Thick film resist composition and method for manufacturing resist film using the same

Abstract

To provide a thick film resist composition capable of reducing environmental impact.SOLUTION: A thick film resist composition comprises a polymer (A), a deprotecting agent (B), a photoreaction quencher (C) composed of a specific cation and an anion, and a solvent (D).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a thick-film resist composition used in the manufacture of semiconductor elements, semiconductor integrated circuits, and the like, and a method for producing a resist film using the same. [Background technology]

[0002] In the manufacturing process of devices such as semiconductors, microfabrication by lithography technology using photoresist is generally performed. The microfabrication process includes forming a thin photoresist layer on a semiconductor substrate such as a silicon wafer, covering the layer with a mask pattern corresponding to the pattern of the target device, exposing the layer to active light such as ultraviolet light through the mask pattern, obtaining a photoresist pattern by developing the exposed layer, and etching the substrate using the obtained photoresist pattern as a protective film, thereby forming fine projections and recesses corresponding to the above-mentioned pattern.

[0003] While there is a demand for finer resist patterns, there is also a demand for thicker resist patterns with higher aspect ratios in order to accommodate high-energy ion implantation, etc. When forming a thick-film resist pattern, unlike a thin-film resist pattern, the performance and process conditions required of the composition are different, and therefore, the required shape cannot be formed by simply adjusting the viscosity of a thin-film resist composition to thicken the film, and there are particular difficulties involved.

[0004] For example, there is a method of increasing the viscosity of the composition to obtain a thick resist film, but this puts a high load on the total liquid of the composition and causes problems such as a lack of uniformity in film thickness. Patent Document 1 discusses a photolithography chemical solution that contains a specific low molecular weight resin component and an organic solvent with a specified saturated vapor pressure and viscosity.

[0005] Patent Document 2 considers a composition containing a chemically amplified polymer, a first photoacid generator, and a second photoacid generator, with the aim of obtaining a composition that can form a pattern with a cross-sectional shape close to a rectangle even if the film is thick, because the thicker the film thickness, the more the precision of the element formed from the resist pattern can deteriorate. These multiple photoacid generators act on the chemically amplified polymer to deprotect the polymer and increase its alkali solubility.

[0006] When using a chemically amplified resist, if the time from exposure to post-exposure baking is long, the shape of the resist pattern may change due to the environmental influence of amines in the air. In response to this, a method is known in which a basic compound such as an amine is added to the composition to reduce the influence. For example, in Patent Document 3, although the film thickness is 0.7 μm, the addition of tri-n-hexylamine or the like is considered to control acid diffusion. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2016-206673 A [Patent Document 2] JP 2018-109701 A [Patent Document 3] Patent No. 3677963 [Non-patent literature]

[0008] [Non-Patent Document 1] Support for cleanliness management in clean rooms (SCAS news 2006, p11-14) Summary of the Invention [Problem to be solved by the invention]

[0009] The present inventors have found that there are one or more problems that need to be improved with respect to resist compositions and their use, including, for example, the following: insufficient coatability of the composition; insufficient sensitivity; inability to obtain sufficient resolution; significant environmental impact during the manufacturing process; significant shrinkage of the top and / or bottom of the pattern due to environmental impact from exposure to post-exposure baking; inability to form a thick film due to poor film formation and / or cracking; low aspect ratio of the resist pattern; poor solubility of solid components in solvents; large number of defects; poor storage stability; and insufficient etching resistance of the resist film. The present invention has been made based on the above-mentioned technical background, and provides a thick-film resist composition and a method for producing a resist film using the same. [Means for solving the problem]

[0010] The thick-film resist composition according to the present invention (A) a polymer; (B) a deprotecting agent; (C) a photoreactive quencher; and (D) a solvent; (C) A photoreactive quencher having the formula (C-1): C m+ Cation C m- Anion Formula (C-1) (In the formula, C m+ The cation is a cation represented by the formula (CC1): [ka] (In the formula, R c1 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 aryl, and each nc1 is independently 0, 1, 2 or 3; and Cation represented by formula (CC2): [ka] (In the formula, R c2 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 aryl, and Each nc2 is independently 0, 1, 2 or 3. and having a total valency of m, where m is 1 to 3; C m- The anion is an anion represented by formula (CA): [ka] (In the formula, X is C 1-20 is a hydrocarbon of R c3 are each independently hydroxy, C 1-6 Alkyl, or C 6-10 is aryl, nc3 is 1, 2 or 3, and nc4 is 0, 1 or 2) and having a valency of m as a whole, It is expressed as follows.

[0011] Further, a method for producing a resist film according to the present invention includes the following steps: (1) applying the composition above over a substrate; (2) Heating the composition to form a resist film. The present invention relates to a method for producing a semiconductor device comprising the steps of: Effect of the Invention

[0012] By using the thick film resist composition of the present invention, one or more of the following effects can be expected. It is possible to obtain a composition with good coatability. A film with sufficient sensitivity can be obtained. Sufficient resolution can be obtained. The environmental impact in the manufacturing process can be reduced. The environmental impact from exposure to post-exposure bake can be reduced, and shrinkage between the tops and bottoms of the pattern can be suppressed. A thick resist film can be formed due to good film formation and / or suppression of cracks. A resist pattern with a high aspect ratio can be formed. The solid components have good solubility in solvents. The number of defects can be reduced. Good storage stability. A resist film with high etching resistance can be obtained. [Brief description of the drawings]

[0013] [Figure 1] 1A and 1B are conceptual diagrams showing the cross-sectional shapes of a resist pattern when PED is short and when PED is long. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] definition In this specification, unless otherwise specifically stated, the definitions and examples set forth in this "Definitions" paragraph shall apply. The singular includes the plural, and "a" or "the" means "at least one." An element of a concept may be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of the elements as well as its use alone. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "C x-y ", "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown by structural formulas, the n or m in parentheses indicates the number of repeats. Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius.

[0015] Hereinafter, an embodiment of the present invention will be described in detail.

[0016] <Thick Film Resist Composition> The thick-film resist composition (hereinafter sometimes simply referred to as the composition) according to the present invention comprises (A) a polymer, (B) a deprotecting agent, (C) a photoreactive quencher, and (D) a solvent. The thick film resist composition refers to a resist composition capable of forming a thick resist film. In the present invention, the thick film refers to a film having a thickness of 1 to 25 μm (preferably 1.5 to 20 μm), and the thin film refers to a film having a thickness of less than 1 μm. The viscosity of the composition according to the present invention is preferably 5 to 900 cP, more preferably 7 to 700 cP, where the viscosity is measured at 25° C. using a capillary viscometer. The composition according to the present invention is preferably a positive-type chemically amplified thick-film resist composition. The compositions according to the invention are preferably subsequently exposed to a light source of 248 nm±1% or 193 nm±1%.

[0017] (A) Polymer The polymer used in the present invention is one that reacts with an acid to increase its solubility in an alkaline aqueous solution. For example, such a polymer has an acid group protected by a protecting group, and when an acid is added from the outside, the protecting group is eliminated, thereby increasing the solubility in an alkaline aqueous solution. Such a polymer can be arbitrarily selected from those generally used in lithography methods.

[0018] In the present invention, the polymer (A) contains at least one structural unit selected from the group consisting of structural units represented by the following formulas (P-1), (P-2), and (P-3). It is preferable that the compound further comprises one of the following:

[0019] Equation (P-1) is as follows. [ka] During the ceremony, R p1 is hydrogen, C 1-5 Alkyl, C 1-5 alkoxy, or -COOH; R p2 is C 1-5 alkyl (wherein -CH2- may be replaced by -O-); m1 is a number from 0 to 4, and m2 is a number from 1 to 2, and m1+m2≦5. As one embodiment of the polymer (A) of the present invention, it may have only (P-1) as a structural unit, and the ratio of (P-1) with m2=1 to (P-1) with m2=2 may be 1:1. In this case, m2=1.5. The same applies hereinafter to the polymer unless otherwise specified.

[0020] R p1 is preferably hydrogen or methyl, more preferably hydrogen. R p2 is preferably methyl, ethyl or methoxy, more preferably methyl. m2 is preferably 1. m1 is preferably 0.

