Electronic device manufacturing aqueous solution, method for producing resist pattern, and method for manufacturing device

Abstract

An earth environment-friendly fluorine-free electronic device manufacturing aqueous solution that enables suppression of defects is provided. The electronic device manufacturing aqueous solution comprises a compound (A) having a specific structure that does not contain fluorine, a solvent (B) comprising water, and optionally a diol compound (C) having a specific structure. The electronic device manufacturing aqueous solution is a high- performance material that can be used in a semiconductor device manufacturing step of a nanotechnology process, for example, a step of manufacturing a semiconductor device that controls liquid crystals, quantum dots, or OLED displays formed on a substrate.

Description

Description Title of invention: Electronic device manufacturing aqueous solution, resist pattern manufacturing method, and device manufacturing method Technical field

[0001] The present invention relates to an aqueous solution for manufacturing electronic devices, a method for manufacturing a resist pattern, and a method for manufacturing a device.

[0002] In recent years, there has been an increasing need for higher integration of LSIs, and there has been a demand for finer patterns. To meet these needs, lithography processes using short-wavelength light such as KrF excimer lasers, Ar excimer lasers, extreme ultraviolet rays, X-rays, and electron beams are becoming practical. To meet this demand for finer resist patterns, photosensitive resin compositions used as resists during fine processing are also required to have high resolution. Although finer patterns can be formed by exposure to short-wavelength light, the creation of extremely fine structures poses yield problems, such as collapse of the fine pattern.

[0003] Patent Document 1 discloses a method for removing stains by using a rinse solution containing a sulfonic acid compound and a diol derivative. Patent Document 2 discloses that a rinse solution containing a surfactant having a monovalent anion moiety and a monovalent cation moiety has excellent properties in suppressing pattern collapse and bridge defects.

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 2019-519804 Patent Document 2: Japanese Patent Application Laid-Open No. 2021-535619 Summary of the Invention Problem that the invention aims to solve [0005I] The present inventors have considered the following: From the viewpoint of preventing destruction of the global environment and reducing harmful effects on the human body, it is desirable to use chemical products that do not contain fluorine atoms. However, it is not easy to achieve performance that is applicable to processes for manufacturing highly integrated patterns using compounds or compositions that do not contain fluorine atoms, and it is even more difficult to produce compatible compounds or compositions. The inventors have considered that there are still one or more problems that require improvement. These include, for example, avoiding the use of chemicals containing fluorine atoms, reducing defects in fine resist patterns, suppressing the occurrence of bridges in resist patterns, enabling the formation of finer resist patterns, preventing resist pattern collapse in fine resist patterns, suppressing non-uniformity in resist pattern width, reducing residues after removing the aqueous solution used in the manufacture of electronic devices, reducing the number of rinse steps required after using the aqueous solution used in the manufacture of electronic devices, reducing the deposition of solids due to mixing of the aqueous solution used in the manufacture of electronic devices with a developer, lowering the surface tension of the aqueous solution used in the manufacture of electronic devices, providing an aqueous solution used in the manufacture of electronic devices that is less dangerous to handle, providing an aqueous solution used in the manufacture of electronic devices that has excellent storage stability (e.g., long-term storage), and providing an aqueous solution used in the manufacture of electronic devices that has little effect on the resist pattern. The present invention has been made based on the above-mentioned technical background, and provides an aqueous solution used in the manufacture of electronic devices. Means for Solving the Problems [0006I] The aqueous solution for manufacturing electronic devices according to the present invention comprises a compound (A) and a solvent (B). The compound (A) comprises a monovalent anion moiety (Aa) and a monovalent cation moiety, and the anion moiety (Aa) is represented by the formula (Aa-a). [chemical gate (In the formula, X and X" are each independently -S (=0) 2 or -C (=0), Z and Z" are each independently a C-16 hydrocarbon group; One or more H in Z 11 is 〇 H, SH, COOH, CO NH 2S may be substituted with N H2^ or 〇 C H3, One or more Hs in Z 12 are 〇 H, SH, COO H s CO NH 2S may be substituted with NH2 or H3, one or more non-adjacent methylenes in z may be substituted with oxy, one or more non-adjacent methylenes in Z" may be substituted by oxy; Y" is H or OH, n12, m12 and n12 are each independently 0 or 1, and when m12 = 1, 0 = 0, and when m12 = 0, 0 = 1. The solvent (B) comprises water (B-1). [0007I] The method for producing a resist pattern according to the present invention uses the above-described aqueous solution for manufacturing electronic devices.

[0008] The device manufacturing method according to the present invention comprises the resist pattern manufacturing method described above.

[0009] By using the aqueous solution for manufacturing electronic devices according to the present invention, one or more of the following effects can be expected: An aqueous solution for manufacturing electronic devices can be provided using chemicals that do not contain fluorine atoms. It is possible to reduce defects in fine resist patterns. It is possible to suppress the occurrence of bridges in resist patterns. It is possible to form finer resist patterns. It is possible to prevent resist pattern collapse in fine resist patterns. It is possible to suppress non-uniformity in resist pattern width. It is possible to reduce residues after removing the aqueous solution for manufacturing electronic devices. It is possible to reduce the number of rinsing steps after using the aqueous solution for manufacturing electronic devices. It is possible to suppress precipitation of solids due to mixing of the aqueous solution for manufacturing electronic devices with the developer. It is possible to reduce the surface tension of the aqueous solution for manufacturing electronic devices. It is possible to reduce the risk of handling the aqueous solution for manufacturing electronic devices. It is possible to improve the storage stability of the aqueous solution for manufacturing electronic devices. It is possible to reduce the impact of the aqueous solution for manufacturing electronic devices on the resist pattern. Modes for carrying out the invention [0010I] The embodiments of the present invention will be described in detail below.

