Displacement liquid between resist patterns, and method for manufacturing resist patterns using the same

Abstract

Problem: An inter-resist pattern displacement liquid, and a manufacturing method of a resist pattern using the same. Solution: An inter-resist pattern displacement liquid containing (A) a sulfonyl-containing compound, (B) a nitrogen-containing compound, and (C) a solvent is provided.

Description

Technical Field

[0001] This invention relates to a displacement solution between resist patterns and a method for manufacturing resist patterns using the same. The invention also relates to a method for manufacturing a substrate and a method for manufacturing an apparatus. Background Technology

[0002] In recent years, the demand for high integration of LSIs has been increasing, and there is a growing need for finer resist patterns. To meet this demand, photolithography processes using short-wavelength KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet (EUV; 13 nm), X-rays, electron beams, etc., have been practically used. To address this need for finer resist patterns, high-resolution photosensitive resin compositions used as resists in fine processing are also required. However, with the refinement described above, there is a tendency for resist pattern collapse, an increase in the number of defects, and a deterioration in pattern roughness.

[0003] It is believed that the collapse of the resist pattern is caused by the negative pressure generated between the patterns due to the surface tension of water when washing the pattern with water (deionized water) after development. To improve the collapse of the resist pattern, there are methods that use a washing solution containing specific components instead of water for washing (e.g., Patent Document 1). Furthermore, to improve the surface roughness of the resist, there are methods that apply a composition containing specific components to the dried resist pattern (e.g., Patent Document 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2018 / 095885

[0007] Patent Document 2: International Publication No. 2016 / 060116 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] The inventor believes that more than one problem still needs improvement. These can be listed as follows:

[0010] In fine resist patterns, this technology aims to prevent pattern collapse; reduce defects in fine resist patterns; suppress uneven surface energy of the resist film; reduce components of the developer remaining in the resist film; suppress swelling of the resist pattern; reduce the frequency of water droplet formation during the drying process; increase the hardness and / or elastic modulus of the resist pattern; and suppress unevenness in the shape of the resist pattern.

[0011] Solution for solving the problem

[0012] The displacement solution between the resist patterns of the present invention contains (A) a sulfonyl compound, (B) a nitrogen-containing compound, and (C) a solvent, wherein,

[0013] (A) Compounds containing a sulfonyl group are represented by formula (a).

[0014]

[0015] R 11 C 1-20 C atoms with alkyl groups, or C atoms partially or wholly replaced by halogens or -OH groups. 1-20 Alkyl, non-substituted or derived from R 13 Replacement C 6-10 Aryl group, -OH group, or nitrogen group, with H group ionically bonded to nitrogen. + It can be changed to NH4 + ,

[0016] R 12 -OH, C 1-15 C atoms in which alkyl groups, or partially or wholly of the hydrogen atoms are replaced by halogens. 1-15 alkyl,

[0017] R 13 C 1-5 C atoms in which alkyl groups, or partially or wholly of the hydrogen atoms are replaced by halogens. 1-5 alkyl,

[0018] R 11 R 12 Or R 13 The alkyl groups in the compound can form rings, or they can form rings through the bonding of two or more of them.

[0019] n 11 = 1, 2 or 3; and (C) solvent contains water.

[0020] The method for manufacturing the resist pattern of the present invention includes the following steps:

[0021] (1) A photosensitive resin composition is applied to a substrate with or without an intermediate layer to form a photosensitive resin layer.

[0022] (2) Expose the aforementioned photosensitive resin layer to radiation;

[0023] (3) Apply a developer to the exposed photosensitive resin layer to form a resist pattern;

[0024] (4) Apply the displacement solution between the resist patterns to the resist patterns to replace the liquid existing between them; and

[0025] (5) Remove the replacement solution between the anti-corrosion patterns.

[0026] The method for manufacturing the substrate of the present invention includes the following steps:

[0027] The resist pattern is manufactured using the method described above; and

[0028] (6) Use the anti-corrosion pattern as a mask for processing.

[0029] The manufacturing method of the device of the present invention includes the following steps:

[0030] The substrate is manufactured using the method described above.

[0031] The effects of the invention

[0032] By using the displacement solution between the anti-corrosion patterns according to the present invention, one or more of the following effects can be obtained.

[0033] In fine resist patterns, it can prevent pattern collapse; reduce defects in fine resist patterns; suppress uneven surface energy distribution in the resist film; reduce residual developer components within the resist film; suppress resist swelling; reduce the frequency of water droplet formation during the resist drying process; and increase the hardness and / or elastic modulus of the resist pattern. It can also suppress irregularities in the shape of the resist pattern. Detailed Implementation

[0034] Model for implementing invention

[0035] The embodiments of the present invention will now be described in detail.

[0036] definition

[0037] In this specification, unless otherwise stated, follow the definitions and examples provided in this section.

[0038] The singular form includes the plural form, and "one" or "that" means "at least one". Elements of a concept may be represented by multiple kinds, and in the case of recorded quantities (e.g., mass % or mole %), the quantity refers to the sum of multiple kinds.

[0039] "And / or" includes all combinations of elements, as well as individual uses.

[0040] When a numerical range is expressed using "to" or "~ / -", both endpoints are included, and the units are interchangeable. For example, 5–25 mol% means 5 mol% or more and 25 mol% or less.

[0041] “C x-y “C” x ~Cy "and "C x Descriptions such as "" refer to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having one or more but no more than six carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0042] If a polymer has multiple types of repeating units, these repeating units will copolymerize. These copolymers can be any of alternating copolymers, random copolymers, block copolymers, graft copolymers, or mixtures thereof. When a polymer or resin is represented by a structural formula, n, m, etc., written in parentheses indicate the number of repetitions.

[0043] Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius.

[0044] An additive refers to the compound itself that has this function (e.g., in the case of a base-generating agent, the compound itself that generates a base). It can also be added to the composition by dissolving or dispersing the compound in a solvent. As an embodiment of the invention, it is preferred that the solvent be included in the composition of the invention as (C) solvent or other components.

[0045] <Displacement fluid between anti-corrosion patterns>

[0046] The displacement solution between the resist patterns of the present invention (hereinafter sometimes referred to as displacement solution) contains (A) a sulfonyl compound, (B) a nitrogen-containing compound and (C) a solvent.

