1-6 Fluorine-substituted alkyl.

[0133] Exemplary embodiments of Formula (BA2) include the following:

[0134] C4F9SO3 - and C3F7SO3 -

[0135] Formula (BA3) is as follows:

[0136]

[0137] Among them, R b7 Each independently is C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorinated acyl or C 6-12 Fluorine-substituted alkoxyaryl, preferably C 2-6 Fluorine-substituted alkyl; R b7 The alkyl portion of is preferably methyl, ethyl, propyl, butyl or pentyl, more preferably methyl, ethyl or butyl, further preferably butyl; R b7 The alkyl portion of is preferably linear.

[0138] Among them, the two R b7 They may be bonded to each other to form a fluorine-substituted heterocyclic structure. In this case, the heterocyclic ring may be a monocyclic ring or a polycyclic ring, but is preferably a monocyclic structure having 5 to 8 members.

[0139] Exemplary embodiments of Formula (BA3) include the following:

[0140]

[0141] Formula (BA4) is as follows:

[0142]

[0143] Among them, R b8 For hydrogen, C 1-6 Alkyl, C 1-6 The alkoxy group or the hydroxy group is preferably hydrogen, methyl, ethyl, methoxy or hydroxy, and more preferably hydrogen or hydroxy.

[0144] L b It is a carbonyl group, an oxy group or a carbonyloxy group, preferably a carbonyl group or a carbonyloxy group, more preferably a carbonyl group.

[0145] Y b Each is independently hydrogen or fluorine, and preferably at least one or more of them is fluorine.

[0146] nb5 is an integer from 0 to 10, and preferably 0.

[0147] nb6 is an integer from 0 to 21, and is preferably 4, 5 or 6.

[0148] Exemplary embodiments of Formula (BA4) include the following:

[0149]

[0150] The molecular weight of component (B) is preferably 400 to 2,500, more preferably 400 to 1,500.

[0151] The component (B) may be one kind or two or more kinds, preferably one kind or two or more kinds, more preferably one kind.

[0152] The content of the component (B) is preferably from 0.05 to 5% by mass, more preferably from 0.1 to 5% by mass, further preferably from 1 to 4% by mass of the polymer (A).

[0153] Photoreaction quencher (C)

[0154] The composition according to the present invention may also contain a photoreaction quencher (C). The photoreaction quencher (C) releases an acid by light irradiation, but the acid does not directly act on the polymer. In this regard, the photoreaction quencher is different from the photoacid generator (B) that directly acts on the polymer by eliminating the protective group of the polymer through the released acid.

[0155] Component (C) functions as a quencher that inhibits the diffusion of the acid generated by the detachment of component (B) in the exposed area. This is not bound by theory, but is considered to be the following mechanism. Upon exposure, component (B) releases an acid, and when the acid diffuses to the unexposed area (unexposed area), a salt exchange occurs with component (C). That is, the anion of component (B) and the cation of component (C) become a salt. This inhibits the diffusion of the acid. At this time, the anion of component (C) is released, but this is a weak acid and cannot deprotect the polymer, so it is believed that the unexposed area is not affected.

[0156] Component (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.

[0157] Component (C) is preferably at least one selected from the group consisting of photoreaction quenchers represented by formula (C-1).

[0158] C m+ Cation C m- Anionic formula (C-1)

[0159] in,

[0160] C m+ The cation is composed of at least one cation selected from the group consisting of cations represented by Formula (CC1) and Formula (CC2), and is m-valent as a whole (wherein m is 1 to 3).

[0161] C m- The anion is composed of at least one anion represented by the formula (CA), and has a valence of m as a whole.

[0162] The valence m is preferably monovalent or divalent, and more preferably monovalent.

[0163] Formula (CC1) is as follows:

[0164]

[0165] Among them, R c1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 The aryl group is preferably a methyl group, an ethyl group, a tert-butyl group, a methoxy group, an ethoxy group, a phenylthio group or a phenoxy group, more preferably a tert-butyl group, a methoxy group, an ethoxy group, a phenylthio group or a phenoxy group, further preferably a tert-butyl group or a methoxy group.

[0166] nc1 is each independently 0, 1, 2 or 3, more preferably 0 or 1.

[0167] In a preferred embodiment, all nc1 are zero.

[0168] In another preferred embodiment, all nc1 are 1, and all R c1 are the same.

[0169] Exemplary embodiments of Formula (CC1) include the following:

[0170]

[0171] Formula (CC2) is as follows:

[0172]

[0173] Among them, R c2 Independently for C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, preferably, R c2 For C 4-6 The alkyl groups of the branched structure may be the same or different, and are more preferably the same; R c2 More preferred is a tert-butyl group or a 1,1-dimethylpropyl group, and still more preferred is a tert-butyl group.

[0174] nc2 is each independently 0, 1, 2 or 3, preferably each is 1.