[0011] Definitions In this specification, unless otherwise specified, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "one" and "the" mean "at least one." Elements of a concept may be expressed by multiple species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the multiple species. "And / or" includes all combinations of the elements as well as any single use thereof. When numerical ranges are indicated using "to" or "-", they include both endpoints and have the same units. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less. Designations such as "Cx-y," "Cx through Cy," and "Cx" refer to the number of carbons in a molecule or substituent. For example, C-6 alkyl refers to 1 to 6 carbons, inclusive. The term "additive" refers to an alkyl chain (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.) having a repeating unit. When a polymer has multiple types of repeating units, these repeating units are copolymerized. This copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When a polymer or resin is represented by a structural formula, the n or m in parentheses indicates the number of repeating units. The unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to the compound itself that has the function (for example, in the case of a base generator, it is the compound itself that generates a base). The compound may be dissolved or dispersed in a solvent and added to the aqueous solution for manufacturing electronic devices. In one aspect of the present invention, such a solvent is preferably contained in the aqueous solution for manufacturing electronic devices according to the present invention as solvent (B) or another component. <Aqueous Solution for Electronic Device Manufacturing> The aqueous solution for electronic device manufacturing according to the present invention comprises a compound (A) (hereinafter, sometimes referred to as component (A)). The same applies to other components.) and a solvent (B). The aqueous solution for electronic device manufacturing is used in the process of manufacturing an electronic device. It may be used in the process of manufacturing an electronic device, and may be removed or disappear during the process. Examples of the aqueous solution for electronic device manufacturing include display devices, LEDs, and semiconductor devices. The aqueous solution for electronic device manufacturing is, for example, an aqueous solution for semiconductor substrate manufacturing, preferably an aqueous solution for semiconductor substrate manufacturing; more preferably a cleaning solution for semiconductor substrate manufacturing process; even more preferably a lithography cleaning solution; and even more preferably a resist pattern cleaning solution. The aqueous solution for electronic device manufacturing, which is an aqueous solution for semiconductor substrate manufacturing, can also be referred to as an aqueous solution for semiconductor substrate manufacturing consisting solely of the aqueous solution for electronic device manufacturing of the present invention. In another aspect of the present invention, the aqueous solution for manufacturing electronic devices can be a rinse composition used to rinse an exposed and developed resist pattern.

[0013] Compound (A) The compound (A) used in the present invention comprises a monovalent anion moiety (Aa) and a monovalent cation moiety. The anion moiety (Aa) is represented by the formula (Aa-a): [Case 2] X and X are each independently -S (=0) 2 or -c (=0). 2i and 2" are each independently a C-hydrocarbon group, preferably a C-14 hydrocarbon group, more preferably a C-12 hydrocarbon group. One or more H in Z 11 is 〇 H, SH, COOH, CO NH 2S It may be substituted with NH2 or OC H3. Preferably it is not substituted. One or more Hs in Z 12 are 〇 H, SH, COO H s CO NH 2S It may be substituted with NH2 or oc H3, but is preferably not substituted. One or more non-adjacent methylenes in Z may be substituted with oxy, but preferably are not substituted. One or more non-adjacent methylenes in Z" may be substituted with oxy. Preferably, they are not substituted. Y" is H or OH. n 1 2 S m12 and m12 are each independently 0 or 1. When m12 = 1, 012 = 0, and when m12 = 0, 012 = 1. [0014I] The anion portion (Aa) of compound (A) contains a linking group X1 and optionally X2, each of which is independently -S(=0)2- or -C(=0)-. Commonly used rinse compositions for rinsing exposed and developed resist patterns often contain a fluorine-containing compound to achieve a sufficient rinsing effect. In contrast, the aqueous solution for manufacturing electronic devices according to the present disclosure uses a compound (A) that does not contain fluorine and contains -S(=0)2- and / or -C(=0)-, thereby achieving a sufficient rinsing effect. By using a fluorine-free compound (A), adverse effects on the human body and the environment can be suppressed during the electronic device manufacturing process. In an embodiment of the present invention, X is -S(=0)2- or -C(=0)- and X is -C(=0)-. X 1 It is preferable that \ X" or both are -S (=0) 2-, as this will produce a higher effect.

[0015] The hydrocarbon groups Zi and Z" preferably have different numbers of carbon atoms. Specifically, Zi preferably has more carbon atoms than Z". More specifically, Zi preferably has 4 or more carbon atoms, more preferably 5 or more carbon atoms, and Zi2 preferably has 1 or more and 4 or less carbon atoms, more preferably 1 or more and 3 or less carbon atoms.

[0016] It is preferred that Z i is a straight chain alkyl, a branched alkyl, a cyclic alkyl, or a combination of any of these, and Z" includes a straight chain alkylene, a branched alkylene, a cyclic alkylene, or a combination of any of these. Here, alkyl means a group obtained by removing one arbitrary hydrogen from a saturated hydrocarbon, and straight chain alkyl includes methyl, ethyl, n-propyl, n-butyl, etc., branched alkyl includes i-propyl, i-butyl, neo-butyl, etc., and cyclic alkyl includes cyclobutyl, cyclopentyl, cyclohexyl, etc. Alkylene means a group obtained by removing two arbitrary hydrogens from a saturated hydrocarbon, that is, straight chain alkylene, branched alkylene, and cyclic alkylene are groups obtained by further removing one hydrogen from a straight chain alkyl, branched alkyl, and cyclic alkylene, respectively. 2 i or 2" may be one or more aromatic hydrocarbons. It is also preferred that the alkyl group contains a substituted or unsubstituted alkyl group or one or more unsaturated bonds, specifically one or more -CH=CH- or one or more -c=c-. In a preferred embodiment, the combination of X, X', n12, m12, Y' and Y' in the anionic portion (Aa) of compound (A) is X 】 1 is - S (=0) 2 -, ・" is - $ (=0) 2 -, n 1 2 = 1, m 1 2 = 0, 〇 1 2 = 1 s Y" = OH; X 】 1 is - S (=0) 2 -, ・12 is -〇 (=〇) -, n 1 2 = 1, m 1 2 = 0, 〇 1 2 = 1 s Y 12 = OH : X 】 1 is C (= 〇) , ・" is $ (= 0) 2, n 1 2 = 1, m 1 2 = 0, 〇 1 2 = 1 s Y 12 = OH : X 】 1 is C (= 〇) -, ・" is. (= 〇) -, n 1 2 = 1, m 1 2 = 0, ○ 1 2 = 1 s Y 12 = 0 H ; X 】 1 is - S (=0) 2 -, ・" is -$ (=0) 2 -, n 1 2 = 1, m 1 2 = 1, 〇 1 2 = 0; X 】 1 is - S (=0) 2 -, ・" is -. (=〇) -, n 1 2 = 1, m 1 2 = 1, 〇 1 2 = 0; X 】 1 is - C (= 〇) -, ・" is -$ (= 0) 2-, n 1 2 = 1, m 1 2= 1, 〇 1 2 = 0; X 】 1 is C (=〇) -, ・" is. (=〇) -, n 1 2 = 1, m 1 2 = 1, 〇 1 2 = 0 ; X iger S (=〇) 2-, n 1 2 = 0, m 1 2 = 0, 〇 1 2 = 1 s Y 12 =H : and X Iga C (=〇) -, n 1 2 = 0 s m 1 2 = 0, 〇 1 2 = 1 s Y 12 = H is an example.