[0047] Here, the characteristic of the displacement solution between resist patterns is that it replaces the liquid existing between the resist patterns by being applied between them. That is, the displacement solution between resist patterns of the present invention is applied between resist patterns in a wetted state after development treatment, which is different from the resist pattern treatment solution applied to resist patterns after drying after development treatment.

[0048] (A) Compounds containing sulfonyl groups

[0049] The sulfonyl group-containing compound (A) used in this invention is represented by formula (a).

[0050]

[0051] Among them, R 11 C 1-20 C atoms with alkyl groups, some or all of which have hydrogen atoms replaced by halogens (preferably fluorine) or -OH 1-20 Alkyl, non-substituted or derived from R 13 Replacement C 6-10 Aryl group, -OH group, or nitrogen group. Here, nitrogen is in the n group. 11 =1 is -NH2, in n 11=2 is -NH-. H ions that ionize with nitrogen. + It can be changed to NH4 + For example, n 11 When = 2, the H of -NH- + Change to NH4 + The formation of ammonium salts is also permitted. In one preferred embodiment of the invention, H+ ions are ionically bonded to nitrogen. + Unchanged and replaced with NH4 + Here, the aforementioned C 1-20 Alkyl groups in n 11 When it is 2 or 3, it means C 1-20 Divalent or trivalent saturated hydrocarbon groups.

[0052] R 12 -OH, C 1-15 C atoms in which alkyl groups, or partially or wholly of the hydrogen atoms are replaced by halogens. 1-15 alkyl.

[0053] R 13 C 1-5 C atoms in which alkyl groups, or partially or wholly of the hydrogen atoms are replaced by halogens. 1-5 alkyl.

[0054] R 11 R 12 Or R 13 The alkyl groups in the compound can form rings or can form rings by bonding two or more of them together.

[0055] Unbound by theory, it is believed that by containing sulfonyl groups (more preferably sulfonic acid or sulfonylimide skeleton), residual components of the developer (more preferably alkaline aqueous solution, and even more preferably tetramethylammonium hydroxide (TMAH) aqueous solution) remaining in the resist pattern can be removed.

[0056] As one of the preferred methods, equation (a) is represented by equation (a-1).

[0057] R 14 -SO3H (a-1)

[0058] in,

[0059] R 14 C 1-20 C atoms with alkyl groups, or partially or wholly substituted with fluorine or -OH 1-20 Alkyl, non-substituted or derived from R 13 Replacement C 6-10 Aryl or -OH

[0060] R 13 C 1-5 alkyl.

[0061] Equation (a-1) is preferably represented by equations (a-1-1), (a-1-2), or (a-1-3).

[0062] R 15 -SO3H (a-1-1)

[0063] in,

[0064] R 15 -OH, C 1-9 C atoms in which alkyl groups, or partially or wholly of the hydrogen atoms, are replaced by fluorine or -OH 1-9 Alkyl group. R 15 Preferably -OH, straight-chain C 1-3 C atoms whose alkyl, hydroxymethyl, hydroxyethyl, or partially or wholly hydrogenated forms are replaced by fluorine. 1-8 Alkyl; more preferably -OH, methyl, ethyl, hydroxymethyl, or C whose hydrogen atoms are all substituted with fluorine. 1-4 Alkyl groups, or C groups whose hydrogen atoms are partially replaced by fluorine 5-8 alkyl.

[0065] Examples of these include sulfuric acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, hydroxymethanesulfonic acid, nonafluorobutanesulfonic acid, and tridecylfluorooctanesulfonic acid.

[0066] C m H 2m+1 SO3H (a-1-2)

[0067] in,

[0068] m is a number from 10 to 20. m is preferably a number from 11 to 19, more preferably a number from 12 to 18, and even more preferably a number from 13 to 18.

[0069] Examples of these include decanesulfonic acid, 1-dodecanesulfonic acid, and 1-tetradecanesulfonic acid. For example, alkylsulfonic acids represented by (a-1-2) with 11 to 19 carbon atoms (m = 11 to 19 above) are one of the preferred forms of the sulfonyl group-containing compounds of (A) of the present invention.

[0070]

[0071] Among them, R 16 It is hydrogen or C 1-5 Alkyl, preferably hydrogen, methyl or tert-butyl, more preferably hydrogen or methyl.

[0072] Examples of these include benzenesulfonic acid and toluenesulfonic acid.

[0073] As one of the preferred methods, equation (a) is represented by equation (a-2).

[0074]

[0075] in,

[0076] L 11 C 1-5 Alkylene or -NH-; preferably C 1-3 Alkylene or -NH-; more preferably -NH-. H+ ionically bonded to nitrogen. + It can also be changed to NH4 + One preferred embodiment of the present invention is H+ ionically bonded to nitrogen. + Unchanged and replaced with NH4 + .

[0077] R 17 and R 18 They are independently -OH and C, respectively. 1-15 C10 with alkyl groups, or C20 with some or all of its hydrogen atoms replaced by fluorine. 1-15 Alkyl group; preferably -OH or C4 with all hydrogen atoms replaced by fluorine. 1-5 alkyl.

[0078] R 17 and R 18 The alkyl groups can bond with each other to form rings. Examples of such rings include ethanedisulfonic acid, bis(trifluoromethanesulfonyl)amide, bis(nonafluorobutanesulfonyl)imide, and cyclohexafluoropropane-1,3-bis(sulfonamide).

[0079] For example, the compound on the left below, cyclohexafluoropropane-1,3-bis(sulfonamide), can be included in formula (a-2). In this case, it can be understood as L 11 -NH-, R 17 It is fluoroethyl (C2), R 18 For fluoromethyl (C1), R 17 and R 18 The way in which they bond together to form a ring. The compound on the right below is an H-ring that is ionicly bonded to the nitrogen of the compound on the left below. + Change to NH4 + The resulting ammonium salt.

[0080]

[0081] (A) The molecular weight of the sulfonyl compound is preferably 90 to 600; more preferably 90 to 300; and even more preferably 220 to 350.

[0082] (A) The content of the sulfonyl compound, based on the total mass of the replacement solution between the resist patterns, is preferably 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, and even more preferably 0.1 to 1% by mass.

[0083] (B) Nitrogen-containing compounds

[0084] The displacement solution of the present invention contains (B) a nitrogen-containing compound. (B) The nitrogen-containing compound acts to control the acidity of the displacement solution of the present invention. Although not bound by theory, it is believed that in the absence of the nitrogen-containing compound (B), acidic components (e.g., (A) a sulfonyl compound or (D) a polymer) can cause deprotection of the resist, resulting in pattern collapse.