[0021] Specific examples of formula (P-1) are as follows. [ka]

[0022] Equation (P-2) is as follows. [ka] During the ceremony, R p3 is hydrogen, C 1-5 Alkyl, C 1-5 alkoxy, or -COOH; R p4 is C 1-5 Alkyl, or C 1-5 Alkoxy (wherein -CH2- contained in alkyl or alkoxy may be replaced by -O-); and m3 is a number from 0 to 5.

[0023] R p3 is preferably hydrogen or methyl, more preferably hydrogen. R p4 is C 1-5 In this embodiment, R is preferably an alkoxy group (wherein -CH2- contained in the alkoxy group may be replaced by -O-), and in this case, m3 is preferably 1. p4 Examples include methoxy, t-butyloxy, and -O-CH(CH3)-O-CH2CH3. m3 is preferably 0, 1, 2, 3, 4 or 5, and more preferably 0 or 1. In one preferred embodiment, m3 is 0.

[0024] Specific examples of formula (P-2) are as follows. [ka]

[0025] Equation (P-3) is as follows. [ka] During the ceremony, R p5 is hydrogen, C 1-5 Alkyl, C 1-5 alkoxy, or -COOH; and Rp6 is C 1-15 Alkyl or C 1-5 Alkyl ether (preferably C 1-15 alkyl), and R p6 may have a ring structure. p6 The alkyl portion of is preferably branched or cyclic.

[0026] R p5 is preferably hydrogen, methyl, ethyl, methoxy, or -COOH, more preferably hydrogen or methyl, and even more preferably hydrogen. R p6 is preferably methyl, isopropyl, t-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl or ethyladamantyl, more preferably t-butyl, ethylcyclopentyl, ethylcyclohexyl or ethyladamantyl, and even more preferably t-butyl.

[0027] Specific examples of formula (P-3) are as follows. [ka]

[0028] These constituent units are appropriately blended depending on the purpose, and there are no particular limitations on the blending ratio thereof. However, it is preferable that they are blended so that the rate of increase in solubility in an alkaline aqueous solution due to the acid is appropriate. Preferably, in the (A) polymer, the number of repetitions of formulas (P1), (P2), and (P3), n p1 , n p2 , and n p3 But the following formula: 40%≦n p1 / (n p1 +n p2 +n p3 )≦80%, 3%≦n p2 / (n p1 +n p2 +n p3) ≦40%, and / or 10%≦n p3 / (n p1 +n p2 +n p3 )≦40%, Meet the following. n p1 / (n p1 +n p2 +n p3 ) is more preferably 50 to 80%, further preferably 55 to 75%, and even more preferably 60 to 70%. n p2 / (n p1 +n p2 +n p3 ) is more preferably 3 to 30%, further preferably 5 to 25%, and even more preferably 10 to 20%. n p3 / (n p1 +n p2 +n p3 ) is more preferably 10 to 25%, even more preferably 12 to 25%, and even more preferably 10 to 20%.

[0029] The polymer (A) may contain structural units other than (P-1) to (P-3), but preferably, the total number n of all repeating units contained in the polymer (A) is total But the following expression: 80%≦(n p1 +n p2 +n p3 ) / n total ≦100% Meet the following. (n p1 +n p2 +n p3 ) / n total is more preferably 90 to 100%, and further preferably 95 to 100%. (n p1 +n p2 +n p3 ) / n total = 100%, that is, it does not contain any structural units other than (P-1), (P-2) and (P-3).

[0030] Specific examples of the (A) polymer are as follows: [ka] JPEG2025075037000012.jpg77153

[0031] The mass average molecular weight (hereinafter sometimes referred to as Mw) of the (A) polymer is preferably from 5,000 to 50,000, more preferably from 5,000 to 25,000, and even more preferably from 5,000 to 20,000. The number average molecular weight (hereinafter sometimes referred to as Mn) of the (A) polymer is preferably 1,600 to 39,000, and more preferably 1,600 to 20,000. In the present invention, Mw and Mn can be measured by gel permeation chromatography (GPC). In one preferred example, the GPC column is set at 40° C., the elution solvent is tetrahydrofuran at 0.6 mL / min, and monodisperse polystyrene is used as the standard.

[0032] Needless to say, in the composition of the present invention, these polymers can be used in combination of two or more kinds as long as they are represented by the above formula. For example, a composition containing both of the following two kinds of (A) polymers is also one embodiment of the present invention. [ka] In addition, for example, a composition containing the following two types of (A) polymers together is also one embodiment of the present invention. [ka] In addition, for example, a composition containing the following two types of (A) polymers together is also one embodiment of the present invention. [ka] In addition, for example, a composition containing the following two types of (A) polymers together is also one embodiment of the present invention. [ka] Preferably, the composition of the present invention contains one or two types of polymer (A), and more preferably, the composition of the present invention contains one type of polymer (A). Needless to say, Mw distribution and polymerization variations are allowed.

[0033] The content of the (A) polymer is preferably from 10 to 60 mass %, more preferably from 15 to 60 mass %, and even more preferably from 15 to 50 mass %, based on the total mass of the composition. The composition according to the present invention is allowed to contain a polymer other than the polymer (A). The polymer other than the polymer (A) is a polymer that does not satisfy the condition of containing at least one structural unit selected from the group consisting of structural units represented by the above formulae (P-1), (P-2), and (P-3). A preferred embodiment of the composition of the present invention is one that does not contain any polymer other than the (A) polymer.

[0034] (B) Deprotection Agent The composition according to the present invention comprises a deprotecting agent. The deprotecting agent releases an acid when irradiated with light, 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 removed by the acid. The deprotecting agent used in the composition according to the present invention can be selected from conventionally known agents. In the present invention, the deprotecting agent refers to a compound having the above-mentioned function itself. The compound may be dissolved or dispersed in a solvent and contained in the composition, but it is preferable that such a solvent is contained in the composition as the (D) solvent or other components. Hereinafter, the same applies to various additives that may be contained in the composition.

[0035] (B) The deprotecting agent, upon exposure to light, releases an acid having an acid dissociation constant pKa(H2O) of preferably -20 to 1.4, more preferably -16 to 1.4, even more preferably -16 to 1.2, and even more preferably -16 to 1.1.

[0036] Preferably, the (B) deprotecting agent has the formula (B-1): B n+ Cation B n- Anion Formula (B-1) It is expressed as: During the ceremony, B n+ The cation is composed of at least one cation selected from the group consisting of cations represented by formulae (BC1) to (BC3), and has a valency of n (wherein n is 1 to 3) as a whole; B n- The anion is composed of at least one anion selected from the group consisting of anions represented by formulae (BA1) to (BA4), and has a valency of n as a whole. The n-valency is preferably monovalent or divalent, and more preferably monovalent.

[0037] Equation (BC1) is as follows: [ka] During the ceremony, R b1 are each independently 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, or C 6-12 aryloxy, and Each nb1 is independently 0, 1, 2 or 3.

[0038] R b1 is preferably methyl, ethyl, t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy, and more preferably t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy. All nb1 are 1 and all R b1 In a preferred embodiment, they are the same. In addition, nb1 being 0 is also a suitable embodiment.

[0039] Specific examples of formula (BC1) are as follows: [ka]

[0040] Equation (BC2) is as follows. [ka] During the ceremony, R b2 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 aryl, and Each nb2 is independently 0, 1, 2 or 3.

[0041] R b2 is preferably C 4-6 Each R in the formula is an alkyl having a branched structure. b2 may be the same or different, and it is more preferable that they are the same. b2 More preferably, is t-butyl or 1,1-dimethylpropyl, and even more preferably is t-butyl. Each nb2 is preferably 1.

[0042] Specific examples of formula (BC2) are as follows: [ka]

[0043] Equation (BC3) is as follows: [ka] During the ceremony, R b3 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 is aryl, R b4 are each independently 1-6is alkyl, and Each nb3 is independently 0, 1, 2 or 3.

[0044] R b3 is preferably methyl, ethyl, methoxy, or ethoxy, and more preferably methyl or methoxy. b3 may be different from each other. R b4 is preferably methyl or ethyl, more preferably methyl. nb3 is preferably 1, 2 or 3, and more preferably 3.

[0045] Specific examples of formula (BC3) are as follows: [ka]

[0046] B n+ The cation is preferably selected from the group consisting of cations represented by formula (BC1) or (BC2) since these cations have a more pronounced effect.