[0018] For example, the following compound A7 has the formula (A a — a) where X is a group S (= 〇) 2ー, n 1 2 = 0, m 1 2 = 0, 〇 1 2 = 1 s Y 12 = H s Z is n-octyl and the monovalent cation moiety is H+. [C3]

[0019] The following compound A16 is a compound represented by the formula (Aa-a), wherein X is -S (=0)2-, X is -c (=0), n 12 = 1 s m 1 2=〇, 〇"= 1, y 1 2 = 0 H sZ 11 is n-hexyl and the monovalent cation moiety is H+. [C4]

[0020] Compound (A) has a monovalent cation moiety combined with the above-described anion moiety (Aa). This cation moiety is preferably H+ or the monovalent cation K(Ac). The monovalent cation moiety is more preferably H+. In one preferred embodiment of the present invention, the monovalent cation moiety is represented by the formula (Ac-a). + NH P R%_ P The formula (A c — a) where: Each Ra is independently a C-3 alkyl. One or more H of the C-3 alkyl may be substituted with OH. Preferably, it is not substituted. p is O, 1, 2, 3, or 4. Preferably, it is O, 1, or 4. More preferably, it is O or 4. Still more preferably, it is 4. The cation moiety (Ac) represented by formula (Ac-a) is a so-called ammonium ion. In the present invention, a compound (A) in an aqueous solution for manufacturing electronic devices is prepared by adding water (B-1). This includes an embodiment in which compound (A) is ion-separated (more preferably in an equilibrium state). In this disclosure, specific embodiments of compound (A) are based on the state before it is added to solvent (B). Here, specific embodiments include the content. In this disclosure, the same applies to other components unless otherwise specified.

[0021] Compound (A) is preferably a compound having a relatively small molecular weight, in which the anion of formula (Aa-a) and the cation of formula (Ac-a) are bonded. The molecular weight of compound (A) is preferably 100 to 450, more preferably 100 to 400, and even more preferably 100 to 380.

[0022] Compound (A) preferably acts as a surfactant that reduces the surface tension of an aqueous solution used in the manufacture of electronic devices. Specifically, the surface tension of an aqueous solution containing compound (A) at a concentration of 500 ppm is preferably 0 to 30% lower than the surface tension of water, more preferably 0.5 to 30%, and even more preferably 1 to 30% lower. The surface tension can be measured using a capillary rise surface tensiometer.

[0023] Specific examples of the compound (A) used in the present invention include the following A1 to A21. [C5]

[0024] Compound (A) is A 1 A 8 S Preferably, A1 is 2 and A2 is 1. Component (A) may be one type or a mixture of two or more types.

[0025] One of the effects of the aqueous solution for electronic device manufacturing according to the present invention is that it Without being bound by theory, it is possible to suppress defects after development of the film. The presence of -S(=0)2- and / or -C(=0)- in the molecular structure of component A ensures dispersibility in aqueous solutions, while other structures in the molecular structure are thought to be able to lower surface tension. Component (A) has a high affinity for water in aqueous solutions used in the manufacture of electronic devices, making it easy to exist in water. This is thought to reduce the risk of defects occurring in patterns, not just in photosensitive resin patterns. The content of compound (A) can be appropriately adjusted depending on the purpose, but is preferably 0.01 to 10 mass%, more preferably 0.01 to 5 mass%, and even more preferably 0.03 to 1 mass%, based on the total mass of the aqueous solution used in manufacturing electronic devices.

[0027] Solvent (B) The aqueous solution for manufacturing electronic devices according to the present invention comprises a solvent (B). The solvent (B) comprises water (B-1). The water is preferably deionized water. Considering that the solvent (B) is used in the manufacturing process of electronic devices, and more preferably in the manufacturing process of semiconductors, it is preferable that the solvent (B) has a low impurity content. Solvent The impurity concentration of (B) is preferably 1 ppm or less, more preferably 100 ppb or less, and even more preferably 10 ppb or less. The content of solvent (B) is preferably 80-99.999 mass%, more preferably 85-99.99 mass%, based on the total mass of the aqueous solution for manufacturing electronic devices. The content of water (B-1) is preferably 80-99.999 mass%, more preferably 85-99.99 mass%, based on the total mass of the aqueous solution for manufacturing electronic devices. The content of water (B-1) is preferably 90-100% by mass, more preferably 98-100% by mass, even more preferably 99-100% by mass, and even more preferably 99.9-100% by mass, based on the total mass of the solvent (B). In a preferred embodiment of the present invention, the solvent (B) is substantially composed of only water (B-1). However, a preferred embodiment of the present invention is one in which the additive is dissolved and / or dispersed in a solvent other than water (e.g., a surfactant) and contained in the aqueous solution for manufacturing electronic devices of the present invention. In a more preferred embodiment of the present invention, the content of water (B-1) in the solvent (B) is 100 mass %. [0028I] Specific examples of the solvent (B) excluding 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, arbutyrolactone, ethyl lactate, and mixtures thereof. These solvents are preferred in terms of the storage stability of the solution. Two or more of these solvents can also be used as a mixture. [0029I Diol Compound (C) The aqueous solution for manufacturing electronic devices according to the present invention may further contain a diol compound. As the diol compound, a diol compound (C) represented by formula (C-a) is preferred. [6] During the ceremony, R C1 , R C2 , R C3 , and R C4 are each independently hydrogen, fluorine, or C1-5 alkyl. Preferably, they are each independently hydrogen, methyl, ethyl, t-butyl, or isopropyl. More preferably, they are each independently hydrogen, methyl, ethyl, t-butyl, or isopropyl. independently hydrogen, methyl, or ethyl. L" and LC2 are each independently C-C alkylene, C-C cyclohexane, and arylene having a carbon number of 20. These groups may be substituted with fluorine, alkyl, or hydroxy. Preferably, they are unsubstituted. Here, alkenylene refers to a divalent hydrocarbon group having one or more double bonds, and alkynylene refers to a divalent hydrocarbon group having one or more triple bonds. Preferably, !-" and !_C2 are each independently C2-5 alkylene, C2-4 alkenylene, C2-4 alkynylene, or C6 arylene. More preferably, they are each independently C2-4 alkylene, C2 alkenylene, C2 alkynylene, or phenylene. Even more preferably, they are each independently C2 alkenylene or C2 alkynylene. Most preferably, they are each independently C2 alkynylene. nC is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0030] Specific examples of the compound (C) used in the present invention include the following C1 to C5. [C7] Further, other specific examples of the diol compound (C) used in the present invention include 3-hexyne-2,5-diol, 1,4-butyne-diol, 2,4-hexadiyne-1,6-diol, 1,4-butane-diol, 2,2, 3,3-Tetrafluoro-1,4-butanediol, 2,2,3,3,4, Examples of the hydroxybenzoates include 4,5,5-octafluoro-1,6-hexanediol, cis-1,4-dihydroxy-2-butene, 1,4-benzenedimethanol, 4,7-dihydroxy-2,4,7,9-tetramethyl-5-decyne, and combinations thereof.