[0085] (B) The nitrogen-containing compound is (B1) a monoamine compound, (B2) a diamine compound, or (B3) a heteroaryl compound containing 1 to 3 nitrogen atoms.

[0086] (B1) Monoamine compounds

[0087] (B1) Monoamine compounds are represented by formula (b1).

[0088]

[0089] in,

[0090] R 21 R 22 and R 23 H and C are independent of each other. 1-5 Alkyl, or C 1-5 Alkyl group,

[0091] R 21 R 22 and R 23 The alkyl groups in R can form rings, and two or more of them can bond to each other. 21 R 22 and R 23 The -CH2- portion of the alkyl group can be replaced by -O-.

[0092] In this invention, (B1) monoamine compounds include ammonia (R 21 R 22 and R 23 (All are H). Ammonia is also a preferred method as a (B1) monoamine compound.

[0093] Examples of (B1) monoamine compounds other than ammonia include the following compounds.

[0094] (i) Primary amines, such as propylamine, butylamine, pentanamine, 2-methylbutylamine, 2-aminoethanol, 3-amino-1-propanol, aminoethoxyethanol, cyclohexylamine, and cyclopentylamine.

[0095] (ii) Secondary amines, such as diethylamine, dipropylamine, dibutylamine, diethanolamine, diethanolamine, piperidine, morpholine, and pyrrolidine, and

[0096] (iii) Tertiary amines, such as triethylamine, tripropylamine, N-methyldiethylamine, triethanolamine and triethanolamine.

[0097] (B2) diamine compounds

[0098] (B2) Diamine compounds are represented by formula (b2).

[0099]

[0100] in,

[0101] R 31 R 32 R 33 and R 34 H and C are independent of each other. 1-5 Alkyl, or C 1-5 Alkyl group,

[0102] R 31 R 32 R 33 and R 34 The alkyl groups in R can form rings, and two or more of them can bond to each other. 31 R 32 R 33 and R 34 The -CH2- moiety of the alkyl group can be replaced by -O-, L 31 C 1-5 Alkylene, where the -CH2- portion of the alkylene group can be replaced by -O-.

[0103] (B2) Examples of diamine compounds include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetrapropylethylenediamine, N,N,N',N'-tetraisopropylethylenediamine, N,N,N',N'-tetrabutylethylenediamine, N,N,N',N'-tetraisobutylethylenediamine, N,N,N',N'-tetramethyl-1,2-propanediamine, N,N,N',N'-tetraethyl-1,2-propanediamine, N,N,N',N'-tetrapropyl-1,2-propanediamine, N,N,N',N'-tetraisopropyl-1,2-propanediamine, N,N,N',N'-tetramethyl- 1,3-Propanediamine, N,N,N',N'-Tetraethyl-1,3-Propanediamine, N,N,N',N'-Tetrapropyl-1,3-Propanediamine, N,N,N',N'-Tetraisopropyl-1,3-Propanediamine, N,N,N',N'-Tetraisobutyl-1,3-Propanediamine, N,N,N',N'-Tetramethyl-1,2-Butanediamine, N,N,N',N'-Tetraethyl-1,2-Butanediamine, N,N-Dimethylaminoethylamine, N,N-Diethylaminoethylamine, N,N-Dimethylaminopropylamine, N,N-Diethylaminopropylamine, N-Methylaminoethylamine, N-Ethylaminoethylamine, N-(2-Aminoethylamino)ethanol, piperazine, and 1,4-diazabicyclo[2.2.2]octane.

[0104] (B3) contains 1 to 3 heteroaryl groups.

[0105] The heteroaryl group containing 1 to 3 nitrogen atoms is preferably a 5-membered or 6-membered ring, such as pyridine, imidazole, and triazine. The number of nitrogen atoms is preferably 1 or 2, more preferably 1.

[0106] (B) The content of nitrogen-containing compounds, based on the total mass of the replacement solution between the anti-corrosion patterns, is preferably 0.01 to 20% by mass; more preferably 0.01 to 5% by mass; further preferably 0.01 to 1% by mass; and even more preferably 0.1 to 1% by mass.

[0107] (B) The molecular weight of the nitrogen-containing compound is preferably 17 to 170; more preferably 17 to 150; even more preferably 17 to 120; and even more preferably 50 to 120.

[0108] (C) Solvent

[0109] The displacement solution of the present invention contains solvent (C). Solvent (C) contains water. Water is preferably deionized water. For use in fine resist patterns, solvent (C) preferably has few impurities. Preferred impurities in solvent (C) are 1 ppm or less; more preferably 100 ppb or less; and even more preferably 10 ppb or less. Filtering the liquid is also a preferred method of the present invention for use in fine processes.

[0110] The water content, based on the total mass of solvent (C), is preferably 90–100% by mass; more preferably 98–100% by mass; further preferably 99–100% by mass; and even more preferably 99.9–100% by mass. As a preferred embodiment of the invention, solvent (C) is substantially composed of only water. However, the state in which additives are dissolved and / or dispersed in solvents other than water (e.g., surfactants), and the manner in which they are included in the displacement solution of the invention, is permitted as a preferred embodiment of the invention.

[0111] Specific examples of solvents (C) other than water include cyclohexanone, cyclopentanone, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, or mixtures thereof. These are preferred in terms of the storage stability of the solution. Two or more of these solvents can also be used in mixture.

[0112] (C) The solvent content, based on the total mass of the replacement fluid between the resist patterns, is preferably 80 to 99.98% by mass, more preferably 90 to 99.5% by mass, and even more preferably 95 to 99% by mass.

[0113] Furthermore, based on the total mass of the replacement solution between the resist patterns, the water content in the solvent (C) is preferably 80–99.94% by mass; more preferably 90–99.94% by mass, and even more preferably 95–99.94% by mass.

[0114] The displacement solution of the present invention is essential to include the above-mentioned components (A) to (C), but may further contain compounds as needed. This will be described in detail below. It should be noted that the percentage of components other than (A) to (C) in the total composition (total if multiple components are present) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 3% by mass, based on the total mass of the displacement solution. A preferred embodiment of the present invention is one in which the displacement solution does not contain any components other than (A) to (C) (0% by mass).