[0047] Equation (BA1) is as follows: [ka] In the formula, R b5 are each independently 1-6 Fluorine-substituted alkyl, or C 1-6 For example, -CF3 means that the hydrogen of methyl (C1) is replaced by a fluorine atom. 1-6 All of the hydrogens present in the fluorine-substituted alkyl are replaced with fluorine. R b5 The alkyl portion of is preferably methyl, ethyl or t-butyl, more preferably methyl.

[0048] R b5 is preferably a fluorine-substituted alkyl, more preferably -CF3.

[0049] Specific examples of formula (BA1) are as follows: [ka]

[0050] Equation (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 6-12 Fluorine-substituted alkoxyaryl. For example, -CF3 means that the hydrogen of methyl (C1) is replaced by fluorine. 1-6 All of the hydrogens present in the fluorine-substituted alkyl are replaced with fluorine. R b6 The alkyl portion of is preferably methyl, ethyl, propyl, butyl or pentyl, more preferably propyl, butyl or pentyl, and even more preferably butyl. R b6 The alkyl portion of R is preferably linear. b6 is preferably C 1-6 It is a fluorine-substituted alkyl.

[0051] R b6 is C 2-6 It is preferably a fluorine-substituted alkyl.

[0052] Specific examples of formula (BA2) are as follows: C4F9SO3 - , C3F7SO3 -

[0053] Equation (BA3) is as follows: [ka] In the formula, R b7are each independently 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, where two R b7 may be bonded to each other to form a fluorine-substituted heterocyclic structure. For example, -CF3 means that the hydrogen of methyl (C1) is replaced by a fluorine. Preferably, C 1-6 All of the hydrogens present in the fluorine-substituted alkyl are replaced with fluorine.

[0054] 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. b6 The alkyl portion of is preferably straight chain. R b7 is C 2-6 It is preferably a fluorine-substituted alkyl. The Two R's b7 are also preferably bonded to each other to form a fluorine-substituted heterocyclic structure, in which case the heterocyclic ring may be a monocyclic ring or a polycyclic ring. A monocyclic structure having 5 to 8 members is preferred.

[0055] Specific examples of formula (BA3) are as follows: [ka]

[0056] Anion represented by formula (BA4): [ka] During the ceremony, R b8 is hydrogen, C 1-6 Alkyl, C 1-6 alkoxy, or hydroxy; L bis carbonyl, oxy or carbonyloxy, 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.

[0057] R b8 is preferably hydrogen, methyl, ethyl, methoxy, or hydroxy, more preferably hydrogen or hydroxy. L b is preferably carbonyl or carbonyloxy, more preferably carbonyl. Y b At least one of the groups is preferably fluorine. nb4 is preferably 0. nb5 is preferably 4, 5 or 6.

[0058] Specific examples of formula (BA4) are as follows: [ka]

[0059] The molecular weight of the deprotecting agent (B) is preferably 400 to 2,500, and more preferably 400 to 1,500.

[0060] The content of the (B) deprotecting agent is preferably from 0.05 to 5 mass %, and more preferably from 0.1 to 4 mass %, based on the total mass of the (A) polymer. The deprotecting agent (B) may be a known one, and may be any one that generates an acid by exposure to deprotect the protecting group of the polymer (A), for example, one that has an acid dissociation constant pKa(H2O) of -20 to 1.4 by exposure as described above. Known examples include photoacid generators, specifically acid generators that generate strong acids.

[0061] (C) Photoreactive quencher The composition according to the present invention comprises a photoreactive quencher. The photoreactive quencher releases an acid upon irradiation with light, but the acid does not directly act on the polymer. In this respect, it is different from the (B) deprotecting agent, which has a direct effect on the polymer by removing the protecting group of the polymer with the released acid.

[0062] The (C) photoreactive quencher functions as a quencher to suppress the diffusion of acid derived from the (B) deprotecting agent generated in the exposed area. Without being bound by theory, this is thought to be due to the following mechanism. Upon exposure, acid is released from the (B) deprotecting agent, and when this acid diffuses to the unexposed area (unexposed area), a salt exchange occurs with the (C) photoreactive quencher. In other words, the anion of the deprotecting agent and the cation of the (C) photoreactive quencher form a salt. This suppresses the diffusion of acid. At this time, the anion of the (C) photoreactive quencher is released, but since this is a weak acid and cannot deprotect the polymer, it is thought that there is no effect on the unexposed area.

[0063] Furthermore, the (C) photoreactive quencher has the effect of suppressing the deactivation of acid on the resist film surface due to components such as amines contained in the air. This is thought to be due to the following mechanism, without being bound by theory. In the exposed area, exposure generates acid (weak acid derived from the (C) photoreactive quencher and acid derived from the (B) deprotecting agent). The amines in the air penetrate the resist film surface, neutralizing the acid present there. However, the presence of weak acid released from the (C) photoreactive quencher reduces the frequency with which the acid released from the (B) deprotecting agent is neutralized. It is thought that by increasing the amount of acid in the exposed area in this way, the deactivation of acid is suppressed. It is believed that the composition according to the present invention, by containing the photoreactive quencher (C), is less susceptible to changes in shape even if the PED after exposure is long, as described below.

[0064] In order to obtain the above two effects, in the prior art, it was common to add a basic compound such as a tertiary amine. When the composition contains a photoreactive quencher (C), the above two effects are higher than when a basic compound is contained, and the sensitivity tends to be higher. Although not bound by theory, when a basic compound is added as a quencher for the acid diffusing from the exposed area to the unexposed area, it is thought that the acid is neutralized (quenched) even in the exposed area. Also, although not bound by theory, when a basic compound is added to suppress the deactivation of the acid on the resist film surface due to the influence of components such as amines contained in the air, the amount of amines that have penetrated from the air is relatively reduced due to the presence of a basic composition in the film. On the other hand, the penetration of amines and the like in the air is not intentionally controlled. In this way, it is thought that using a photoreactive quencher (C) as in the present invention is more suitable for resist pattern design and stable production. As described above, the assumed action mechanism is different between the case where a basic compound is added and the case where a photoreactive quencher is added.

[0065] Without being bound by theory, it is believed that when the (C) photoreactive quencher is a solid, it has better dispersibility in the film than a basic compound, and therefore a stable effect can be obtained.

[0066] (C) The photoreactive quencher 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.

[0067] (C) The photoreactive quencher has the formula (C-1): C m+ Cation C m- Anion Formula (C-1) It is expressed as: During the ceremony, C m+ The cation is composed of at least one cation selected from the group consisting of cations represented by formulae (CC1) and (CC2), and has a valency of m (where m is 1 to 3) as a whole; C m-The anions consist of at least one anion represented by formula (CA) and have a valency of m overall. The m-valent is preferably monovalent or divalent, and more preferably monovalent.

[0068] Equation (CC1) is as follows: [ka] During the ceremony, R c1 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 aryl, and Each nc1 is independently 0, 1, 2 or 3.

[0069] R c1 is 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. All nc1 are 1 and all R c1 In a preferred embodiment, they are the same. In addition, nc1 being 0 is also a preferred embodiment.

[0070] Specific examples of formula (CC1) are as follows: [ka]

[0071] Equation (CC2) is as follows: [ka] During the ceremony, R c2 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 aryl, and Each nc2 is independently 0, 1, 2 or 3.

[0072] R c2 is C 4-6 In the formula, each R c2 may be the same or different, and it is more preferable that they are the same. c2 More preferably, is t-butyl or 1,1-dimethylpropyl, and even more preferably is t-butyl. Preferably, each of nc2 is 1.

[0073] Specific examples of formula (CC2) are as follows: [ka]

[0074] The formula (CA) is as follows: [ka] During the ceremony, X is C 1-20 is a hydrocarbon of R c3 are each independently hydroxy, C 1-6 Alkyl, or C 6-10 is aryl, nc3 is 1, 2 or 3, and nc4 is 0, 1 or 2.

[0075] X may be linear, branched, or cyclic, but is preferably linear or cyclic. 1-4 It is preferable that 1-2 ), preferably has one double bond in the chain or is saturated. If it is cyclic, it may be an aromatic monocyclic ring, or a saturated monocyclic or polycyclic ring, if it is a monocyclic ring, it is preferably a six-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. nc3 is preferably 1 or 2, and more preferably 1. nc4 is preferably 0 or 1, and more preferably 1. R c3 is preferably hydroxy, methyl, ethyl, 1-propyl, 2-propyl, t-butyl, or phenyl, more preferably hydroxy.