[0031] The content of diol compound (C), based on the total mass of the aqueous solution for manufacturing electronic devices, is preferably 0.001 to 10 mass%, more preferably 0.005 to 5 mass%, even more preferably 0.01 to 1 mass%, and even more preferably 0.01 to 0.1 mass%. Without being bound by theory, it is believed that the inclusion of component (C) makes it possible to suppress aggregation of component (A) during the manufacturing process for electronic devices (e.g., a resist pattern cleaning process). [0032I] The aqueous solution for manufacturing electronic devices according to the present invention contains the above-described components (A) and (B), and, if necessary, component (C), and may contain further compounds, if necessary.

[0033] Resin (D) The aqueous solution for manufacturing electronic devices according to the present invention can contain resin (D). Resin (D) refers to an organic polymer with a relatively large molecular weight, and in the present invention refers to a compound with a molecular weight of 1,000 or more. Examples of resin (D) include novolak derivatives, phenol derivatives, polystyrene derivatives, polyacrylic acid derivatives, polymethacrylic acid derivatives, polyacrylamide derivatives, polyethylene oxide derivatives, polyvinylamide derivatives, polyamine derivatives, polymaleimide derivatives, polycarbonate derivatives, polyvinylpyrrolidone derivatives, polyvinyl alcohol derivatives, and copolymers of combinations thereof. Preferred are polyacrylic acid derivatives, polymethacrylic acid derivatives, and polyvinyl The resin (D) is selected from the group consisting of alcohol derivatives. The weight average molecular weight Mw of the resin (D) is preferably 1,500 to 300,000, more preferably 2,000 to 250,000, and even more preferably 2,500 to 200,000. Here, the weight average molecular weight is the weight average molecular weight converted to polymethyl methacrylate and can be measured by gel permeation chromatography using polymethyl methacrylate as the standard. This resin (D) is used to adjust the viscosity of an aqueous solution used in the manufacture of electronic devices or to harden a coating film of an aqueous solution used in the manufacture of electronic devices to form a film. Resin (D) also includes photosensitive resins generally contained in photosensitive resin compositions. The content of resin (D) is preferably 0 to 10 mass% based on the total mass of the aqueous solution for manufacturing electronic devices, and more preferably 0 to 3 mass%. A particularly preferred embodiment of the present invention is one in which no resin (D) is contained (0 mass%).

[0034] Additive (E) The aqueous solution for manufacturing electronic devices according to the present invention may further contain an additive (E). The additive (E) may further contain other nitrogen-containing compounds, other surfactants, other acids, other bases, bactericides, antibacterial agents, preservatives, or antifungal agents. The other nitrogen-containing compounds may contain at least one nitrogen atom. The additive (E) is a compound different from the above-described (A), (B), (C), and (D). By including the other nitrogen-containing compounds, the aqueous solution for manufacturing electronic devices according to the present invention can further suppress pattern collapse. Without being bound by theory, it is believed that including the other nitrogen-containing compounds can reduce the effects of other components on the resist pattern. [0035I] Other nitrogen-containing compounds include, for example: (i) ammonia, (ii) Primary aliphatic amines having 1 to 16 carbon atoms and their derivatives (e.g., methylamine, ethylamine, isopropylamine, n-butylamine, te rt-butylamine, cyclohexylamine, ethylenediamine, tetraethylenediamine, etc.), (iii) secondary aliphatic amines having 2 to 32 carbon atoms and their derivatives (e.g., dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, N,N-dimethylmethylenediamine, etc.), (iv) Tertiary aliphatic amines having 3 to 48 carbon atoms and their derivatives (e.g., trimethylamine, triethylamine, tripropylamine, dimethylethylamine, tricyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N',N'-pentamethyldethylenetriamine, tris [2-(dimethylamino)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, etc.), (v) Aromatic amines having 6 to 30 carbon atoms and their derivatives (e.g., aniline, benzylamine, naphthylamine, N-methylaniline, 2-methylaniline, 4-aminobenzoic acid, phenylalanine, etc.), and (vi) Heterocyclic amines having 5 to 30 carbon atoms and derivatives thereof (for example, pyrrole, oxazole, thiazole, imidazole, 4-methylimidazole, pyridine, methylpyridine, butylpyridine, etc.).

[0036] The other nitrogen-containing compounds are preferably selected from the group consisting of (i), (ii), and (iv), and more preferably selected from the group consisting of ammonia, n-butylamine, ethylenediamine, triethylamine, tripropylamine, and N,N,N',N'-tetraethylethylenediamine.

[0037] The molecular weight of the one or more other nitrogen-containing compounds is preferably 17 to 500, more preferably 17 to 150, and even more preferably 60 to 143.