[0115] (D) Polymer

[0116] The displacement fluid of the present invention may further contain (D) polymer.

[0117] From the viewpoint of affinity with the replacement solution, polymer (D) is preferably a water-soluble polymer. More preferably, the repeating unit has at least one group selected from the group consisting of sulfonyl (-SO3H), carboxyl (-COOH), hydroxyl (-OH), and carbonyl (-CO-) and their salts. Polymer (D) is further preferably having sulfonyl (-SO3H) and / or carboxyl (-COOH) in the repeating unit.

[0118] Examples of (D) polymers include, for example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polystyrene sulfonic acid, fluoroethylene ether alkyl acid polymers, poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(trifluoromethacrylic acid) and their salts, and copolymers of any of them.

[0119] In addition, polyacrylamide or poly(trifluoromethyl)-4-penten-2-ol can also be used as (D) polymers.

[0120] By incorporating (D) polymers, the anti-collapse effect and defect suppression effect can be improved.

[0121] (D) The mass-average molecular weight of the polymer is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 20,000. Here, mass-average molecular weight refers to the mass-average molecular weight converted from styrene, which can be determined by gel permeation chromatography as a reference for styrene.

[0122] (D) The polymer content, based on the total mass of the replacement fluid between the anti-corrosion patterns, is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass; further preferably 0.5 to 10% by mass; and even more preferably 1 to 8% by mass.

[0123] (E) Surfactants

[0124] The displacement solution of the present invention may further contain (E) surfactant. (E) surfactant is a different component from (A) to (D).

[0125] The coating properties can be improved by including surfactants.

[0126] In this invention, (E) surfactant refers to the compound itself having the above-described function. This compound can be dissolved or dispersed in a solvent and included in the composition (liquid), but such solvent is preferably included in the composition as (C) solvent or other component. The same applies below to various additives that can be included in the composition.

[0127] Anionic, cationic, or nonionic surfactants can be listed as surfactants that can be used in this invention. More specifically, examples include laurylpyridinium chloride and laurylmethylammonium chloride, polyoxyethylene octyl ether, polyoxyethylene lauryl ether and polyoxyethylene kynediol ether, fluorinated surfactants (e.g., Fluorad (trade name, Sumitomo 3M), Megafac (trade name, DIC), Surflon (trade name, Asahi Glass), or organosiloxane surfactants (e.g., KP341, trade name, Shin-Etsu Chemical Co., Ltd.).

[0128] The content of (E) surfactant, based on the total mass of the replacement solution of the present invention, is preferably 0.01 to 5% by mass, more preferably 0.03 to 1% by mass. It is also a preferred option to not contain (E) surfactant (0.0% by mass).

[0129] (F) Additives

[0130] The replacement fluid used in this invention may further contain additive (F). Additive (F) is a component different from (A) to (E). Additive (F) preferably contains an acid, a base, a surfactant other than surfactant (E), a bactericide, an antibacterial agent, a preservative, an antifungal agent, or a combination thereof; more preferably it contains an acid, a base, a bactericide, an antibacterial agent, a preservative, or an antifungal agent.

[0131] The content of (F) additive, based on the total mass of the replacement solution between the anti-corrosion patterns, is preferably 0.0005 to 20% by mass, more preferably 0.0005 to 1% by mass. It is also a preferred option to not contain (F) additive (0.0% by mass).

[0132] <Method for Manufacturing Anti-corrosion Patterns>

[0133] The method for manufacturing the resist pattern of the present invention includes the following steps.

[0134] (1) A photosensitive resin composition is applied to a substrate with or without an intermediate layer to form a photosensitive resin layer.

[0135] (2) Expose the photosensitive resin layer to radiation;

[0136] (3) Apply a developer to the exposed photosensitive resin layer to form a resist pattern;

[0137] (4) The displacement liquid between the resist patterns of the present invention is applied between the resist patterns to replace the liquid existing between the resist patterns; and

[0138] (5) Remove the replacement solution between the anti-corrosion patterns.

[0139] For clarity, the numbers in parentheses indicate the order. For example, step (4) is performed before step (5).

[0140] The following is a detailed explanation.

[0141] The photosensitive resin composition is applied to the substrate (e.g., silicon / silica coated substrate, silicon nitride substrate, silicon wafer substrate, glass substrate, and ITO substrate, etc.) using a suitable method. Here, in this invention, "on top" includes both the case where it is formed directly above and the case where it is formed with other layers in between. For example, a planarization film or a photoresist underlayer can be formed directly above the substrate, and the photosensitive resin composition can be applied directly above it. The application method is not particularly limited; for example, coating methods using a spin coater or a coating machine can be listed. After coating, a photosensitive resin layer is formed by heating as needed. Heating is performed, for example, by a hot plate. The heating temperature is preferably 60–140°C; more preferably 90–110°C. Here, the temperature refers to the heating atmosphere, such as the heating surface temperature of a hot plate. The heating time is preferably 30–900 seconds, more preferably 60–300 seconds. Heating is preferably performed in an atmospheric or nitrogen atmosphere.

[0142] The thickness of the photosensitive resin layer can be selected according to the purpose. The thickness of the photosensitive resin layer can also be increased to more than 1 μm.

[0143] In the resist pattern manufacturing method of the present invention, films or layers other than the photosensitive resin layer are also permitted. The substrate and the photosensitive resin layer are not in direct contact; an intermediate layer may be present. The intermediate layer is a layer formed between the substrate and the photosensitive resin layer, also called a lower layer film. Examples of lower layers include substrate modification films, planarization films, lower anti-reflective films (BARC), inorganic hard mask intermediate layers (silicon oxide films, silicon nitride films, and silicon oxide nitride films), and adhesive films. The intermediate layer may consist of one or more layers. Furthermore, an upper anti-reflective film (TARC) may be formed on the photosensitive resin layer.

[0144] The photosensitive resin layer is exposed to radiation using a prescribed mask. If other layers (such as a TARC layer) are also included, they can be exposed together. There are no particular limitations on the wavelength of the light used for exposure, but exposure with wavelengths of 13.5–248 nm is preferred. Specifically, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and extreme ultraviolet light (wavelength 13.5 nm) can be used. These wavelengths are allowed within a range of ±1%. After exposure, post-exposure heating (PEB) can be performed if necessary. The temperature of PEB is suitably selected from 70–150 °C; preferably 80–120 °C, and the heating time is 30–300 seconds; preferably 30–120 seconds. Heating is preferably performed in an atmospheric or nitrogen atmosphere.