[0175] Exemplary embodiments of Formula (CC2) include the following:

[0176]

[0177] Formula (CA) is as follows:

[0178]

[0179] Where X is C 1-20 Hydrocarbon or C 6-12 Aryl. X may be linear, branched or cyclic, but is preferably linear or cyclic. When X is linear, X is preferably C 1-4 (More preferably C 1-2 ), with one double bond in the chain, but preferably saturated. When X is cyclic, X may be a monocyclic aromatic ring or a saturated monocyclic or polycyclic ring, when a monocyclic ring, preferably a 6-membered ring, and when a polycyclic ring, preferably an adamantane ring. X is preferably a methyl, ethyl, propyl, butyl, ethane, phenyl, cyclohexane or adamantane, more preferably a methyl, phenyl or cyclohexane, and further preferably a phenyl.

[0180] R c3 are independently hydroxyl, carboxyl, C 1-6 Alkyl or C 6-10 The aryl group is preferably a hydroxyl group, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a tert-butyl group or a phenyl group, and more preferably a hydroxyl group.

[0181] nc3 is 1, 2 or 3, preferably 1 or 2, and more preferably 1.

[0182] nc4 is 0, 1 or 2, preferably 0 or 1, and more preferably 1.

[0183] Exemplary embodiments of formula (CA) include the following:

[0184]

[0185] The molecular weight of the photoreaction quencher (C) is preferably 300 to 1,400, more preferably 300 to 1,200.

[0186] The content of the photoreaction quencher (C) is preferably 0.01 to 3% by mass, more preferably 0.05 to 1.5% by mass, further preferably 0.08 to 0.8% by mass, based on the total mass of the polymer (A).

[0187] Amide compound (D)

[0188] The composition according to the present invention contains an amide compound (D), the component (D) is represented by the formula (D), and does not contain aniline or imide.

[0189] In the present invention, the presence of the amide compound (D) can significantly suppress the influence of standing waves. Without being bound by theory, it is believed that the component (D) has an amide structure that easily interacts with the acid generated by the photoacid generator (B), thereby suppressing the transfer rate of the acid.

[0190] Formula (D-1) is as follows:

[0191]

[0192] Among them, R d1 For straight chain C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR d4 R d5 ,

[0193] R d2 and R d3 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 alkyl,

[0194] R d4 and R d5 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 alkyl,

[0195] Among them, when R d1 When it is an alkyl group, R d1 Can be used with R d2 To form a ring, when R d1 For-NR d4 R d5 When R d4 or R d5 Can be used with R d2 Form a ring, and

[0196] When R d1 , R d2 , R d3 , R d4 and / or R d5 In the case of an alkyl group, the methylene group (-CH2-) in the alkyl group may be replaced by -NH-, -S- or -O-.

[0197] The amide compound (D) is preferably represented by the formula (D-1a) or the formula (D-1b), and is preferably represented by the formula (D-1b).

[0198] Formula (D-1a) is as follows:

[0199]

[0200] Among them, R da1 For straight chain C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 , preferably a straight chain C 2-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 Rda5 , more preferably amino or methyl.

[0201] R da2 and R da3 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 The alkyl group is preferably hydrogen or methyl.

[0202] R da4 and R da5 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 The alkyl group is preferably hydrogen or methyl.

[0203] Among them, when R da1 , R da2 , R da3 , R da4 and / or R da5 In the case of an alkyl group, the methylene group in the alkyl group may be replaced by -NH-, -S- or -O-.

[0204] Exemplary embodiments of the compound represented by formula (D-1a) include urea, tetramethylurea, acetamide, dimethylacetamide, formamide, N,N-dimethylformamide, and the like.

[0205] Formula (D-1b) is as follows:

[0206]

[0207] Among them, R db1 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 The alkyl group is preferably hydrogen, methyl or ethyl, and the methylene group in the alkyl group may be replaced by -NH-, -S- or -O-, but is preferably not replaced.

[0208] L d C is a straight chain or branched chain 3-8 Alkylene, linear or branched C 3-5 Alkylene, more preferably a straight chain C 3-5 The alkylene group and the methylene group in the alkyl group may be replaced by -NH-, -S- or -O-, preferably replaced by -NH- or unsubstituted, more preferably unsubstituted.

[0209] In a preferred embodiment, the ring in (D-1b) is a 5- or 6-membered ring.

[0210] Exemplary embodiments of the compound represented by formula (D-1b) include ε-caprolactam, σ-valerolactam, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone.

[0211] Considering safety and environmental protection characteristics, 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.

[0212] The molecular weight of component (D) is preferably 17-500, more preferably 60-400.

[0213] The component (D) may be one kind or two or more kinds, preferably one kind or two or more kinds, more preferably one kind.

[0214] The content of component (D) is preferably 0.01 to 7% by mass, more preferably 0.1 to 6% by mass, further preferably 0.7 to 3% by mass, based on the total mass of polymer (A).

[0215] Basic compounds (E)

[0216] The composition according to the present invention may further contain a basic compound (E). The basic compound (E) is expected to have an effect of suppressing environmental influences and an effect of suppressing acid deactivation on the membrane surface due to amine components contained in the air.

[0217] The basic compound (E) is preferably selected from ammonia, C 1-16 Aliphatic primary amine, C 2-32 Aliphatic secondary amine, C 3-48 Aliphatic tertiary amine, C 6-30 Aromatic amines and C 5-30 is selected from the group consisting of heterocyclic amines.