[0038] The content of other nitrogen-containing compounds, if any, based on the total mass of the aqueous solution for manufacturing electronic devices is preferably 0.0001 to 1 mass%, more preferably 0.0005 to 0.5 mass%, and even more preferably 0.0005 to 0.05 mass%, 1% by mass. The aqueous solution for manufacturing electronic devices according to the present invention may further contain other surfactants as additives. The other surfactants are useful for improving the coating properties and solubility. Here, the other surfactants are different from the above-described component (A) or component (C). Other surfactants include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ether compounds such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymer compounds; sorbitan fatty acid ester compounds such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate. In addition, the product names F-TOP EF 301, EF 303, EF 352 (manufactured by Tokem Products Co., Ltd.), the product name MAG AF AC EF 1 7 1 s F1 73 S R-〇 8 SR-30, R-20 1 1 (manufactured by Dai Nippon Ink Co., Ltd.), Fluorard FC 4 3 0, FC4 3 1 (manufactured by Sumitomo 3M Limited), product name Asahi Guard AG 7 1 〇 s Examples of such surfactants include fluorine-based surfactants such as Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.) and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). If other surfactants are included, the content thereof is preferably 0.001 to 5 mass%, more preferably 0.005 to 1 mass%, and even more preferably 0.01 to 0.1 mass%, based on the total mass of the aqueous solution for manufacturing electronic devices. [0040I] Other acids or other bases can be used to adjust the pH value of the aqueous solution used in manufacturing electronic devices or to improve the solubility of additive components. Examples of other acids include aromatic carboxylic acids. The other acids are different from the above-mentioned components (A), (B), and (C). Examples of other bases include quaternary ammonium compounds. The other bases are different from the above-mentioned component (A) and other nitrogen-containing compounds.

[0041] Additives (E) may optionally contain germicides, antibacterial agents, preservatives or fungicides. These chemicals are used to prevent the growth of bacteria and fungi over time. Examples of these chemicals are alcohols such as phenoxyethanol and isothiazolinones. Bestcide (Nippon Soda Co.) is a more effective antibacterial and fungicide.

[0042] When the additive (E) is contained, the content thereof is preferably 0.0001 to 10 mass%, more preferably 0.0001 to 0.1 mass%, and even more preferably 0.0002 to 0.001 mass%, based on the total mass of the aqueous solution for manufacturing electronic devices. A preferred embodiment of the present invention is one in which the additive (E) is not contained.

[0043] After dissolving its components, the aqueous electronics manufacturing solution of the present invention can be filtered to remove impurities and / or insoluble matter.

[0044] <Method for Producing a Resist Pattern> The present invention also provides a method for producing a resist pattern using the above-mentioned aqueous solution for producing electronic devices. The photosensitive resin composition (resist composition) used in this method may be either a positive-type or a negative-type, with a positive-type being more preferred. A typical method for producing a resist pattern using the aqueous solution for producing electronic devices according to the present invention comprises the following steps: (1) applying a photosensitive resin composition to a substrate with or without one or more intermediate layers to form a photosensitive resin layer; (2) exposing the photosensitive resin layer to radiation; (3) developing the exposed photosensitive resin layer; (4) Wash the developed layer with the above-mentioned aqueous electronics manufacturing solution. [0045I] Details are explained below. First, a photosensitive resin composition is applied (e.g., laminated) onto a substrate such as a silicon substrate or a glass substrate, which has been pretreated as necessary, to form a photosensitive resin layer. While known techniques can be used for lamination, a coating method such as spin coating is preferred. The photosensitive resin composition can be laminated directly onto the substrate, or via one or more intermediate layers (e.g., BARC). An anti-reflective film (e.g., TARC) may also be laminated above the photosensitive resin layer (on the opposite side from the substrate). Regarding layers other than the photosensitive resin layer, as described below, by forming an anti-reflective film above or below the photosensitive resin layer, the cross-sectional shape and exposure margin can be improved. Representative examples of positive or negative photosensitive resin compositions that can be used in the resist pattern production method of the present invention include those containing a quinone diazide-based photosensitizer and an alkali-soluble resin, and chemically amplified photosensitive resin compositions. From the viewpoint of forming a high-resolution, fine resist pattern, chemically amplified photosensitive resin compositions are preferred, such as chemically amplified PHS-acrylate hybrid EUV resist compositions. These are more preferably positive photosensitive resin compositions. Without being bound by theory, the inventors have hypothesized as follows: The resist composition to be exposed to EUV is intended to form a finer resist pattern, but there is a problem in that defects are more likely to occur in the formed resist pattern due to the properties of the resist composition (e.g., high hydrophobicity). It is believed that by using the aqueous solution of the present invention, it is possible to clean a fine resist pattern while preventing such defects. [0047I] Examples of the quinone diazide photosensitizer used in the positive photosensitive resin composition containing the quinone diazide photosensitizer and an alkali-soluble resin include 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone Examples of the alkali-soluble resins include diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, and esters or amides of these sulfonic acids. Examples of the alkali-soluble resins include copolymers of polyvinylphenol, polyvinyl alcohol, acrylic acid, or methacrylic acid. [0048I] Examples of chemically amplified photosensitive resin compositions include positive-type chemically amplified photosensitive resin compositions containing a compound (photoacid generator) that generates acid upon irradiation with radiation and a resin whose polarity increases due to the action of the acid generated from the photoacid generator, and whose solubility in a developer changes between exposed and unexposed areas; and negative-type chemically amplified photosensitive resin compositions containing an alkali-soluble resin, a photoacid generator, and a crosslinking agent, in which crosslinking of the resin occurs due to the action of the crosslinking agent under the action of acid, and whose solubility in a developer changes between exposed and unexposed areas. [0049I] Resins whose polarity increases under the action of an acid and whose solubility in a developer changes between exposed and unexposed areas include resins having groups in the main chain or side chain, or both the main chain and the side chain, that decompose under the action of an acid to produce alkali-soluble groups. Typical examples include polymers in which an acetal group or a ketal group has been introduced as a protecting group into a hydroxystyrene polymer (PHS) (e.g., JP-A-2-19847), and similar polymers in which a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group has been introduced as an acid-decomposable group (e.g., JP-A-2-209977). [0050I] The photoacid generator may be any compound that generates an acid upon irradiation with radiation, and examples thereof include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts, organic halogen compounds, organometallic / organic halides, photoacid generators having a -nitrobenzyl type protecting group, compounds that generate sulfonic acid upon photolysis, such as iminosulfonates, disulfone compounds, diazoketosulfone compounds, and diazodisulfone compounds. Furthermore, it is also possible to incorporate these photoacid generating groups or compounds into the main chain of a polymer. Compounds introduced into the chain or side chain can also be used.