[0145] Next, the developer is applied to the exposed photosensitive resin layer to form a resist pattern. As a development method, conventional methods used for developing photoresists, such as swirling immersion development, dip development, and agitation dip development, can be used. Swirling immersion development is preferred. Furthermore, as the developer, an aqueous solution containing inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium silicate; organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, and triethylamine; or quaternary ammonium such as TMAH can be used. A 2.38% (±1%) TMAH aqueous solution is preferred. Additionally, surfactants can be added to these developers. The temperature of the developer is generally 5–50°C; preferably 25–40°C, and the development time is generally 10–300 seconds; preferably 20–60 seconds.

[0146] With developer residue remaining between the resist patterns, further processing steps may be added as needed:

[0147] (3.1) Apply the washing solution to the resist pattern to wash the resist pattern.

[0148] As the washing liquid used here, a washing liquid used by known methods can be used, such as water (deionized water) or a known cleaning liquid.

[0149] When the resist pattern has residual developer or the aforementioned washing solution, the replacement solution of the present invention is applied to the resist pattern to replace the liquid present between the resist patterns.

[0150] When a developer is applied to a photosensitive resin layer to form a resist pattern, components contained in the developer (e.g., alkaline components, TMAH) may sometimes remain within the resist pattern film.

[0151] Although not bound by theory, the inventors believe that the residual components from the developer are difficult to remove with the aforementioned washing solution (water or cleaning solution). It is believed that by applying the replacement solution of the present invention to the resist pattern, the residual components from the developer can be removed from the resist pattern film by means of the sulfonyl compound contained in the replacement solution of the present invention. Its effect can also induce absorption based on neutralization energy. That is, through steps (4) and / or (5), the residual components from the developer are reduced from the resist pattern.

[0152] It is believed that residual components from the developer within the resist pattern film cause swelling of the resist pattern, or that the alkaline components are unevenly present in the resist pattern, resulting in uneven surface energy within the resist pattern. If the surface energy of the resist pattern is uneven, water droplets are generated during the drying process, which is considered a cause of pattern collapse. By applying the replacement solution of the present invention, the residual components from the developer are reduced, swelling of the resist pattern is suppressed, the hardness of the resist pattern is increased, and the surface energy of the resist pattern is homogenized. As a result, it is believed to have the effect of suppressing resist pattern collapse. Therefore, it is more preferable not to dry the resist pattern before applying the replacement solution of the present invention. That is, it is preferable not to dry the resist pattern between steps (3) and (4). Furthermore, as one of the preferred embodiments of the present invention, the replacement solution of the present invention can be considered a resist film surface modifier containing the aforementioned components (A), (B), (C), etc. The resist film referred to here is not limited to patterned resist films, but patterned resist films are more preferred.

[0153] It should be noted that the anti-corrosion pattern obtained in step (5) is considered to have higher hardness and / or elastic modulus than the anti-corrosion pattern obtained in step (3) and previous steps.

[0154] It should be noted that the following is referred to as the stress applied to the resist wall during drying.

[0155] As in equation (8) of Namatsu et al. Appl. Phys. Lett. 1995(66) pp. 2655-2657, as stated in the following equation,

[0156] σ max = 6γcosθ / Dx(H / W) 2

[0157] The stress applied to the wall during the drying process can be expressed by the following formula. Furthermore, a schematic diagram is shown in FIG. 5 of this journal.

[0158] σ max γ: Maximum stress applied to the resist; γ: Surface tension of the liquid.

[0159] θ: Contact angle, D: Wall spacing

[0160] H: Wall height, W: Wall width

[0161] The lengths of D, H, and W can be measured using known methods (e.g., SEM images).

[0162] As can be seen from the above formula, a shorter D or a shorter W will lead to greater stress.

[0163] After applying the displacement solution of the present invention, the displacement solution is removed. There are no particular limitations on the removal method, but it is preferable to apply a washing solution to the resist pattern. The preferred washing solution is water or a cleaning solution as described above.

[0164] Finally, for example, a dried resist pattern is formed by rotating the substrate at high speed.

[0165] The application method of the washing solution or the replacement solution of the present invention is not particularly limited, but the contact time with the resist pattern, i.e., the processing time, is preferably 1 second or more. Furthermore, the processing temperature can be arbitrary. The contact method is also arbitrary; for example, it can be performed by immersing the substrate in the liquid or by dripping the liquid onto the surface of a rotating substrate.

[0166] In the method for manufacturing the resist pattern of the present invention, one of the preferred methods is to replace the developer with water, replace the water with the replacement solution of the present invention, replace the replacement solution with a washing solution, and then dry the substrate by high-speed rotation.

[0167] The resist pattern manufactured by the method of this invention suppresses the formation of defects such as bridging and also inhibits the collapse of the resist pattern. In this specification, a bridge is a type of defect, referring to a structure in the groove of the resist pattern that differs from the expected structure. Reasons may include interconnections between the resist pattern (walls) or foreign objects that should be flushed away remaining stuck in the groove. If the target groove is filled with bridges, it is impossible to design the target circuit in subsequent processes such as etching. The mechanism by which the replacement solution of this invention suppresses the formation of defects such as bridging is not yet elucidated, and this effect is unexpected.

[0168] <Manufacturing Methods for Processed Substrates and Devices>

[0169] After creating the resist pattern as described above, the following steps are performed:

[0170] (6) Use the anti-corrosion pattern as a mask for processing.

[0171] The processing substrate of the present invention is formed.

[0172] The resist pattern manufactured by the method of the present invention can be used as a mask to pattern intermediate layers and / or substrates. Patterning can be performed using known methods such as etching (dry etching, wet etching). For example, the resist pattern can be used as an etching mask to etch an intermediate layer, and the resulting intermediate layer pattern can be used as an etching mask to etch the substrate, thus forming a pattern on the substrate. Alternatively, the resist pattern can be used as an etching mask to etch layers below the photoresist layer (e.g., intermediate layers) while simultaneously etching the substrate directly. Wiring can be formed on the substrate using the formed pattern.

[0173] These layers are preferably removed by dry etching with O2, CF4, CHF3, Cl2 or BCl3, with O2 or CF4 being preferred.

[0174] Then, proceed with the required steps:

[0175] (7) Form wiring on the substrate.