[0076] Specific examples of formula (CA) are: [ka]

[0077] The molecular weight of the photoreactive quencher (C) is preferably 300 to 1,400, and more preferably 300 to 1,200.

[0078] The content of the (C) photoreactive quencher is preferably from 0.01 to 3 mass %, and more preferably from 0.02 to 1 mass %, based on the total mass of the (A) polymer.

[0079] (D) Solvent The composition according to the present invention comprises a (D) solvent. The solvent is not particularly limited as long as it can dissolve each of the components to be blended. The (D) solvent is preferably water, a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or any combination thereof. Specific examples of the solvent include water, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene, methanol, ethanol, n-Propanol, i-Propanol, n-Butanol, i-Butanol, sec-Butanol, t-Butanol, n-Pentanol, i-Pentanol, 2-Methylbutanol, sec-Pentanol, t-Pentanol, 3-Methoxybutanol, n-Hexanol, 2-Methylpentanol, sec-Hexanol, 2-Ethylbutanol, sec-Heptanol, Heptanol-3, n-Octanol, 2-Ethylhexanol, sec-Octanol, n-Nonylalcohol, 2,6-Dimethylheptanol-4, n-Decanol, sec-U nonyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol All-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol,Acetophenone, Fenchone, Ethyl Ether, i-Propyl Ether, n-Butyl Ether (Di-n-Butyl Ether, DBE), n-Hexyl Ether, 2-Ethylhexyl Ether, Ethylene Oxide, 1,2-Propylene Oxide, Dioxolane, 4-Methyldioxolane, Dioxane, Dimethyldioxane, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Diethyl Ether, Ethylene Glycol Mono-n-Butyl Ether, Ethylene Glycol Mono-n-Hexyl Ether, Ethylene Glycol Monophenyl Ether, Ethylene Glycol Mono-2-Ethylbutyl Ether, Ethylene Glycol Dibutyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Diethyl Ether, Diethylene Glycol Mono-n-Butyl Ether, Diethylene Glycol Di-n-Butyl Ether, Diethylene Glycol Mono-n-Hexyl Ether, Ethoxytriglycol, Tetraethylene Glycol Di-n-Butyl Ether, Propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate (normal butyl acetate, nBA), i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate,Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, Examples of the solvent include n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more. As the (D) solvent, preferably, PGME, PGMEA, EL, nBA, DBE, or any mixture thereof, more preferably, PGME, EL, nBA, DBE, or any mixture thereof. As the (D) solvent, PGME, PGMEA, or any mixture thereof is also suitable as another embodiment of the present invention. When two types are mixed, the mass ratio of the first solvent to the second solvent is preferably 95:5 to 5:95 (more preferably 90:10 to 10:90, even more preferably 80:20 to 20:80). When three types are mixed, the mass ratio of the first solvent to the sum of the three types is 30 to 90% (more preferably 50 to 80%, even more preferably 60 to 70%), the mass ratio of the second solvent to the sum of the three types is 10 to 50% (more preferably 20 to 40%), and the mass ratio of the third solvent to the sum of the three types is 5 to 40% (more preferably 5 to 20%, even more preferably 5 to 15%).

[0080] In relation to other layers or films, it is also one embodiment that the (D) solvent does not substantially contain water. For example, the amount of water in the (D) solvent as a whole is preferably 0.1 mass% or less, more preferably 0.01 mass% or less, and even more preferably 0.001 mass% or less. It is also a suitable embodiment that the (D) solvent does not contain water (0 mass%).

[0081] The content of the (D) solvent is 30 to 90 mass % based on the total mass of the composition, more preferably 30 to 85 mass %, and further preferably 50 to 85 mass %. By increasing or decreasing the amount of the solvent in the entire composition, the film thickness after formation can be controlled.

[0082] (E) Basic compounds The composition according to the present invention may further contain (E) a basic compound. The basic compound has the effect of suppressing the diffusion of the acid generated in the exposed area and the effect of suppressing the deactivation of the acid on the resist film surface by the amine component contained in the air. In the composition according to the present invention, as described above, (C) the photoquencher has these effects, so that (E) the basic compound is not essential in the present invention.

[0083] (E) Basic compounds include ammonia, C 1-16 Primary aliphatic amines, C 2-32 Secondary aliphatic amines, C 3-48 Tertiary aliphatic amines, C 6-30 Aromatic amines, C 5-30 and their derivatives.

[0084] Specific examples of the (E) basic compound include ammonia, ethylamine, n-octylamine, n-heptylamine, ethylenediamine, triethylamine, tri-n-octylamine, 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.

[0085] (E) The base dissociation constant pKb(H2O) of the basic compound is preferably -12 to 5, and more preferably 1 to 4.

[0086] The molecular weight of the (E) basic compound is preferably 17-500, and more preferably 60-400.

[0087] The content of the (E) basic compound is preferably 0 to 2 mass %, more preferably 0 to 1 mass %, based on the total mass of the (A) polymer. In consideration of the storage stability of the composition, it is also a suitable embodiment that does not contain the (E) basic compound.

[0088] (F) Plasticizer The composition according to the present invention may further comprise a plasticizer (F). The addition of a plasticizer can suppress film cracking when the film is formed into a thick film.

[0089] Examples of the plasticizer include an alkali-soluble vinyl polymer and an acid-dissociable group-containing vinyl polymer. More specifically, examples of the plasticizer include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoate, polyvinyl ether, polyvinyl butyral, polyvinyl alcohol, polyether ester, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, maleic acid polyimide, polyacrylamide, polyacrylonitrile, polyvinyl phenol, novolac, and copolymers thereof, and more preferably polyvinyl ether, polyvinyl butyral, and polyether ester.

[0090] (F) Specific examples of plasticizers are as follows. [ka]

[0091] The mass average molecular weight of the (F) plasticizer is preferably from 1,000 to 50,000, more preferably from 1,500 to 30,000, even more preferably from 2,000 to 21,000, and still more preferably from 2,000 to 15,000.

[0092] The content of the (F) plasticizer is preferably 0 to 20 mass %, more preferably 0 to 17 mass %, based on the total mass of the (A) polymer. In one preferred embodiment of the present invention, no plasticizer is contained.

[0093] (G) Additives The composition according to the present invention may contain an additive (G) other than the additives (A) to (F). The additive (G) is not particularly limited, but is preferably selected from at least one of the group consisting of a surfactant, a dye, a contrast enhancer, an acid, and a substrate adhesion enhancer. The content of the (G) additive is 0 to 20 mass %, more preferably 0 to 11 mass %, based on the total mass of the (A) polymer. A preferred example of the composition according to the present invention is one that does not contain the (G) additive (0 mass %).

[0094] By including a surfactant, the coating property can be improved. The surfactant that can be used in the present invention can include (I) anionic surfactants, (II) cationic surfactants, or (III) nonionic surfactants, more specifically, (I) alkylsulfonates, alkylbenzenesulfonic acids, and alkylbenzenesulfonates, (II) laurylpyridinium chloride, and laurylmethylammonium chloride, and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene acetylenic glycol ether, fluorine-containing surfactants (e.g., Fluorad (3M), Megafac (DIC), Sulfuron (Asahi Glass), and organic siloxane surfactants (e.g., KF-53, KP341 (Shin-Etsu Chemical)).

[0095] These surfactants can be used alone or in combination of two or more. The content thereof is preferably 2 mass % or less, and more preferably 1 mass % or less, based on the total mass of the (A) polymer.

[0096] By including the dye, the pattern shape can be improved. The dye is not particularly limited as long as it is a compound having a suitable absorption at the exposure wavelength. For example, benzene, naphthalene, anthracene, phenanthrene, pyrene, isocyanuric acid, triazine, and derivatives thereof can be mentioned.