[0218] Exemplary embodiments of component (E) include ammonia, ethylamine, n-octylamine, ethylenediamine, triethylamine, triethanolamine, tripropylamine, tributylamine, triisopropanolamine, diethylamine, tri[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.

[0219] The base dissociation constant pKb(H2O) of the basic compound (E) is preferably from -12 to 5, more preferably from 1 to 4.

[0220] The molecular weight of component (E) is preferably 17-500, more preferably 100-350.

[0221] The component (E) may be one or more, and the content of the component (E) is preferably 0.01 to 3% by mass, more preferably 0.05 to 1.5% by mass, and further preferably 0.08 to 0.8% by mass based on the polymer (A).

[0222] Solvent (F)

[0223] The composition according to the present invention may also 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 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 of these solvents, 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 of these solvents, further preferably PGME, PGMEA or a mixture of these solvents. When two types of 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; more preferably 80:20 to 20:80).

[0224] It is also an embodiment of the present invention that component (F) is substantially free of water relative to other layers or films. Based on the total mass of component (F), the water content is preferably 0.1 mass % or less, more preferably 0.01 mass % or less, and further preferably 0.001 mass % or less. It is also a preferred embodiment that component (F) is free of water (0 mass %).

[0225] The content of component (F) is preferably 30 to 90% by mass, more preferably 60 to 90% by mass, and further preferably 75 to 85% by mass, based on the total mass of the composition.

[0226] Surfactant (G)

[0227] The composition according to the present invention may contain a surfactant (G). When the composition contains component (G), the coatability can be improved. Examples of surfactants that can be used in the present invention include (I) anionic surfactants, (II) cationic surfactants or (III) nonionic surfactants, more specifically, (I) alkyl sulfonates, alkylbenzene sulfonic acids and alkylbenzene sulfonates, (II) dodecyl pyridinium chloride and dodecyl methyl ammonium chloride and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene acetylene glycol ether, fluorine-containing surfactants (e.g., Fluorad (3M), Megaface (DICCorporation) and Surflon (AGC Inc.)) and organosiloxane surfactants (e.g., KF-53 and KP341 (Shin-Etsu Chemical Co., Ltd.)).

[0228] These surfactants may be one or more. The content of component (G) is preferably 0 to 20% by mass, more preferably 0.005 to 3% by mass, and further preferably 0.01 to 1% by mass based on the total mass of polymer (A).

[0229] Additives (H)

[0230] The composition of the present invention may contain an additive (H) in addition to components (A) to (G), wherein the additive (H) is at least one selected from the group consisting of a plasticizer, a dye, a contrast enhancer, an acid, and a substrate adhesion enhancer.

[0231] The content of additive (H) (the total amount when multiple types are present) is preferably 0 to 20% by mass, more preferably 0 to 5% by mass, and further preferably 0 to 1% by 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).

[0232] The present invention also relates to use of the amide compound represented by formula (D-1) or the composition according to the present invention for suppressing standing waves on the side surface of a resist pattern, improving the resolution of the resist pattern, improving rectangularity and / or improving heat resistance.

[0233] <Method for Manufacturing Resist Film>

[0234] The method for manufacturing a resist film according to the present invention comprises the following steps:

[0235] (1) applying the above composition directly onto a substrate; and

[0236] (2) The composition is heated to form a resist film.

[0237] The method for manufacturing a resist pattern according to the present invention comprises the following steps:

[0238] Manufacturing a resist film by the above method;

[0239] (3) exposing the resist film to light; and

[0240] (4) The resist film is developed.

[0241] The numbers in parentheses indicate the order of each step. For example, when describing steps (1), (2), and (3), the order of each step is as described above.

[0242] The composition according to the present invention is applied on the substrate (for example, a substrate coated with silicon / silicon dioxide, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, etc.) by an appropriate method. Wherein, in the present invention, "above" includes the situation of forming a film directly on the substrate and the situation of forming a film on the substrate via another layer. For example, a planarization film or a resist lower film can be formed directly on the substrate, and the composition according to the present invention can be directly applied on the planarization film or the resist lower film. In the present invention, the composition according to the present invention is preferably directly applied on the substrate, because even if the lower anti-reflection film is not formed, the effect can be exerted. The application method is not particularly limited, and its example includes the application method using a spin coater or a coater.

[0243] After the composition is applied, a resist film is formed by heating (pre-baking). The resist film is heated, for example, by a hot plate. The heating temperature is preferably 100 to 250° C., more preferably 80 to 200° C., and further preferably 90 to 180° C. The heating time is preferably 60 to 300 seconds, more preferably 90 to 180 seconds. The heating is preferably carried out in air or a nitrogen atmosphere.

[0244] The film thickness of the resist film varies depending on the exposure wavelength, but is preferably 0.01 to 5 μm, more preferably 0.1 to 2.5 μm.

[0245] The resist film is exposed through a predetermined mask. The wavelength of light used for exposure is not particularly limited, but exposure is preferably performed using a light source of 248 nm±1% or 193 nm±1%.