[0176] Devices are formed. Further processing of these devices can be performed using known methods. After device formation, the substrate can be diced into chips, connected to a lead frame, and encapsulated in resin as needed. A preferred example of this device is a semiconductor device.

[0177] The present invention will be illustrated below with various examples. It should be noted that the invention is not limited to these examples.

[0178] <Examples 101-115, Comparative Examples 102 and 103>

[0179] Ethanol was added to water (deionized water) at a rate of 0.2% by mass as (A) a sulfonyl compound and ammonia was added at a rate of 0.5% by mass as (B) a nitrogen compound, and the mixture was dissolved. The solution was then filtered (pore size = 10 nm) to prepare the displacement solution of Example 101.

[0180] The replacement solutions of Examples 101-115, Comparative Examples 102 and 103 were prepared by using (A) the sulfonyl group-containing compound, (B) the nitrogen-containing compound, and (D) the polymer as listed in Table 1, and otherwise operated in the same manner as in Example 101.

[0181] [Table 1]

[0182]

[0183] In the table,

[0184] A1: Ethanol

[0185] A2: Mesylate

[0186] A3: Decanesulfonic acid

[0187] A4: Sulfuric acid

[0188] A5: Trifluoromethanesulfonic acid

[0189] A6: Bis(trifluoromethanesulfonyl)amide

[0190] A7: A mixture of alkyl sulfonic acid compounds with 13 to 18 carbon atoms.

[0191] B1: Ammonia

[0192] B2: Triethylamine

[0193] B3: 2-Aminoethanol

[0194] B4: Diethanolamine

[0195] B5: N-(2-aminoethylamino)ethanol

[0196] D1: Polyacrylic acid represented by the following structural formula,

[0197]

[0198] D2: Polyvinyl sulfonic acid represented by the following structural formula,

[0199]

[0200] D3: Homopolymer of fluoroethylene ether alkyl acid represented by the following structural formula

[0201]

[0202] D4: Poly(2-acrylamido-2-methyl-1-propanesulfonic acid)

[0203]

[0204] <Evaluation of Anti-collapse Effect>

[0205] A basic antireflective film composition (AZKr-F17B, manufactured by Merck Performance Materials Co., Ltd. (hereinafter referred to as MPM)) was formed by spin-coating a base antireflective film onto a silicon substrate, and then heated on a hot plate at 180°C for 60 seconds to obtain a lower antireflective film with a thickness of 80 nm. A PHS-acrylate-based chemically amplified resist (DX6270P, manufactured by MPM) was then coated onto this resist, and heated on a hot plate at 120°C for 90 seconds to obtain a resist film with a thickness of 620 nm. The substrate was then exposed using a KrF exposure apparatus (FPA3000 EX5, manufactured by Canon) through a mask (250 nm line / space 1:1). At this time, the exposure dose was 25 mJ / cm². 2 ~40mJ / cm 2The changes caused a variation in the resulting linewidth. Then, after 60 seconds of exposure followed by heating (PEB) on a hot plate at 100°C, a 2.38% by mass TMAH aqueous solution of the developer was poured in, and held for 60 seconds (swirling immersion). While the substrate was swirling immersion in the developer, water was introduced, and the substrate was rotated while the developer was being replaced with water. The process was stopped while the substrate was swirling immersion in water, and the substrate was allowed to stand for 90 seconds. Then, while the substrate was swirling immersion in water, the replacement solution prepared in Example 101 was introduced to replace the water. The process was stopped while the substrate was swirling immersion in the replacement solution, and the substrate was allowed to stand for 30 seconds. The substrate was then dried by a 30-second high-speed rotation process, followed by water infusion and washing for 30 seconds. Finally, after the substrate was dried by the high-speed rotation process, the resist pattern was observed for collapse using a length-measuring SEM CG4000 (manufactured by Hitachi High-Technologies Corporation).

[0206] The same procedure was performed using the replacement solutions of Examples 102-115, Comparative Examples 102 and 103, respectively.

[0207] Comparative Example 101 was performed similarly to Example 101, involving immersion in developer solution followed by water immersion for 30 seconds, and drying of the substrate by high-speed rotation. That is, in Comparative Example 101, no replacement solution treatment was performed. At this time, when the linewidth became less than 188 nm, the collapse of the resist pattern was observed.

[0208] The evaluation criteria are shown below. The results are as described in Table 1.

[0209] A: When the linewidth is above 150nm but below 178nm, no collapse of the resist pattern was detected.

[0210] B: When the linewidth is above 178nm but less than 188nm, the collapse of the resist pattern is confirmed.

[0211] C: When the linewidth is above 188nm and below 220nm, the collapse of the resist pattern is confirmed.

[0212] <Evaluation of Defect Suppression Effect>

[0213] EUV-grade PHS-acrylate chemically amplifying resist was spin-coated onto a silicon substrate and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 45 nm. A 2.38% by mass TMAH aqueous solution of developer was then introduced and held for 30 seconds. While the substrate was swirled and submerged in developer, water was introduced to replace the developer while the substrate was rotated, and the process was stopped for 90 seconds while the substrate was swirled and submerged in water. Then, while the substrate was swirled and submerged in water, the displacement solution prepared in Example 101 was introduced to replace the water, and the process was stopped for 30 seconds while the substrate was swirled and submerged in the displacement solution. The substrate was then dried by a 30-second high-speed spin treatment, followed by further water introduction and washing for 30 seconds. Finally, the substrate was dried by a high-speed spin treatment.

[0214] The same operation was performed using the replacement solutions of Examples 102-115 and Comparative Examples 102 and 103, respectively.

[0215] Comparative Example 101 was similar to Example 101, in which the substrate was immersed in the developer solution, then rinsed in water for 30 seconds, and dried by high-speed rotation. That is, no replacement solution was used.

[0216] The number of defects was observed using the LS9110 wafer surface inspection device (manufactured by Hitachi High-Technologies Corporation), and the results are evaluated as follows. The results are shown in Table 1.

[0217] A: Compared with Comparative Example 101, the number of defects is less than 25%.

[0218] B: Compared with Comparative Example 101, the number of defects is more than 25% and less than 50%.

[0219] C: Compared with Comparative Example 101, the number of defects is more than 50% but less than 150%.

[0220] D: Compared with Comparative Example 101, the number of defects is more than 150%.