[0097] Contrast enhancing agents include, for example, compounds having low molecular weight and containing an acid-labile group (hereinafter referred to as a leaving group) derived from an alkali-soluble phenolic compound or a hydroxycyclocyclic compound. Here, the leaving group reacts with the acid released from the deprotecting agent to leave the compound, increasing the solubility of the compound in an alkaline aqueous solution, thereby increasing the contrast. Such leaving groups include, for example, -R r1 , -COOR r1 , or -R r2 -COOR r1(In the formula, R r1 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may contain an oxygen atom between carbon atoms, R r2 is an alkylene group having 1 to 10 carbon atoms) and can be substituted with hydrogen in a hydroxyl group bonded to the compound. Such a contrast enhancing agent preferably contains two or more leaving groups in the molecule. In addition, the mass average molecular weight is 3000 or less, and preferably 100 to 2,000. The following are preferred compounds before introducing a leaving group into the hydroxyl group. [ka]

[0098] These contrast enhancing agents can be used alone or in combination of two or more kinds. The content thereof is preferably 0.5 to 40 mass %, more preferably 1 to 20 mass %, based on the total mass of the (A) polymer.

[0099] The acid can be used to adjust the pH value of the composition or to improve the solubility of additive components. The acid used is not particularly limited, but examples thereof include formic acid, acetic acid, propionic acid, benzoic acid, phthalic acid, salicylic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, and combinations thereof. The content of the acid is preferably 0.005% by mass or more and 0.1% by mass or less (50 ppm to 1,000 ppm) based on the total mass of the composition.

[0100] By using the substrate adhesion enhancer, it is possible to prevent the pattern from peeling off due to the stress applied during film formation. As the substrate adhesion enhancer, imidazoles and silane coupling agents are preferred, and as imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, and 2-aminoimidazole are preferred, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are more preferred. The content of the substrate adhesion enhancer is preferably 0 to 2 mass %, more preferably 0 to 1 mass %, based on the total mass of the (A) polymer.

[0101] <Method of manufacturing resist film> The method for producing a resist film according to the present invention comprises the steps of: (1) applying a composition according to the present invention over a substrate; and (2) Heating the composition to form a resist film. The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0102] An embodiment of the production method according to the present invention will now be described. The composition according to the present invention is applied above a substrate (e.g., silicon / silicon dioxide-coated substrate, silicon nitride substrate, silicon wafer substrate, glass substrate, ITO substrate, etc.) by a suitable method. Here, in the present invention, above includes the case where it is formed directly above and the case where it is formed via another layer. For example, a planarizing film or resist underlayer film may be formed directly above the substrate, and the composition according to the present invention may be applied directly above it. The application method is not particularly limited, and examples include a method of coating with a spinner or coater. The film according to the present invention is formed by coating and heating. The heating in (2) is performed, for example, by a hot plate. The heating temperature is preferably 100 to 250°C, more preferably 100 to 200°C, and even more preferably 100 to 160°C. The temperature here is the heating atmosphere, for example the heating surface temperature of a hot plate. The heating time is preferably 60 to 300 seconds, more preferably 60 to 240 seconds. The heating is preferably performed in air or nitrogen gas atmosphere.

[0103] The thickness of the resist film is selected according to the purpose, but when the composition according to the present invention is used, a pattern with a better shape can be formed when a thick coating film is formed. Therefore, the thickness of the resist film is preferably thick, for example, preferably 1 μm or more, more preferably 1.5 μm or more. The upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 25 μm or less, more preferably 20 μm or less.

[0104] moreover, (3) exposing the resist film to light; (4) Developing the resist film A resist pattern can be produced by a method comprising the steps of: (1) and (2) are carried out before the step (3) for clarity. The numbers in parentheses indicating the steps indicate the order. The same applies hereinafter. The resist film is exposed through a predetermined mask. The wavelength of light used for exposure is not particularly limited, but it is preferable to expose with light having a wavelength of 13.5 to 248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), extreme ultraviolet light (wavelength 13.5 nm), etc. can be used, and KrF excimer laser is preferable. These wavelengths allow a range of ±1%. After exposure, post exposure bake (PEB) can also be performed as necessary. The temperature of post exposure bake is preferably 80 to 150°C, more preferably 100 to 140°C, and the heating time is 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0105] The exposed resist film is developed using a developer. As the development method, a method conventionally used for developing photoresists, such as a paddle development method, an immersion development method, and a swing immersion development method, can be used. As the developer, an aqueous solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium silicate, an organic amine such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, or triethylamine, or a quaternary amine such as tetramethylammonium hydroxide (TMAH), is used, and preferably a 2.38 mass % TMAH aqueous solution. A surfactant can also be added to the developer. The temperature of the developer is preferably 5 to 50°C, more preferably 25 to 40°C, and the development time is preferably 10 to 300 seconds, more preferably 30 to 60 seconds. After development, water washing or rinsing treatment can be performed as necessary. When a positive resist composition is used, the exposed portion is removed by development to form a resist pattern. This resist pattern can be further fined by using, for example, a shrink material.

[0106] It is known that when a resist pattern is formed using a chemically amplified resist, the shape of the resist pattern changes if the post-exposure delay (PED) between exposure and post-exposure baking is long. To be more specific, FIG. 1(a) shows an example of a resist pattern when PED=1 minute. A resist pattern (2) is formed on a substrate (1). At this time, the width of the top between the walls of the resist pattern (i.e., the space portion) is ITW (3), and the width of the bottom is IBW (4). In this case, ITW>IBW. FIG. 1(b) shows an example of a resist pattern when PED=30 minutes. At this time, the width of the top between the walls of the resist pattern (i.e., the space portion) is FTW (6), and the width of the bottom is FBW (7). This phenomenon is believed to occur because the acid generated in the exposed area of ​​the resist is neutralized by basic compounds in the air (e.g., amine components), reducing the solubility of the exposed area of ​​the resist film surface. The top of the resist film is susceptible to this effect, and a resist pattern in which part of the exposed top area remains undeveloped is also called a T-shape. Thus, a resist pattern with a long PED and exposed to environmental effects tends to have a narrower trench width than a resist pattern with a short PED. In other words, a resist film that is resistant to environmental effects does not narrow the trench width very much. As described above, the composition according to the present invention contains the photoquencher (C) and is considered to be resistant to environmental influences. Preferably, ITW-FTW≦400 nm (more preferably, ≦390 nm, even more preferably, ≦320 nm); and / or Preferably, IBW-FBW≦50 nm (more preferably, ≦48 nm, and even more preferably, 45 nm). It is preferable that the conditions for comparing these values ​​are as consistent as possible with those of the Examples described later. For example, it is preferable to form a film having a thickness of 4.3 μm and then form a resist pattern. The resist pattern manufacturing environment requires manufacturing-level conditions, for example, the cleanliness control level of the clean room described in Non-Patent Document 1. As mentioned above, basic compounds in the air change the solubility of the resist film surface, so an environment with extremely low cleanliness cannot fully bring out the performance of the composition of the present invention. For example, a basic compound (such as ammonia) at 3.5 μg / m 3 Cleanliness should be controlled as follows: Even if PED is generated during the manufacturing process, the composition of the present invention can reduce the environmental impact. It is believed that this will have a beneficial effect.

[0107] moreover, (5) Processing using a resist pattern as a mask A processed substrate can be produced by a method comprising the steps of: The formed resist pattern is preferably used to process an underlayer film or a substrate (more preferably a substrate). Specifically, various substrates serving as the base can be processed using a dry etching method, a wet etching method, an ion implantation method, a metal plating method, or the like, with the resist pattern as a mask. The resist pattern according to the present invention can be thickened and have a high aspect ratio, and is therefore preferably used for substrate processing using an ion implantation method. In other words, when impurity doping is performed by ion implantation using the resist pattern as a mask, impurity doping is performed only on the portion of the base substrate that is not covered by the resist pattern. By thus performing impurity doping only on the desired region, it becomes possible to form a smaller semiconductor element structure on the substrate. When processing the underlayer film using a resist pattern, the processing may be performed in stages. For example, the BARC layer may be processed using a resist pattern, the SOC film may be processed using the BARC pattern, and the substrate may be processed using the SOC pattern. It is also possible to form wiring in gaps formed by processing the substrate.