[0246] After exposure, post-exposure baking can be performed as needed. The temperature of the post-exposure baking 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 air or nitrogen atmosphere.

[0247] After exposure, the resist layer is developed using a developer. The developer used is preferably a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution. The temperature of the developer is preferably 5 to 50° C., more preferably 25 to 40° C., and the developing time is preferably 10 to 300 seconds, more preferably 30 to 90 seconds. For example, a surfactant may also be added to these developers.

[0248] When a positive resist composition is used, the resist layer in the exposed area is removed by development, and when a negative resist composition is used, the resist layer in the unexposed area is removed by development, thereby forming a resist pattern. The resist pattern can also be made finer by, for example, using a shrink material.

[0249] Regardless of whether the resist pattern formed is positive or negative, the influence of standing waves is reduced and the side portion of the pattern has a smooth shape.

[0250] Figure 1 It is a schematic diagram of the cross-sectional shape of the resist pattern 2 not affected by the standing wave and the resist pattern 3 affected by the standing wave on the substrate 1. When the resist pattern is affected by the standing wave, when a waveform with a large amplitude is formed on the cross section, the shape of the top of the resist will fluctuate greatly due to a slight difference in film thickness, and the dimensional accuracy will decrease. Therefore, it is best that this amplitude is small.

[0251] Suppose the widths of the anti-etching pattern at the points where the thickness of the anti-etching pattern is the smallest and largest from the point where the substrate contacts the anti-etching pattern upward are Wi and Wo respectively. If Sw is set to Wi / Wo, then the case where Sw is 1 is a rectangular anti-etching pattern. The closer Sw is to 1, the more the influence of standing waves is suppressed, and therefore it is preferred.

[0252] The method of manufacturing a processed substrate of the present invention comprises the following steps:

[0253] Manufacturing a resist pattern by the above method; and

[0254] (5) Processing using the resist pattern as a mask,

[0255] In step (5), the underlying film of the resist pattern or the substrate (more preferably the substrate) is treated.

[0256] Subsequently, if necessary, the substrate is further processed to form a device. This further processing can be performed using known methods. The method for manufacturing a device according to the present invention includes any of the above methods, and preferably also includes the step of forming wiring on the processed substrate. Examples of devices include semiconductor devices, liquid crystal display devices, organic EL display devices, plasma display devices, and solar cell devices, and preferably semiconductor devices.

[0257] The composite material of the present invention is obtained as an intermediate in the manufacturing stage of a processed substrate and comprises at least a substrate and a resist pattern formed on the substrate, wherein the resist pattern contains at least a polymer A' derived from a polymer (A) having a reactive group and an amide compound (D).

[0258] The resist pattern further contains a photoacid generator (B) and / or a quencher (C).

[0259] Preferred embodiments are listed below.

[0260] [Implementation 1]

[0261] A resist composition comprising: a polymer (A); a photoacid generator (B); and an amide compound (D),

[0262] Wherein, the amide compound (D) is a composition represented by formula (D-1),

[0263]

[0264] Among them, R d1 For straight chain C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR d4 R d5 ,

[0265] R d2 and R d3 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 alkyl,

[0266] R d4 and R d5 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 alkyl,

[0267] Among them, when R d1 When it is an alkyl group, R d1 Can be used with R d2 To form a ring, when R d1 For-NR d4 R d5 When R d4 or R d5 Can be used with R d2 Form a ring, and

[0268] When R d1 , R d2 , R d3 , R d4 and / or R d5In the case of an alkyl group, the methylene group (-CH2-) in the alkyl group may be replaced by -NH-, -S- or -O-.

[0269] The content of the amide compound (D) is preferably from 0.01 to 7% by mass, more preferably from 0.1 to 6% by mass, based on the total mass of the polymer (A).

[0270] [Implementation 2]

[0271] The composition according to Embodiment 1, wherein the amide compound (D) is represented by Formula (D-1a) or Formula (D-1b):

[0272]

[0273] Among them, R da1 For straight chain C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 , preferably a straight chain C 2-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 ,

[0274] R da2 and R da3 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 Alkyl, and

[0275] R da4 and R da5 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 alkyl,

[0276] Among them, when R da1 , R da2 , R da3 , R da4 and / or R da5 When it is an alkyl group, the methylene group in the alkyl group may be replaced by -NH-, -S- or -O-, and

[0277]

[0278] Among them, R db1 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 An alkyl group, wherein the methylene group in the alkyl group may be replaced by -NH-, -S- or -O-, and

[0279] L d C is a straight chain or branched chain 3-8The alkylene group may be substituted with -NH-, -S- or -O-.

[0280] 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.

[0281] [Implementation Plan 3]

[0282] The composition according to Embodiment 2, wherein the amide compound (D) is represented by Formula (D-1b).

[0283] 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.