[0221] <Examples 201-208>

[0222] The displacement solutions of Examples 201-208 were prepared by using (A) the sulfonyl compound, (B) the nitrogen compound, and (D) the polymer, respectively, as described in Table 2, except that the procedure was the same as in Example 101.

[0223] [Table 2]

[0224]

[0225] <Evaluation of Limit Pattern Size 1>

[0226] A silicon substrate was treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. An EUV-grade PHS-acrylate chemically amplified resist was then spin-coated onto the substrate and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 45 nm. The substrate was then exposed using an EUV exposure apparatus (NXE: 3300B, manufactured by ASML) through a mask (18 nm line / space 1:1). The exposure amount was varied to change the obtained linewidth. Then, the substrate was exposed to a hot plate at 100°C for 60 seconds followed by heating (PEB), and a 2.38% (w / w) TMAH aqueous solution of developer was poured in and held for 30 seconds (spin-over immersion). While the substrate was spin-over immersion in developer, water was introduced to replace the developer with water while the substrate was rotated. The process was stopped while the substrate was still spin-over immersion in water, and the substrate was allowed to stand for 90 seconds. Then, while the substrate is immersed in water, the replacement solution of Example 201 is introduced to replace the water. The substrate is then immersed in the replacement solution and allowed to stand for 30 seconds. Next, the substrate is dried by high-speed rotation for 30 seconds, then washed for 30 seconds with a cleaning solution containing surfactant (AZSPC-708, MPM), and then dried by high-speed rotation.

[0227] The linewidth of the formed corrosion-resistant pattern and the presence or absence of pattern collapse were observed using a length-measuring SEM CG4000. The smallest line dimension where pattern collapse was not confirmed was taken as the limit pattern dimension.

[0228] The limit pattern size was obtained in the same manner using the replacement solutions of Examples 202 to 208 respectively.

[0229] The process was evaluated using the following methods. The resist film formed by each method described below was used as Comparative Example 301. The samples obtained by treating the resist film of Comparative Example 301 in processes A to E were used as Comparative Example 302, Comparative Example 303, Example 301, Example 302, and Example 303.

[0230] [Formation of resist film]

[0231] The silicon substrate was treated with HMDS at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist was then spin-coated onto the substrate and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 40 nm.

[0232] [Process A]

[0233] After pouring a 2.38% by mass TMAH aqueous solution of the developer onto the substrate, hold for 30 seconds. While the substrate is swirled and submerged in the developer, begin flowing water, rotating to replace the developer with water. Stop while the substrate is swirled and submerged in water, and let stand for 90 seconds. Next, wash for 30 seconds while flowing water, then perform a high-speed rotation process to dry the substrate.

[0234] [Process B]

[0235] After a 2.38% by mass TMAH aqueous solution of the developer is poured into the substrate, it is held for 30 seconds. While the substrate is swirled and submerged in the developer, water is introduced, and the developer is replaced with water while the substrate is swirled and submerged in water. This process is stopped, and the substrate is left to stand for 90 seconds. Next, a cleaning solution containing a surfactant (AZSPC-708, MPM) is introduced, and the substrate is washed for 30 seconds. Then, the substrate is subjected to high-speed rotation to dry it.

[0236] [Process C]

[0237] After a 2.38% by mass TMAH aqueous solution of the developer is poured into the substrate, it is held for 30 seconds. Water is then introduced while the substrate is swirled and submerged in the developer, displacing the developer with water. The process is stopped while the substrate is swirled and submerged in water, and allowed to stand for 90 seconds. Next, the replacement solution from Example 109 is introduced, displacing the water and the replacement solution. The substrate is then swirled and submerged in the replacement solution and allowed to stand for 30 seconds. Then, a 30-second high-speed rotation process is performed to dry the substrate. The substrate is then washed with water for 30 seconds, followed by another high-speed rotation process to dry it.

[0238] [Process D]

[0239] After a 2.38% by mass TMAH aqueous solution of the developer was poured into the substrate, it was held for 30 seconds. Water was then introduced while the substrate was swirled and submerged in the developer, displacing the developer with water. The process was stopped while the substrate was swirled and submerged in water, and allowed to stand for 90 seconds. Next, the replacement solution from Example 109 was introduced, displacing the water and the replacement solution. The substrate was then swirled and submerged in the replacement solution and allowed to stand for 30 seconds. Then, a 30-second high-speed rotation process was performed to dry the substrate. A cleaning solution containing a surfactant (AZSPC-708, MPM) was then poured into the substrate, and the substrate was washed for 30 seconds, followed by a high-speed rotation process to dry the substrate.

[0240] [Process E]

[0241] After a 2.38% by mass TMAH aqueous solution of the developer is poured into the substrate, it is held for 30 seconds. Water is then introduced while the substrate is swirled and submerged in the developer, displacing the developer with water as it is swirled. This process is stopped while the substrate is swirled and submerged in water, and allowed to stand for 90 seconds. Next, the replacement solution from Example 109 is introduced, displacing the water and the replacement solution. The substrate is then swirled and submerged in the replacement solution and allowed to stand for 30 seconds. Finally, a 30-second high-speed rotation process is performed to dry the substrate.

[0242] <TMAH Strength>

[0243] The resist film obtained by forming the resist film described above is used as Comparative Example 301.

[0244] Using a time-of-flight secondary ion mass spectrometer (TOF-SIMS5, ION-TOF), the residual TMAH on the surface of the resist film of Comparative Example 302 (the resist film after process A of Comparative Example 301) was measured to a depth of 2 nm using argon sputtering, and the TMAH intensity was used as 1.0 (reference). The residual TMAH was similarly measured on the resist film of Comparative Example 301 and on the resist films after processes B to E of Comparative Example 301, and the TMAH intensity relative to the reference was evaluated.

[0245] The results are shown in Table 3. It can be confirmed that by using the replacement solution of the present invention, the amount of TMAH remaining on the resist film is reduced.

[0246] [Table 3]

[0247]

[0248] <Evaluation of Limit Pattern Size 2>

[0249] A silicon substrate was treated with HMDS at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist was spin-coated and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 45 nm. The substrate was then exposed using an EUV exposure apparatus (NXE: 3300B, manufactured by ASML) through a mask (18 nm line / space 1:1). The exposure amount was varied to change the obtained linewidth. Then, exposure followed by heating (PEB) was performed on a hot plate at 100°C for 60 seconds. Processes A through D (Comparative Examples 302, 303, Example 301, and Example 302) were then performed.