[0108] Thereafter, if necessary, the substrate is further processed to form a device. This further processing can be performed by using known methods. After the device is formed, if necessary, the substrate is cut into chips, which are connected to a lead frame and packaged with resin. In the present invention, this packaged product is called a device. Examples of the device include a semiconductor element, a liquid crystal display element, an organic EL display element, a plasma display element, and a solar cell element. The device is preferably a semiconductor. EXAMPLES

[0109] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0110] Preparation of Composition 1 To obtain a thick resist film of 4.3 μm, composition 1 is prepared as follows. 100 parts by mass of polymer (A1) is added to 275 parts by mass of a mixed solvent with a mass ratio of PGME:EL=70:30. To this, 1.7% by mass of deprotecting agent (B1), 0.1% by mass of photoreactive quencher (C1), and 0.1% by mass of surfactant KF-53 (Shin-Etsu Chemical Co., Ltd.) are added based on the total mass of polymer (A1). This is stirred at room temperature for 30 minutes. It is visually confirmed that the additives are dissolved. This is filtered through a 0.05 μm filter. Thus, composition 1 is obtained. [ka] (A1) Hydroxystyrene:styrene:t-butyl acrylate copolymer, Maruzen Petrochemical, molar ratio 60:20:20, respectively, Mw approx. 12,000 [ka] (B1)DTBPIO-C1, Heraeus [ka] (C1) Toyosei

[0111] Preparation of Compositions 2 to 12 and Comparative Compositions 1 and 2 Compositions 2 to 12 and comparative compositions 1 and 2 were obtained in the same manner as in the preparation of composition 1, except that the composition was changed as shown in Table 1.

[0112] Preparation of Comparative Composition 3 In order to obtain a thin 0.76 μm resist film, Comparative Composition 3 is prepared as follows. 100 parts by mass of polymer (A1) is added to 746 parts by mass of a mixed solvent with a mass ratio of PGME:EL=70:30. To this, 1.7% by mass of deprotecting agent (B1), 0.1% by mass of photoreactive quencher (C1), and 0.1% by mass of surfactant KF-53 (Shin-Etsu Chemical) are added based on the total mass of polymer (A1). This is stirred at room temperature for 30 minutes. It is visually confirmed that the additives are dissolved. This is filtered through a 0.05 μm filter. This gives comparative composition 3.

[0113] Preparation of Comparative Compositions 4 to 7 Comparative compositions 4 to 7 were obtained in the same manner as in the preparation of comparative composition 3, except that the composition was changed as shown in Table 1.

[0114] Resist film formation The composition obtained above is used to obtain a resist film by carrying out the following operations. Using a coater Mark 8 (Tokyo Electron), each composition is dropped onto an 8-inch silicon wafer and spin-coated. The wafer is baked on a hot plate at 150°C for 130 seconds. Using the thick and thin compositions, resist films of 4.3 μm and 0.76 μm are obtained, respectively. The film thickness is measured using an M-1210 optical interference film thickness measuring device (Dainippon Screen). The film thickness is measured at eight points on the wafer excluding the center, and the average value is used.

[0115] Example of resist pattern formation The resist film formed in the above resist film formation example is exposed using a KrF stepper (FPA 300-EX5, CANON). The wafer is subjected to PEB at 110°C for 160 seconds on a hot plate. The time from exposure to PEB (i.e., PED) is 1 minute. This is paddle developed for 60 seconds using AZ300MIF developer (2.38% TMAH aqueous solution, Merck Performance Materials (MPM)). This results in a resist pattern with line = 1700 nm and space (trench) = 340 nm (line:space = 5:1). Note that the trench width at the bottom between the pattern walls (corresponding to 4 in Figure 1(a)) is 340 nm, but the width at the top between the pattern walls is wider, and the pattern walls may become tapered. Exposure energy (mJ / cm) when the mask size and pattern size are 1:1 2 The results are shown in Table 1 below.

[0116] The evaluation criteria for sensitivity are as follows: Sensitivity under thick film (4.3μm) conditions X:≦200mJ / cm 2 Y:>200mJ / cm 2 , ≦350mJ / cm 2 Z:>350mJ / cm 2

[0117] Sensitivity under thin film (0.76μm) conditions X:≦100mJ / cm 2 Y:>100mJ / cm 2 , ≦200mJ / cm 2 Z:>200mJ / cm 2

[0118] Resolution measurement A mask pattern with a line:space ratio of 5:1 and space widths that gradually decrease by 20 nm starting from 340 nm is used. Exposure is performed with an exposure dose that allows a 340 nm slit to reproduce a 340 nm pattern. An FPA-3000EX5 exposure tool (Canon) is used. A cross-sectional SEM is used to check the pattern shapes, starting from the 340 nm pattern. The space width just before the pattern where the space is collapsed is taken as the resolution. The results are shown in Table 1 below.

[0119] The evaluation criteria for resolution are as follows: Resolution under thick film conditions X:≦300nm Y:>300nm,≦340nm Z:>340nm

[0120] Resolution under thin film conditions X:≦260nm Y:>260nm [Table 1] In the above table, (A) means a polymer, (B) means a deprotecting agent, (C) means a photoreactive quencher, and (E) means a base compound. In the above table, the numbers in parentheses in the (B), (C), and (E) columns are mass % based on the total mass of the (A) polymer. The same applies to the following tables. [ka] (Base E1) 301248, Sigma-Aldrich

[0121] As shown in the above table, it can be confirmed that each composition containing the photoreactive quencher of the present invention has a suitable sensitivity and resolution as a thick-film resist, and also has a suitable sensitivity and resolution when used as a thin-film resist.

[0122] PED evaluation test The composition shown in Table 2 below is used to evaluate the environmental impact as follows.

[0123] Resist pattern measurement example The shape of the resist pattern formed in the above resist pattern formation example is confirmed using a scanning electron microscope (SEM). The width of the pattern surface is measured. The width between the top pattern walls is ITW (nm) and the width between the bottom pattern walls is IBW (nm).

[0124] Formation and measurement of resist patterns exposed to cleanroom atmosphere The composition obtained in Preparation Example is used to obtain a resist film by carrying out the following operations. The resist film formed in the above resist film formation example is exposed using a KrF stepper (FPA 3000-EX5). The exposure energy is the same as that used in the above resist pattern formation example for each composition and film thickness. The wafer is removed from the KrF stepper and placed on the laboratory bench (in the clean room) for 30 minutes (i.e., PED = 30 minutes). The wafer is PEBed on a hot plate at 110°C for 160 seconds. It is paddle developed with AZ300MIF developer for 60 seconds. This results in a resist pattern that has been affected by the environment. The shape of the resist pattern obtained is confirmed using an SEM, and the width of the pattern surface is measured. The width between the top pattern walls is FTW (nm) and the width between the bottom pattern walls is FBW (nm). The environmental impact is calculated and evaluated as follows: TG(nm)=ITW-FTW BG(nm)=IBW-FBW

[0125] The evaluation criteria for TG are as follows: TG under thick film conditions X:≦400nm Y:>400nm, the top is connected and the trench disappears

[0126] TG under thin film conditions X:≦150nm Y:>150nm, the top is connected and the trench disappears.

[0127] The evaluation criteria for BG are as follows: BG under thick film conditions X:≦50nm Y:>50nm Z: The bottom is connected and the trench disappears

[0128] BG under thin film conditions X:≦40nm Y:>40nm Z: The bottom is connected and the trench disappears [Table 2] As shown in the above table, it can be confirmed that each composition containing the photoreactive quencher of the present invention is less affected by the environment when used as a thick-film resist than the comparative composition. In addition, it is expected that the effect of reducing the environmental influence is greater when used as a thick-film resist than when used as a thin-film resist.

[0129] Preparation of Reference Composition 1 In order to obtain a resist film having a thickness of 4.3 μm, Reference Composition 1 is prepared as follows. 100 parts by mass of polymer (A1) is added to 275 parts by mass of a mixed solvent having a mass ratio of PGME:EL=70:30. To this, 0.5% by mass and 1.9% by mass of (B2) and (B3) as deprotecting agents, 0.2% by mass of photoreactive quencher (C1), and 0.1% by mass of surfactant KF-53 (Shin-Etsu Chemical Co., Ltd.) are added based on the total mass of polymer (A1). This is stirred at room temperature for 30 minutes. It is visually confirmed that the additives are dissolved. This is filtered through a 0.05 μm filter. Thus, Reference Composition 1 is obtained. [ka] (B2) ZK-0231, DSP GOKYO FOOD & CHEMICAL CO., LTD. [ka] (B3) ZK-1542, DSP GOKYO FOOD & CHEMICAL CO., LTD.