[0284] [Implementation 4]

[0285] The composition according to at least any one of embodiments 1 to 3, wherein polymer (A) comprises at least one of repeating units represented by formula (A-1) and formula (A-2), and optionally further comprises at least one of repeating units represented by formula (A-3) and formula (A-4):

[0286]

[0287] Among them, C y 11 and C y 21 are each independently an aryl or heteroaryl group having 5 or 6 ring atoms, preferably an aryl group having 5 or 6 ring atoms,

[0288] R 11 , R 21 , R 41 , R 45 Each independently is C 1-5 Alkyl (wherein the methylene group in the alkyl group may be replaced by -O-);

[0289] 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 independently hydrogen, C1-5 Alkyl, C 1-5 Alkoxy or -COOH;

[0290] p11 is 0 to 4, p15 is 1 to 2, p11+p15≤5,

[0291] p21 is 0 to 5,

[0292] p41 is 0 to 4, p45 is 1 to 2, p41+p45≤5; and

[0293] P 31 C 4-20 Alkyl (wherein a part or all of the alkyl group may form a ring, a part or all of the H in the alkyl group may be substituted by halogen, and the methylene group in the alkyl group may be replaced by -O- or a carbonyl group),

[0294] Preferably, in the composition according to embodiment 1 or 2, the number of repeating units n of the repeating units (A-1), (A-2), (A-3) and (A-4) in the polymer (A) is A-1 、n A-2 、n A-3 and n A-4 for

[0295] n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 )=0 to 100%,

[0296] n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 )=0 to 100%,

[0297] n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) = 0 to 50%, or

[0298] n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 )=0 to 50%

[0299] Preferably, the total number of all repeating units contained in the polymer (A) is n total The following conditions are met:

[0300] (n A-1 +nA-2 +n A-3 +n A-4 ) / n total = 80 to 100%, or

[0301] Preferably, the mass average molecular weight Mw of the polymer (A) is 3,000 to 50,000.

[0302] [Implementation 5]

[0303] The composition according to at least any one of embodiments 1 to 4, wherein the photoacid generator (B) is represented by formula (B-1):

[0304] B n+ Cation B n- Anionic formula (B-1)

[0305]

[0306] in,

[0307] B n+ The cation is composed of at least one cation selected from the group consisting of: a cation represented by formula (BC1):

[0308] (Among them, R b1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, C 6-12 Aryloxy, nitro, sulfonyl, carboxyl, hydroxyl, amino, cyano, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbon, and

[0309] nb1 is each independently 0, 1, 2 or 3),

[0310] The cation represented by the formula (BC2):

[0311]

[0312] (Among them, R b2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfonyl, carboxyl, hydroxyl, amino, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbon, and

[0313] nb2 is each independently 0, 1, 2 or 3), and

[0314] The cation represented by the formula (BC3):

[0315]

[0316] (Among them, R b3 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfonyl, carboxyl, hydroxyl, amino, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbon,

[0317] R b4 Each independently is C 1-6 Alkyl, provided that both R b4 can be connected to form a ring, and

[0318] nb3 are each independently 0, 1, 2 or 3), and

[0319] The valence is n (where n is 1 to 3); and

[0320] B n- The anion is composed of at least one anion selected from the group consisting of an anion represented by formula (BA1):

[0321]

[0322] (Among them, R b5 Each independently is C 1-6 Fluorine-substituted alkyl or C 1-6 alkyl),

[0323] Anion represented by formula (BA2):

[0324]

[0325] (Among them, R b6 C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorinated acyl or C 6-12 fluorine-substituted alkoxyaryl),

[0326] Anion represented by formula (BA3):

[0327]

[0328] (Among them, R b7 Each independently is C 1-6Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorinated acyl or C 6-12 Fluorine-substituted alkoxyaryl, wherein two R b7 may be bonded to each other to form a fluorine-substituted heterocyclic structure), and

[0329] Anion represented by formula (BA4):

[0330]

[0331] (Among them, R b8 For hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy or hydroxyl,

[0332] L b is a carbonyl group, an oxy group or a carbonyloxy group,

[0333] Y b are each independently hydrogen or fluorine,

[0334] nb4 is an integer from 0 to 10, and

[0335] nb5 is an integer from 0 to 21), and

[0336] The overall price is n.

[0337] [Implementation Plan 6]

[0338] The composition according to at least any one of embodiments 1 to 5, further comprising a photoreaction quencher (C) and / or a basic compound (E):

[0339] 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 selected from ammonia, C 1-16 Aliphatic primary amine compounds, C 2-32 Aliphatic secondary amine compounds, C 3-48 Aliphatic tertiary amine compounds, C 6-30 Aromatic amine compounds and C 5-30 At least one selected from the group consisting of heterocyclic amine compounds;

[0340] C m+ Cation C m- Anionic formula (C-1)

[0341] in,

[0342] C m+The cation is composed of at least one cation selected from the group consisting of: a cation represented by formula (CC1):

[0343]

[0344] (Among them, R c1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, and

[0345] nc1 are each independently 0, 1, 2 or 3), and

[0346] The cation represented by the formula (CC2):

[0347]

[0348] (Among them, R c2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, and

[0349] nc2 are each independently 0, 1, 2 or 3), and

[0350] are generally m-valent (where m is 1 to 3); and

[0351] C m- The anion consists of at least one anion selected from the group consisting of an anion represented by formula (CA):

[0352]

[0353] (Where X is C 1-20 Hydrocarbon or C 6-12 Aryl,

[0354] R c3 are independently hydroxyl, carboxyl, C 1-6 Alkyl or C 6-10 Aryl,

[0355] nc3 is 1, 2, or 3, and

[0356] nc4 is 0, 1, or 2), and

[0357] Overall, the price is m.