[0051] The chemically amplified photosensitive resin composition may further contain, as necessary, an acid-decomposable dissolution-inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, a compound that promotes solubility in a developer, and the like.

[0052] The photosensitive resin composition is applied to a substrate using an appropriate coating device such as a spinner or coater and by an appropriate coating method, and then heated to remove the solvent in the photosensitive resin composition, thereby forming a photosensitive resin layer. The heating temperature is preferably 70 to 150° C., more preferably 90 to 150° C. The heating time is preferably 10 to 600 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[0053] The resist pattern manufacturing method of the present invention also allows the presence of films or layers other than the photosensitive resin layer. An intermediate layer may be interposed between the substrate and the photosensitive resin layer without direct contact. The intermediate layer is a layer formed between the substrate and the photosensitive resin layer and is also called an underlayer film. Examples of underlayer films include substrate modification films, planarizing films, bottom antireflective coatings (BARCs), inorganic hard mask intermediate layers (silicon oxide films, silicon nitride films, and silicon oxide nitriding films), and adhesion films. An example of a planarizing film is SOC. For details on the formation of inorganic hard mask intermediate layers, see Japanese Patent No. 5336306. The intermediate layer may consist of one layer or multiple layers. An upper layer film may also be formed on the photosensitive resin layer. An example of an upper layer film is a top antireflective coating (TAC).

[0054] In the resist pattern manufacturing process of the present invention, the layer structure can be formed by a known method according to the process conditions, and examples of the layer structure include the following: substrate / photosensitive resin layer substrate / underlayer film / photosensitive resin layer substrate / planarizing film / photosensitive resin layer substrate / planarizing film / photosensitive resin layer / upper layer film substrate / planarizing film / BARC / photosensitive resin layer Substrate / planarizing film / inorganic hard mask intermediate layer / photosensitive resin layer Substrate / planarizing film / adhesion film / photosensitive resin layer Substrate / substrate modification layer / planarizing film / photosensitive resin layer Substrate / substrate modification layer / planarizing film / adhesion film / photosensitive resin layer These layers can be cured by heating and / or exposure after application, or can be formed using known techniques such as CVD. These layers can be removed by known techniques (etching, etc.), and each upper layer can be used as a mask for patterning. A preferred embodiment of the present invention is to apply the photosensitive resin composition directly onto the substrate without an intermediate layer. In another embodiment of the present invention, a TARC is not formed on the photosensitive resin layer. In another embodiment of the present invention, a thickened resist pattern may be formed by forming a thickened layer on the photosensitive resin layer, as in WO 2022 / 129015. [0055I] The photosensitive resin layer is exposed through a predetermined mask. When other layers are also included (such as an upper layer), they may all be exposed. The wavelength of the radiation (light) used for exposure is not particularly limited, but exposure with light having a wavelength of 13.5 to 248 nm is preferred. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet (EUV, wavelength 13.5 nm) can be used, with EUV being more preferred. These wavelengths have an allowable range of ±5%, preferably ±1%. After exposure, post-exposure baking (PEB) can be performed if necessary. The PEB temperature is preferably 70 to 150°C, more preferably 80 to 120°C, and the heating time is preferably 0.3 to 5 minutes, more preferably 0.5 to 2 minutes. [0056I] Next, development is carried out using a developer. For development in the resist pattern production method of the present invention, a 2.38 mass % (±1% is acceptable) aqueous solution of tetramethylammonium hydroxide (TMAH) is preferably used. Furthermore, a surfactant or the like can be added to these developers. The temperature of the developer is preferably The development temperature is preferably 5 to 50°C, more preferably 25 to 40°C, and the development time is preferably 10 to 300 seconds, more preferably 20 to 60 seconds. Known development methods such as puddle development can be used. As mentioned above, the resist pattern of the present invention includes not only resist films that have been exposed and developed, but also those in which the walls have been thickened by covering them with other layers or films. The resist pattern (developed photosensitive resin layer) formed through the above steps is in an unwashed state. This resist pattern can be washed with the aqueous solution for manufacturing electronic devices according to the present invention. The time for which the aqueous solution for manufacturing electronic devices is brought into contact with the resist pattern, i.e., the treatment time, is preferably 1 second or more. The treatment temperature may also be arbitrary. The method for bringing the aqueous solution for manufacturing electronic devices into contact with the resist is also arbitrary, and can be carried out, for example, by immersing the resist substrate in the aqueous solution for manufacturing electronic devices, or by dropping the aqueous solution onto the surface of a rotating resist substrate. In the resist pattern manufacturing method according to the present invention, the developed resist pattern can be washed with another cleaning liquid before and / or after the cleaning process with the aqueous solution for manufacturing electronic devices. The other cleaning liquid is preferably water, more preferably pure water (DW, deionized water, etc.). Cleaning before the process is useful for cleaning the developer adhering to the resist pattern. Cleaning after the process is useful for cleaning the aqueous solution for manufacturing electronic devices. A preferred embodiment of the manufacturing method according to the present invention is a method in which pure water is poured into the developed resist pattern to replace the developer while cleaning the pattern, and then, while maintaining the pattern immersed in pure water, the aqueous solution for manufacturing electronic devices is poured in to replace the pure water while cleaning the pattern. Cleaning with the aqueous solution for manufacturing electronic devices may be performed by a known method. For example, it can be performed by immersing the resist substrate in the aqueous solution for manufacturing electronic devices, or by dropping the aqueous solution for manufacturing electronic devices onto the surface of a rotating resist substrate. These methods may be used in combination as appropriate. One of the conditions that makes pattern collapse likely is the location where the spacing between the walls of the resist pattern is narrowest. This condition is severe where the walls of the resist pattern are parallel. In this specification, the minimum space size is defined as the distance where this spacing is smallest on one circuit unit. Preferably, one circuit unit will become one semiconductor in a subsequent process. Also, it is preferable that one semiconductor includes one circuit unit in the horizontal direction and multiple circuit units in the vertical direction. Of course, unlike the test sample, if the frequency of narrow wall-to-wall spacing is low, the frequency of defects will decrease, and the frequency of defective products will also decrease. In the present invention, the minimum space size of the resist pattern in one circuit unit is preferably 5 to 30 nm, more preferably 10 to 20 nm, and even more preferably 10 to 17 nm. <Device Manufacturing Method> The device manufacturing method of the present invention comprises a method for manufacturing a resist pattern using an aqueous solution for manufacturing electronic devices. Preferably, the device manufacturing method of the present invention comprises etching a substrate using the resist pattern manufactured by the above method as a mask, or ion doping the substrate or an underlying film using the resist pattern as a mask. After processing, the resist film is peeled off as necessary. Preferably, the device is a semiconductor. In the manufacturing method of the present invention, the intermediate layer and / or the substrate can be processed by etching using the resist pattern as a mask. For etching, known techniques such as dry etching and wet etching can be used, with dry etching being more preferred. For example, the intermediate layer can be etched using the resist pattern as an etching mask, and the substrate can be etched using the resulting intermediate layer pattern as an etching mask. Alternatively, the resist pattern can be used as an etching mask to etch the layer below the resist layer (for example, the intermediate layer), while simultaneously etching the substrate. The processed substrate may be, for example, a patterned substrate. The pattern can be used to form wiring on the substrate. These layers are preferably made of 0.2, cF 4 S CHF 3 S It can be removed by dry etching with C12 or BCI3, preferably O2 or CF4. In the manufacturing method of the present invention, ion doping can be performed on a substrate or an underlayer film using a resist pattern as a mask. Ion doping is performed on a substrate or an underlayer film using the formed resist pattern as a mask, or a lower layer below the resist pattern is processed using the formed resist pattern as a mask to form an underlayer pattern, and ion doping is performed on a substrate using the underlayer pattern as a mask. Ion doping can be performed by a known method using a known ion doping device. In general, in the manufacture of semiconductor devices, liquid crystal display devices, etc., an impurity diffusion layer is formed on the surface of a substrate. The formation of an impurity diffusion layer is usually performed in two stages: introduction and diffusion of impurities. One introduction method is ion doping, in which impurities such as phosphorus or boron are ionized in a vacuum, accelerated by a high electric field, and implanted into the surface of a support. The ion acceleration energy during ion doping is generally 10 to 200 keV. The ion source (impurity element) may be ions of boron, phosphorus, arsenic, argon, etc. The thin film on the substrate may be a thin film of silicon, silicon dioxide, silicon nitride, aluminum, etc. In a preferred embodiment, the method for manufacturing a device according to the present invention further comprises forming wiring on the processed substrate.