[0130] Preparation of Reference Composition 2 In order to obtain a resist film having a thickness of 4.3 μm, Reference Composition 2 is prepared as follows. 100 parts by mass of polymer (A1) is added to 275 parts by mass of a mixed solvent having a mass ratio of PGME:EL=70:30. To this, 0.5% by mass and 1.9% by mass of (B2) and (B3) as deprotecting agents, 0.1% by mass of photoreactive quencher (C1), 0.1% by mass of base (E1), and 0.1% by mass of surfactant KF-53 (Shin-Etsu Chemical Co., Ltd.) are added based on the total mass of polymer (A1). This is stirred at room temperature for 30 minutes. It is visually confirmed that the additives are dissolved. This is filtered through a 0.05 μm filter. Thus, Reference Composition 2 is obtained.

[0131] Comparison of compositions 2 and 6 with reference compositions 1 and 2 By carrying out the same operations as in the above resist film formation example and resist pattern formation example, resist patterns are obtained from the reference compositions 1 and 2. The sensitivity, resolution, and environmental impact are evaluated by the above-mentioned methods. The sensitivity of compositions 2 and 6 is equal to or higher than that of reference compositions 1 and 2. The resolution of compositions 2 and 6 is slightly better than that of reference compositions 1 and 2. The environmental impact of compositions 2 and 6 is equal to or higher than that of reference compositions 1 and 2.

[0132] Preparation of Composition 20 To obtain a thick resist film of 7.0 μm, composition 20 is prepared as follows. 100 parts by mass of polymer (A2) is added to 198 parts by mass of a mixed solvent having a mass ratio of PGME:nBA:DBE=60:30:10. 0.3% by mass of deprotecting agent (B4), 0.05% by mass of photoreactive quencher (C1), 2.5% by mass of plasticizer (F1), and 0.1% by mass of surfactant KF-53 (Shin-Etsu Chemical Co., Ltd.) are added to the mixture based on the total mass of polymer (A2). The mixture is stirred at room temperature for 30 minutes. It is visually confirmed that the additives are dissolved. The mixture is filtered through a 0.05 μm filter. Thus, composition 20 is obtained. [ka] (A2) Hydroxystyrene:styrene:t-butyl acrylate copolymer, Toho Chemical Industry, molar ratio 60:10:30, respectively, Mw approx. 12,000 [ka] (B4) TPS-C1, Heraeus Corporation [ka] (F1) Sanyo Chemical Industries, Ltd. SANNIX PL-2100

[0133] Example of resist film formation Composition 20 is dropped onto an 8-inch silicon wafer using a coater Mark 8 (Tokyo Electron) and spin-coated. The wafer is baked on a hot plate at 150°C for 130 seconds. This results in a 7.0 μm resist film. The film thickness is measured using an M-1210 optical interference film thickness measuring device (Dainippon Screen).

[0134] Example of resist pattern formation The resist film formed in the above resist film formation example is exposed using a KrF stepper (FPA 3000-EX5, CANON). The wafer is post-exposure baked (PEB) on a hot plate at 110°C for 160 seconds. This is paddle developed with AZ300MIF developer (2.38% TMAH aqueous solution, MPM Co., Ltd.) for 60 seconds. This results in a resist putty turn with line = 1500 nm and space (trench) = 300 nm (line:space = 5:1). Note that the trench width at the bottom between the pattern walls is 300 nm, but the width at the top between the pattern walls is wider, and the pattern walls may have a tapered shape. Exposure energy used (mJ / cm 2 ) is the sensitivity. The sensitivity is 82mJ / cm 2 It is.

[0135] Resolution measurement A mask pattern with a line:space ratio of 5:1 and space widths that gradually decrease by 20 nm starting from 300 nm is used. Exposure is performed with an exposure dose that allows a 300 nm slit to reproduce a 300 nm pattern. An FPA-3000EX5 (Canon) exposure tool is used. A cross-sectional SEM is used to confirm the pattern shape, starting from the 300 nm pattern. The space width just before the pattern where the space is collapsed is taken as the resolution. The resolution is 280 nm.

[0136] Preparation of Comparative Composition 8 In order to obtain a thick resist film of 10.5 μm, comparative composition 8 is prepared as follows. 100 parts by mass of polymer (A3) is added to 177 parts by mass of a mixed solvent having a mass ratio of PGME:PGMEA=70:30. 3.5% by mass of deprotecting agent (B5), 2.8% by mass of basic compound (E1), and 0.15% by mass of surfactant KF-53 are added to this, based on the total mass of polymer (A3). This is stirred at room temperature for 30 minutes. It is visually confirmed that the additives are dissolved. This is filtered through a 0.05 μm filter. Thus, comparative composition 8 is obtained. [ka] (A3) Hydroxystyrene:styrene:t-butyl acrylate copolymer, Toho Chemical Industry, molar ratio 60:20:20, respectively, Mw approx. 12,000 [ka] (B5)ZK-0518, DSP GOKYO FOOD & CHEMICAL CO., LTD.

[0137] Preparation of compositions 21 to 24 Compositions 21 to 24 are obtained in the same manner as in the preparation of comparative composition 8, except that the composition is changed as shown in Table 3. In Table 3, the numbers in parentheses for polymer (A) indicate the mass ratio between the polymers. The numbers in parentheses for (B), (C), and (E) are mass % based on the mass of polymer (A) (or the sum of the masses if multiple polymers are used). This will be explained with Composition 21. 100 parts by mass of a mixture of polymer (A4):polymer (A5)=70:30 by mass is added to 177 parts by mass of a mixed solvent of PGME:PGMEA=70:30 by mass. To this, 1.7% by mass of deprotecting agent (B4), 0.1% by mass of photoreaction quencher (C1), and 0.15% by mass of surfactant KF-53 are added based on the total mass of the polymer. No basic compound (E) is added. This is stirred at room temperature for 30 minutes. It is visually confirmed that the additives are dissolved. This is filtered through a 0.05 μm filter. Composition 21 is thus obtained. [Table 3] [ka] (A4) Hydroxystyrene:styrene:t-butyl acrylate copolymer, Toho Chemical Industry, molar ratio 60:20:20, respectively, Mw approx. 18,000 [ka] (A5) Hydroxystyrene: 4-t-butoxystyrene: 4-(1-ethoxyethoxy)styrene copolymer, Toho Chemical Industry, molar ratio 60:20:20, respectively, Mw approx. 12,000 [ka] (A6) Hydroxystyrene:styrene:4-(1-ethoxyethoxy)styrene copolymer, Toho Chemical Industry, molar ratio 60:20:20, respectively, Mw approx. 12,000 [ka] (A7) Hydroxystyrene:styrene:4-(1-ethoxyethoxy)styrene copolymer, Gun-ei Chemical Industry, molar ratio 59:15:26, respectively, Mw approx. 12,000 [ka] (B6)ZK-0517, DSP GOKYO FOOD & CHEMICAL CO., LTD. [ka] (C2) TPSA, Takemoto Oil

[0138] Formation of resist films of comparative composition 8 and compositions 21 to 24 Using a coater Mark 8 (Tokyo Electron), each composition is dropped onto an 8-inch silicon wafer and spin-coated. The wafer is baked on a hot plate at 140°C for 90 seconds. Using each composition, a resist film of 10.5 μm is obtained. The film thickness is measured using an M-1210 optical interference film thickness measuring device (Dainippon Screen). The film thickness is measured at eight points on the wafer excluding the center, and the average value is used.