[0358] [Implementation Plan 7]

[0359] The composition according to at least any 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 photoreaction 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.

[0360] [Implementation Plan 8]

[0361] The composition according to at least any 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 photoreaction 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).

[0362] [Implementation Plan 9]

[0363] The composition according to at least any one of embodiments 1 to 8 further comprises a solvent (F), preferably, the solvent (F) is water, a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent or any combination of these solvents.

[0364] [Implementation Plan 10]

[0365] The composition according to at least any one of embodiments 1 to 9, wherein the content of the polymer (A) is 10 to 60% by mass, based on the total mass of the composition, and / or

[0366] The content of the photoacid generator (B) is 0.05 to 5% by mass based on the total mass of the polymer (A).

[0367] Preferably, the content of the photoreaction quencher (C) is 0.01 to 3% by mass based on the total mass of the polymer (A).

[0368] Preferably, the content of the basic compound (E) is 0.01 to 3 mass % based on the total mass of the polymer (A), or

[0369] Preferably, the content of the solvent (F) is 30 to 90% by mass based on the total mass of the composition.

[0370] [Implementation Plan 11]

[0371] The composition according to at least any one of embodiments 1 to 10, further comprising a surfactant (G):

[0372] Preferably, the composition further comprises an additive (H), wherein the additive (H) is at least one selected from the group consisting of a plasticizer, a dye, a contrast enhancer, an acid and a substrate adhesion enhancer.

[0373] Preferably, the content of the surfactant (G) is 0 to 20% by mass based on the total mass of the polymer (A), and

[0374] Preferably, the content of the additive (H) is 0 to 20% by mass based on the total mass of the polymer (A).

[0375] [Implementation Plan 12]

[0376] The composition according to at least any one of embodiments 1 to 11, wherein the composition is a positive chemically amplified resist composition.

[0377] [Implementation Plan 13]

[0378] Use of the composition of at least any one of Embodiments 1 to 12 or the amide compound represented by formula (D-1) for suppressing standing waves on the side surface of a resist pattern, improving the resolution of the resist pattern, improving rectangularity, and / or improving heat resistance.

[0379] [Implementation Plan 14]

[0380] A method for manufacturing a resist film, comprising the following steps:

[0381] (1) applying the composition according to at least any one of Embodiments 1 to 12 onto a substrate; and

[0382] (2) heating the composition to form a resist film,

[0383] Preferably, the heating in step (2) is performed at 100 to 250° C. and / or lasts for 60 to 300 seconds,

[0384] Preferably, the heating in step (2) is carried out in an air or nitrogen atmosphere, or

[0385] Preferably, the resist film is formed to have a film thickness of 0.01 to 5 μm, more preferably 0.1 to 2.5 μm.

[0386] [Implementation Plan 15]

[0387] A method for manufacturing an anti-etching pattern comprises the following steps:

[0388] Manufacturing a resist film by the above method;

[0389] (3) exposing the resist film; preferably, using a light source of 248 nm ± 1% or 193 nm ± 1% for exposure; and

[0390] (4) The resist film is developed.

[0391] [Implementation Plan 16]

[0392] The method according to Embodiment 15 further comprises performing a post-exposure bake between step (3) and step (4).

[0393] [Implementation Plan 17]

[0394] A method for manufacturing a processed substrate comprises the following steps:

[0395] manufacturing a resist pattern according to the method of embodiment 15 or 16; and

[0396] (5) using the resist pattern as a mask for processing,

[0397] Preferably, step (5) is to process the underlying film or substrate (more preferably the substrate).

[0398] [Implementation Plan 18]

[0399] A method for manufacturing a device, comprising the method according to at least any one of Embodiments 15 to 17.

[0400] [Implementation Plan 19]

[0401] A composite material comprises at least a substrate and a resist pattern formed on the substrate, wherein the resist pattern contains at least a polymer A' derived from a polymer (A) having a reactive group and an amide compound (D):

[0402] Preferably, the resist pattern further contains a photoacid generator (B) and / or a quencher (C).

[0403] The present invention is described below by various examples, but the embodiments of the present invention are not limited to these examples.

[0404] <Preparation of Composition of Example 101>

[0405] PGME and EL are 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) are added to the mixed solvent to make the solid content concentration 17% by mass. The solid content concentration refers to the concentration of all components other than the solvent (including the mixed solvent) contained in the composition in the entire composition. Stir at room temperature for 30 minutes. Visually confirm that the added components are dissolved. The resultant is filtered through a 0.05μm filter. Thus, the composition of Example 1 is obtained.

[0406] Polymer 1: hydroxystyrene: styrene: tert-butyl acrylate copolymer, molar ratio 6:2:2, Mw: 12,000,

[0407] The above ratios represent the constituent ratios of the respective repeating units. The same shall apply hereinafter.