[0062] [Examples] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0063] Synthesis Example 1 (Synthesis of Compound (A1)) In a 1000 ml single-neck flask, sulfonamide and lithium hydroxide (11.2 g, 2 ml), Tokyo Chemical Industry Co., Ltd. (hereafter referred to as TCI), and distilled water (500 ml, 〇・2 M) and stir using a magnetic stirrer. 0 C The reaction mixture is cooled to 0°C and 12N-HCl is added to the reaction mixture, followed by filtration. The reaction mixture is cooled to 0°C and 12N-HCl is added to the reaction mixture, followed by filtration. The reaction mixture is cooled to 0°C and 12N-HCl is added to the reaction mixture, followed by filtration. The reaction mixture is cooled to 0°C and 12N-HCl is added to the reaction mixture, followed by filtration. The reaction mixture is then filtered and dried at 60°C for 3 hours. The white solid obtained by synthesis of A1 was 14.5 g, with a yield of 51%. [0064I Synthesis Examples 2 to 4 (Synthesis of Compounds (A2) to (A4), (A12), and (A21)) The target compounds were synthesized by the same method as in the synthesis of A1, but varying the carbon numbers of the sulfonamide and sulfonyl chloride. A21 was synthesized by the same method as in the synthesis of A1, using hexane-1-sulfonamide and benzenesulfonyl chloride. The yields were A2: 16.3 g and 57%, A3: 15.7 g and 61%, A4: 9.6 g and 42%, A12: 16.8 g and 45%, and A21: 18.6 g and 52%, respectively. Synthesis Example 8 (Synthesis of Compound (A8)) In a 1000 ml flask, sulfonamide, dimethylaminopyridine (1.2 g, 0.01 ml, Wako Pure Chemical Industries), and triethylamine (22. To the reaction mixture, add 250 ml of 2 mol / L HCl (2 mol / L, 0.22 mO, TCI) and dichloromethane (500 ml, 10.2 M). In the synthesis of A8, butane-1-sulfonamide (13.7 g, 0.1 mO, Enamine) is used as the sulfonamide. The mixture is cooled to 0°C while stirring using a magnetic stirrer. After adding hexanoyl chloride (14.9 g, 0.11 mol, TCI) as the alkylcarboxylic acid chloride dropwise, the mixture is slowly warmed to room temperature and stirred for 16 hours. 250 ml of 2 mol / L HCl is then added to the reaction mixture, and the organic layer is separated. This process is repeated three times. Sodium sulfate is added to the organic layer, and the mixture is left to stand for 30 minutes. After stirring, the solid was removed by suction filtration, and the organic layer solvent was evaporated under reduced pressure using an evaporator. 100 mL of heptane was added to the resulting reaction mixture to precipitate a white solid. This white solid was collected by suction filtering and dried at 50°C for 3 hours. The amount of white solid obtained in the synthesis of A8 was 14.6 g, a yield of 62%. Synthesis Example 5 (Synthesis of Compound (A5)) The target compound was synthesized in the same manner as in Synthesis Example 8, except that the carbon numbers of the sulfonamide and alkylcarboxylic acid chloride were varied. The yield of A5 was 12.2 g, or 63%.

[0067] Synthesis Example 6 (Synthesis of Compound (A6)) The target compound was synthesized by the same method as in Synthesis Example 8, except that the sulfonamide was replaced with an alkylamide and the number of carbon atoms was varied. The yield of A6 was 7.5 g, a 48% yield.