[0139] Etching resistance evaluation Dry etching is performed using O2 gas and CF4 gas once each. The thickness of the film remaining after etching is measured using an M-1210 optical interference film thickness measuring device. The film thickness is measured at eight points on the wafer excluding the center, and the average value is used. The film thickness obtained with the comparative composition 8 is taken as 100%, and the etching resistance of compositions 21 to 24 is evaluated. The results are shown in Table 3. It is confirmed that the etching resistance of the example composition is higher than that of the comparative composition 8. [Explanation of symbols]

[0140] 1. Substrate 2. Resist pattern when PED is short 3.ITW 4.IBW 5. Resist pattern when PED is long 6.FTW 7.FBW

Claims

1. A thick-film resist composition comprising: (A) a polymer; (B) a deprotecting agent; (C) a photoreactive quencher; and (D) a solvent, (C) The photoreactive quencher is represented by the formula (C-1): C ｍ＋ Cation C ｍ－ Anion Formula (C-1) (In the formula, C ｍ＋ The cation is a cation represented by formula (CC1): 【Chemistry 1】 (In the formula, R ｃ１ are each independently １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ aryl, and Each ncl is independently 0, 1, 2 or 3; and Cation represented by formula (CC2): 【Chemistry 2】 (In the formula, R ｃ２ are each independently １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ aryl, and Each n c2 is independently 0, 1, 2 or 3. and having a valency of m, where m is 1 to 3; C ｍ－ The anion is an anion represented by formula (CA): 【Chemistry 3】 (In the formula, X is C １－２０ is a hydrocarbon of R ｃ３ Each independently represents hydroxy, C １－６ Alkyl, or C ６－１０ is aryl, n c3 is 1, 2 or 3, and n c4 is 0, 1 or 2) and the total valency is m. The thick-film resist composition is represented by the formula:

2. The polymer (A) comprises a structural unit represented by formula (P-1): 【Chemistry 4】 (In the formula, R ｐ１ is hydrogen, C １－５ Alkyl, C １－５ alkoxy, or -COOH; R ｐ２ is C １－５ Alkyl (which is -CH ２ - may be replaced by -O-; m1 is a number from 0 to 4; and m2 is a number from 1 to 2, and m1+m2≦5; A structural unit represented by formula (P-2): 【Chemistry 5】 (In the formula, R ｐ３ is hydrogen, C １－５ Alkyl, C １－５ alkoxy, or -COOH; R ｐ４ is C １－５ Alkyl or C １－５ Alkoxy (herein, —CH included in alkyl and alkoxy) ２ - may be replaced by -O-; and m3 is a number from 0 to 5; and A structural unit represented by formula (P-3): 【Chemistry 6】 (In the formula, R ｐ５ is hydrogen, C １－５ Alkyl, C １－５ alkoxy, or -COOH; and R ｐ６ is C １－１５ Alkyl or C １－５ is an alkyl ether, R ｐ６ may have a ring structure) At least one constitutional unit selected from the group consisting of Preferably, the number of repetitions of formulas (P1), (P2), and (P3) is n ｐ１ , n ｐ２ , and n ｐ３ is expressed by the following formula: 40%≦n ｐ１ / (n ｐ１ +n ｐ２ +n ｐ３ ) ≦80%, 3% ≦n ｐ２ / (n ｐ１ +n ｐ２ +n ｐ３ ) ≦40%, and / or 10% ≦n ｐ３ / (n ｐ１ +n ｐ２ +n ｐ３ )≦40% The composition according to claim 1 , wherein

3. (B) The deprotecting agent is represented by the formula (B-1): B ｎ＋ Cation B ｎ－ Anion Formula (B-1) (In the formula, B ｎ＋ The cation is a cation represented by the formula (BC1): 【Chemistry 7】 (In the formula, R ｂ１ are each independently １－６ Alkyl, C １－６ Alkoxy, C ６－１２ Aryl, C ６－１２ Arylthio, or C ６－１２ aryloxy, and Each nb1 is independently 0, 1, 2 or 3; Cation represented by formula (BC2): 【Chemistry 8】 (In the formula, R ｂ２ are each independently １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ aryl, and Each nb2 is independently 0, 1, 2 or 3. Cation represented by formula (BC3): 【Chemistry 9】 (In the formula, R ｂ３ are each independently １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ is aryl, R ｂ４ are each independently １－６ is alkyl, and Each nb3 is independently 0, 1, 2 or 3. and having an overall valency of n (where n is 1 to 3); B ｎ－ The anion is an anion represented by formula (BA1): 【Chemistry 10】 (In the formula, R ｂ５ are each independently １－６ Fluorine-substituted alkyl, or C １－６ alkyl), Anion represented by formula (BA2): 【Chemistry 11】 (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) Anion represented by formula (BA3): 【Chemistry 12】 (In the formula, R ｂ７ are each independently 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, where two R ｂ７ may be bonded to each other to form a fluorine-substituted heterocyclic structure, and Anion represented by formula (BA4): 【Chemistry 13】 (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; and nb5 is an integer from 0 to 21. and wherein the anion is selected from the group consisting of: The composition according to claim 1 or 2, wherein

4. The composition according to at least one of claims 1 to 3, characterized in that it is capable of producing a resist film having a thickness of 1 to 25 µm, preferably characterized in that a light source of 248 nm ± 1% or 193 nm ± 1% is used for the subsequent exposure.

5. The content of the (A) polymer is 10 to 60% by mass, based on the total mass of the composition; (C) the content of the photoreactive quencher is 0.01 to 3 mass % based on the total mass of the (A) polymer; Preferably, the content of the deprotecting agent (B) is 0.05 to 5% by mass based on the total mass of the polymer (A); The composition according to at least one of claims 1 to 4, wherein the content of the solvent (D) is preferably 30 to 90% by mass, based on the total mass of the composition.

6. (E) further comprises a basic compound, and preferably 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, or C ５－３０ The composition according to at least any one of claims 1 to 5, wherein the content of the (E) basic compound, which is a heterocyclic amine compound, is preferably 0 to 2 mass% based on the total mass of the (A) polymer.

7. (B) The deprotecting agent changes the acid dissociation constant pKa(H ２ O) is an acid dissociation constant pKa (H) of −20 to 1.4, and preferably, (C) a photoreactive quencher is an acid dissociation constant pKa (H ２ (O) a weak acid having a dissociation constant pKb (H) of 1.5 to 8, and preferably (E) a basic compound having a dissociation constant pKb (H ２ The composition according to at least one of claims 1 to 6, wherein O) is from -12 to 5.

8. The composition according to at least any one of claims 1 to 7, wherein (A) the polymer has a mass average molecular weight (Mw) of 5,000 to 50,000 (preferably 5,000 to 25,000), (B) the deprotecting agent has a molecular weight of 400 to 2,500 (preferably 400 to 1,500), (C) the photoreactive quencher has a molecular weight of 300 to 1,400 (preferably 300 to 1,200), and (E) the basic compound has a molecular weight of 17 to 500 (preferably 60 to 400).

9. 9. The composition according to at least one of claims 1 to 8, further comprising a (F) plasticizer, preferably further comprising a (G) additive, the (G) additive being selected from at least one of the group consisting of surfactants, dyes, contrast enhancers, acids, and substrate adhesion enhancers, preferably the content of the (F) plasticizer is 0 to 20% by weight based on the total weight of the (A) polymer, and preferably the content of the (G) additive is 0 to 20% by weight based on the total weight of the (A) polymer.

10. The composition according to at least one of claims 1 to 9, wherein the solvent (D) is water, a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or any combination thereof.

11. The composition according to at least one of claims 1 to 10, wherein the thick film resist composition is a positive chemically amplified thick film resist composition.

12. The following steps: (1) applying a composition according to at least one of claims 1 to 11 above a substrate; and (2) heating the composition to form a resist film. A method for producing a resist film, comprising: Preferably, the heating in (2) is carried out for 100 to 250° C. and / or 60 to 300 seconds, Preferably, the heating in (2) is carried out in air or nitrogen gas atmosphere.

13. The following steps: Producing a resist film by the method according to claim 12; (3) exposing the resist film to light; (4) Developing the resist film. The method for producing a resist pattern comprising the steps of:

14. and further comprising performing a post-exposure bake between (3) and (4). The time from exposure to post-exposure bake is 1 minute, and the resist pattern is produced by the method according to claim 13. The top width ITW and bottom width IBW between the resist walls are When the time from exposure to post-exposure baking is 30 minutes and a resist pattern is produced by the method according to claim 13, the top width FTW and bottom width FBW between the resist walls are: The method according to claim 13, wherein ITW-FTW≦400 nm and / or IBW-FBW≦50 nm are satisfied.

15. The following steps: Producing a resist pattern by the method according to claim 13 or 14; (5) Processing is performed using a resist pattern as a mask. A method for producing a processed substrate, comprising: Preferably, the method (5) is a step of subjecting the underlayer film or the substrate (more preferably the substrate) to a processing treatment.

16. A method for manufacturing a device, comprising the method according to at least one of claims 12 to 15.

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