[0408]

[0409] Photoacid generator 1

[0410]

[0411] Photoreaction quencher 1

[0412]

[0413] Basic compound 1: tris[2-(2-methoxyethoxy)ethyl]amine

[0414] Surfactant 1: KF-53 (Shin-Etsu Chemical Co., Ltd.)

[0415] <Preparation of Compositions of Examples 102 to 107 and Comparative Examples 101 to 108>

[0416] The compositions of Examples 102 to 107 and Comparative Examples 101 to 108 were obtained in the same manner as in "Preparation of the composition of Example 101", except that the ε-caprolactam of Example 1 was replaced with the compounds and blending amounts shown in Tables 1 and 2. The numerical units of the compositions in the tables are parts by mass.

[0417]

[0418]

[0419] <Formation of Resist Pattern>

[0420] Each composition was dropped onto an 8-inch Si wafer using a coating developer Mark 8 (Tokyo Electron Ltd.) and spin-coated. The wafer was heated at 130° C. for 140 seconds using a hot plate under atmospheric conditions to form a resist film. The film thickness of the resist film at this time was measured to be 1.5 μm using an optical interference film thickness measuring device M-1210 (SCREEN).

[0421] The resist layer was exposed using a KrF stepper FPA3000-EX5 (Canon). The exposed wafer was heated (PEB) at 120°C for 90 seconds using a hot plate under atmospheric conditions. Afterwards, the resist layer was subjected to suspension immersion development for 60 seconds using a 2.38 mass % TMAH aqueous solution, washed with water, and spin dried at a speed of 1,000 rpm. Thus, a groove pattern with a line width of 0.36 μm and a gap width of 0.18 μm was formed. The line width and gap width are values ​​measured at the bottom of the pattern.

[0422] Figure 2 The pattern shape is schematically shown, and a resist pattern 5 is formed on a substrate 4. The exposure amount for forming a groove pattern with a line width of 0.36 μm and a gap width of 0.18 μm is defined as an optimal exposure amount, and the following evaluation is performed at this optimal exposure amount.

[0423] In Comparative Example 102, no resist pattern was formed.

[0424] <Evaluation of Cross-Sectional Shape>

[0425] A cross section of the substrate formed in "Formation of resist pattern" was made, and a vertical cross section was observed with a scanning electron microscope (SEM). From the point where the substrate and the resist pattern contacted each other, the width of the resist pattern at the point where the thickness of the resist pattern was the smallest and the largest was expressed as Wi and Wo, respectively. These Wi and Wo were measured, and the ratio Sw=Wi / Wo was calculated.

[0426] The value of Sw was evaluated according to the following criteria. The results are shown in Tables 1 and 2.

[0427] A: Sw is greater than 0.95.

[0428] B: Sw is greater than 0.9 and 0.95 or less.

[0429] C: Sw is greater than 0.8 and 0.9 or less.

[0430] D: Sw is 0.8 or less.

[0431] <Resolution Evaluation>

[0432] The resist pattern was formed by the same method as in "Formation of the resist pattern", except that a mask pattern having a spatial size of 0.50 to 0.08 μm was used for exposure, and exposure was performed at the optimal exposure amount described in "Formation of the resist pattern". The minimum size that the resist pattern can be formed is defined as resolution (nm), and the resolution is evaluated according to the following criteria. The evaluation results are listed in Tables 1 and 2.

[0433] [Explanation of symbols]

[0434] 1 substrate

[0435] 2 Resist pattern not affected by standing waves

[0436] 3 Resist pattern affected by standing waves

[0437] 4 substrate

[0438] 5. Resist pattern.

Claims

1. A resist composition comprising: a polymer (A); a photoacid generator (B); and an amide compound (D), in, The amide compound (D) is a composition represented by the formula (D-1), Among them, R d1 For straight chain C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR d4 R d5 , R d2 and R d3 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 Alkyl, and R d4 and R d5 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 Alkyl, and Among them, when R d1 When it is an alkyl group, R d1 Can be used with R d2 To form a ring, when R d1 For-NR d4 R d5 When R d4 or R d5 Can be used with R d2 Form a ring, and When R d1 , R d2 , R d3 , R d4 and / or R d5 When it is an alkyl group, the methylene group (-CH2-) in the alkyl group can 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): in, R da1 For straight chain C 1-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 , preferably a straight chain C 2-10 Alkyl, branched chain C 3-10 Alkyl or -NR da4 R da5 , R da2 and R da3 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 Alkyl, and R da4 and R da5 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 alkyl, Among them, when R da1 , R da2 , R da3 , R da4 and / or R da5 When it is an alkyl group, the methylene group in the alkyl group may be replaced by -NH-, -S- or -O-, and Among them, R db1 Each independently is hydrogen, a straight chain C 1-10 Alkyl or branched C 3-10 Alkyl, and the methylene group in the alkyl may be replaced by -NH-, -S- or -O-, and L d C is a straight chain or branched chain 3-8 The alkylene group may be substituted with -NH-, -S- or -O-. 3 . The composition according to claim 2 , wherein the amide compound (D) is represented by formula (D-1b).