[0250] For each formed resist pattern, the linewidth and the presence or absence of pattern collapse were observed using a length-measuring SEM CG4000. The smallest line dimension for which pattern collapse was not confirmed was taken as the limit pattern dimension. The results are shown in Table 3.

[0251] <Evaluation of Defect Reduction Rate>

[0252] Except for not changing the exposure amount, the resist film was obtained in the same order as in the evaluation of the limit pattern size described above (2). Processes A through D were performed on this resist film to form resist patterns (Comparative Example 302, Comparative Example 303, Example 301, and Example 302). The number of defects on the formed resist patterns was measured using a defect inspection device (UVsion4, manufactured by Applied Materials). The defect reduction rate during processes B through D was calculated based on the number of defects during process A. It should be noted that the higher the defect reduction rate, the more defects are suppressed. The results are shown in Table 3.

[0253] <Evaluation of contact angle and contact angle uniformity>

[0254] The silicon substrate was treated with HMDS at 90°C for 30 seconds. EUV PHS-acrylate chemically amplified resist was spin-coated and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 40 nm (untreated, Comparative Example 301). The same resist film was then treated with process A or process C (Comparative Example 302, Example 301). DIW was dropped onto the upper surface of the resist film, and the contact angle was measured. Measurements were taken at 100 locations on the same sample, yielding 3 sigma. The results are shown in Table 3. Although not bound by theory, it is believed that the TMAH residue on the film surface caused by TMAH liquid treatment can be deviated from the desired uniformity by treating it with the displacement solution of the present invention as a surface modifier.

Claims

1. A method for manufacturing a resist pattern, comprising the following steps: (1) A photosensitive resin composition is applied to a substrate with or without an intermediate layer to form a photosensitive resin layer. (2) Expose the aforementioned photosensitive resin layer to radiation; (3) Apply a developer to the exposed photosensitive resin layer to form a resist pattern; (3.1) Apply the washing solution to the resist pattern to wash the resist pattern; (4) Apply the replacement solution between the resist patterns to replace the developer or washing solution between the resist patterns; and (5) Remove the replacement solution between the resist patterns. The characteristic is that the resist pattern is not dried between steps (3) and (4). In step (4), the replacement solution between the resist patterns contains (A) a sulfonyl compound, (B) a nitrogen-containing compound, (C) a solvent, and (D) a polymer. (A) Compounds containing a sulfonyl group are represented by formula (a-1). R 14 -SO3H(a-1) Among them, R 14 C 1-20 alkyl, Of which, solvent (C) contains water; In this case, (D) polymers have sulfonyl or carboxyl groups in the repeating units.

2. The method for manufacturing the resist pattern according to claim 1, wherein, (B) Nitrogen-containing compounds are (B1) monoamine compounds, (B2) diamine compounds, or (B3) heteroaryl compounds containing 1 to 3 nitrogen groups: Here, (B1) monoamine compounds are represented by formula (b1). in, R 21 R 22 and R 23 H and C are independent of each other. 1-5 Alkyl, or C 1-5 Alkyl group, R 21 R 22 and R 23 The alkyl groups in R may or may not form a ring, and two or more of them may or may not be bonded to each other. 21 R 22 and R 23 The -CH2- portion of the alkyl group is either not replaced or is replaced by -O-. (B2) The diamine compound is represented by formula (b2). in, R 31 R 32 R 33 and R 34 H and C are independent of each other. 1-5 Alkyl, or C 1-5 Alkyl group, R 31 R 32 R 33 and R 34 The alkyl groups in R may or may not form a ring, and two or more of them may or may not be bonded to each other. 31 R 32 R 33 and R 34 The -CH2- portion of the alkyl group is either not replaced or is replaced by -O-. L 31 C 1-5 Alkylene, where the -CH2- portion of the alkylene is not replaced or is replaced by -O-.

3. The method for manufacturing the resist pattern according to claim 1 or 2, wherein, Based on the total mass of the replacement fluid between the resist patterns, (A) the content of sulfonyl compounds is 0.01 to 10% by mass.

4. The method for manufacturing the resist pattern according to claim 1 or 2, wherein, Based on the total mass of the replacement fluid between the anti-corrosion patterns, (B) the content of nitrogen-containing compounds is 0.01–20% by mass.

5. The method for manufacturing the resist pattern according to claim 1 or 2, wherein, Based on the total mass of the displacement fluid between the resist patterns, (C) solvent content is 80–99.98% by mass.

6. The method for manufacturing the resist pattern according to claim 1 or 2, wherein, Based on the total mass of the replacement fluid between the resist patterns, (C) the water content in the solvent is 80–99.94% by mass.

7. The method for manufacturing the resist pattern according to claim 1 or 2, wherein, Based on the total mass of the displacement fluid between the anti-corrosion patterns, the content of (D) polymer is 0.1–20% by mass.

8. The method for manufacturing the resist pattern according to claim 1 or 2, further comprising (E) a surfactant.

9. The method for manufacturing the resist pattern according to claim 1 or 2, further comprising (F) an additive; in, (F) The additive is an acid, alkali, (E) a surfactant other than a surfactant, a bactericide, an antibacterial agent, a preservative, an antifungal agent, or a combination thereof.

10. The method for manufacturing the resist pattern according to claim 9, wherein, Based on the displacement fluid between the anti-corrosion patterns, the content of additive (F) is 0.0005–20% by mass.

11. The method for manufacturing resist patterns according to claim 1 or 2, wherein the removal of the displacement liquid between the resist patterns in step (5) is performed by applying a washing liquid between the resist patterns.

12. The method for manufacturing the resist pattern according to claim 1 or 2, wherein, The residual components from the developer are reduced from the resist pattern through processes (4) and (5); The anti-corrosion pattern obtained in step (5) has a higher hardness and / or elastic modulus than the anti-corrosion pattern obtained in step (3) and previous steps.

13. A method for manufacturing a substrate, comprising the following steps: The resist pattern is manufactured by any one of claims 1 to 12; and (6) the resist pattern is used as a mask for processing.

14. A method for manufacturing a device, comprising the following steps: The substrate is manufactured using the method described in claim 13.

15. The method for manufacturing the device according to claim 14, further comprising the following steps: (7) Form wiring on the substrate.

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