4. The composition according to any one of claims 1 to 3, wherein the polymer (A) comprises at least one of the repeating units represented by formula (A-1) and formula (A-2), and optionally further comprises at least one of the repeating units represented by formula (A-3) and formula (A-4): in, C y 11 and C y 21 are each independently an aryl or heteroaryl group having 5 or 6 ring atoms, preferably an aryl group having 5 or 6 ring atoms, R 11 , R 21 , R 41 and R 45 Each independently is C 1-5 Alkyl (wherein the methylene group in the alkyl group 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 independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH; p11 is 0 to 4, p15 is 1 to 2, p11+p15≤5, p21 is 0 to 5, p41 is 0 to 4, p45 is 1 to 2, p41+p45≤5; and P 31 C 4-20 Alkyl (wherein a part or all of the alkyl group may form a ring, a part or all of the H in the alkyl group may be substituted by halogen, and the methylene in the alkyl group may be replaced by -O- or a carbonyl group), Preferably, in the composition according to claim 1 or 2, the number of repeating units n of the repeating units (A-1), (A-2), (A-3) and (A-4) in the polymer (A) is A-1 、n A-2 、n A-3 and n A-4 for n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 )=0 to 100%, n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 )=0 to 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 The following conditions are met: (n A-1 +n A-2 +n A-3 +n A-4 ) / n total = 80 to 100%, or Preferably, the mass average molecular weight Mw of the polymer (A) is 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- Anionic formula (B-1) in, B n+ The cation is composed of at least one cation selected from the group consisting of: a cation represented by formula (BC1): (Among them, R b1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, C 6-12 Aryloxy, nitro, sulfonyl, carboxyl, hydroxyl, amino, cyano, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbon, and nb1 is each independently 0, 1, 2 or 3), The cation represented by the formula (BC2): (Among them, R b2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfonyl, carboxyl, hydroxyl, amino, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbon, and nb2 is each independently 0, 1, 2 or 3), and The cation represented by the formula (BC3): (Among them, R b3 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, nitro, sulfonyl, carboxyl, hydroxyl, amino, halogen, C 1-6 Halogen-substituted alkyl or C 2-8 Hydrocarbon, R b4 Each independently is C 1-6 Alkyl, provided that both R b4 can be connected to form a ring, and nb3 are each independently 0, 1, 2 or 3), and The valence is n (where n is 1 to 3); and B n- The anion is composed of at least one anion selected from the group consisting of an anion represented by formula (BA1): (Among them, R b5 Each independently is C 1-6 Fluorine-substituted alkyl or C 1-6 alkyl), Anion represented by formula (BA2): (Among them, R b6 C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorinated acyl or C 6-12 fluorine-substituted alkoxyaryl), Anion represented by formula (BA3): (Among them, R b7 Each independently is C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorinated acyl or C 6-12 Fluorine-substituted alkoxyaryl, wherein two R b7 may be bonded to each other to form a fluorine-substituted heterocyclic structure), and Anion represented by formula (BA4): (Among them, R b8 For hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy or hydroxyl, L b is a carbonyl group, an oxy group or a carbonyloxy group, Y b are each independently hydrogen or fluorine, nb4 is an integer from 0 to 10, and nb5 is an integer from 0 to 21), and The overall price is n.

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 selected from ammonia, C 1-16 Aliphatic primary amine compounds, C 2-32 Aliphatic secondary amine compounds, C 3-48 Aliphatic tertiary amine compounds, C 6-30 Aromatic amine compounds and C 5-30 At least one selected from the group consisting of heterocyclic amine compounds; C m+ Cation C m- Anionic formula (C-1) in, C m+ The cation is composed of at least one cation selected from the group consisting of: a cation represented by formula (CC1): (Among them, R c1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, and nc1 are each independently 0, 1, 2 or 3), and The cation represented by the formula (CC2): (Among them, R c2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, and nc2 are each independently 0, 1, 2 or 3), and are generally m-valent (where m is 1 to 3); and C m- The anion consists of at least one anion selected from the group consisting of an anion represented by formula (CA): (Where X is C 1-20 Hydrocarbon or C 6-12 Aryl, R c3 are independently hydroxyl, carboxyl, C 1-6 Alkyl or C 6-10 Aryl, nc3 is 1, 2, or 3, and nc4 is 0, 1, or 2), and Overall, the price is m.

7. The composition according to any one of claims 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 photoreaction quencher (C) releases a weak acid having an acid dissociation constant pKa (H2O) of 1.5 to 8 upon exposure. Preferably, the base dissociation constant pKb (H2O) of the basic compound (E) 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 photoreaction 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, wherein the composition is a positive chemically amplified resist composition.

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

11. A method for manufacturing a resist pattern, comprising the following steps: Manufacturing a resist film by the method according to claim 10; (3) exposing the resist film; preferably, using a light source of 248 nm ± 1% or 193 nm ± 1% for exposure; and (4) The resist film is developed.

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

13. A method of manufacturing a processed substrate, The following steps are involved: Manufacturing a resist pattern according to the method of claim 11 or 12; and (5) using the resist pattern as a mask for processing, Preferably, step (5) is to process the underlying film or substrate (more preferably the substrate).

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

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

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