[0068] <Examples of preparing aqueous solutions for electronics manufacturing> Add the respective amounts of the components listed in Table 1 to deionized water. Stir at room temperature for 5 minutes. Visually check that each component has dissolved. Filter the resulting solution (pore size = 10 nm) to obtain the aqueous solutions for electronics manufacturing for each example. [Table 1] Table 1 In Table 1, [8] RA2: Evaluation (1): Chemical Mixing Test The aqueous solutions for manufacturing electronic devices of Examples E1-E10 and Comparative Examples R1-R2 were mixed with a developer (2.38% by mass TMAH aqueous solution) at mass ratios of 1:9, 5:5, and 9:1, respectively, and the mixtures were allowed to stand for 3 days. The presence or absence of precipitates in the mixtures was confirmed using a turbidity meter TR-55 (Kasahara Chemical Industries), and the results were evaluated according to the following criteria. The results are shown in Table 2. Evaluation rank A indicates that no precipitates were present. A: The turbidity is less than 1 degree. B: Turbidity is 1 degree or more.

[0070] [Table 2] Table 2: Chemical Mixing Ball

[0071] <Evaluation 2: Surface tension> For the aqueous solutions for manufacturing electronic devices of Examples E1-E1 and Comparative Examples R1-R2, The surface tension of each aqueous solution used in the manufacture of electronic devices was measured using a capillary rise type surface tensiometer D G-1 (Surfgauge INSTRUMENTS (Hymen Sokki Seisakusho)). The results are shown in Table 3.

[0072] [Table 3] Table 3: Surface tension Evaluation 3: Defect performance evaluation (1) The silicon substrate was etched with hexamethyldisilazane (HMDS) for 90 seconds. 0 C sThe substrate is then processed for 30 seconds. A chemically amplified PHS-acrylate hybrid resist is then spin-coated on top of the substrate and soft-baked at 110°C for 60 seconds to form a resist film with a thickness of 35 nm. The resulting substrate is then exposed to an EUV exposure system (ASML, NXE: 3 The wafer was exposed to light through a mask with a line:space ratio of 1:1 (400) and a size of 18 nm, followed by PEB at 110°C for 60 seconds. 2. Puddle development was performed using a 38% TMA H2O solution for 30 seconds. While the developer was puddled on the wafer, deionized water was started and the developer was replaced with deionized water while rotating. The process was stopped while the wafer was still puddling with deionized water. The wafer was rinsed at low speed for 30 seconds while dripping an electronics manufacturing solution, and the deionized water was replaced with the electronics manufacturing solution. The wafer was then spun at high speed and dried. The number of foreign particles present in the pattern obtained using the above method was counted using a defect inspection system, UV isi 0 n 4 (Applied Materials), and this was taken as the number of defects. Evaluation was performed using the number of foreign particles in Comparative Example R3 as a comparison, based on the following criteria. The shape of the foreign matter was evaluated using a defect observation device, DR 7280 (KLA Tencor). The results are shown in Table 4. A: The number of defects is less than 30%. B: The number of defects is between 30% and 100%. C: The number of defects is between 100% and 300%. D: All patterns are dissolved or the number of defects exceeds 300%. <Evaluation 4: Defect Performance Evaluation (2)> The same operations as in defect performance evaluation (1) are carried out up to the PEB process. The obtained substrate is puddle-developed for 30 seconds in 2.38% TMA H aqueous solution, and while the developer is puddled on the wafer, the flow of electronic device manufacturing aqueous solution is started, and while rotating, the developer is replaced with the rinse electronic device manufacturing aqueous solution. While dripping the electronic device manufacturing aqueous solution, the wafer is rinsed at low speed for 30 seconds, and then rotated at high speed to dry. Evaluation is carried out in the same way as defect performance evaluation (1). The results obtained are listed in Table 4.

[0075] [Table 4] Surface: Defective M [0076I <Evaluation 5: Pattern Collapse Evaluation> A silicon substrate is treated with HMDS at 90°C for 30 seconds. A chemically amplified PHS-acrylate hybrid resist is spin-coated on top of it and soft-baked at 110°C for 60 seconds to form a 35 nm thick resist film. The resulting substrate is exposed using an EUV exposure system NXE:3400 through a mask with a size of 18 nm (line:space = 1:1), followed by PEB at 110°C for 60 seconds. 2. The wafer is puddled with a 38% TMAH aqueous solution for 30 seconds. While the developer is puddled on the wafer, deionized water is started to flow, and the developer is replaced with deionized water while the wafer is rotating. The process is stopped while the deionized water is puddled. The wafer is washed for 30 seconds at low speed while dripping an electronic device manufacturing solution, and the deionized water is replaced with the electronic device manufacturing solution. The wafer is then dried at high speed by spinning. The pattern obtained by the above method was observed using UV Vision 4, DR 7280. The results are shown in Table 5.

[0077] <Evaluation 6: Critical Pattern Size Evaluation> A silicon substrate is treated with HMDS at 90°C for 30 seconds. A chemically amplified PHS-acrylate hybrid resist is spin-coated on top of it and soft-baked at 110°C for 60 seconds to form a 50 nm thick resist film. The resulting substrate is exposed to light at NXE: 340°C through a mask with a 16 nm (line:space = 1:1) pattern, followed by PEB at 110°C for 60 seconds. 2.3 Puddle development is performed with a 8% TMA H2O solution for 30 seconds. While the developer is puddled on the wafer, deionized water is started to flow, and the developer is replaced with deionized water while the wafer is rotating. The process is stopped while the wafer is puddled with deionized water. The wafer was rinsed for 30 seconds at low speed while dripping an electronics manufacturing solution onto it, replacing the deionized water with the electronics manufacturing solution. The wafer was then dried at high speed using a high-speed spinning process. A scanning SEM CG6300 (Hitachi High-Tech) was used to confirm the line width and the presence or absence of pattern collapse. As the exposure dose increased, the line width decreased. The minimum line width at which pattern collapse did not occur was defined as the "critical pattern size." Comparative Example R3 differs from the above examples in that the substrate was spin-dried immediately after the water puddle, but was otherwise similar. In this case, pattern collapse was observed at a line width of 16.4 nm, but no collapse was observed at a line width of 16.8 nm, so the critical pattern size was determined to be 16.8 nm. The results are shown in Table 5.

[0078] [Table 5] Table 5: Pattern collapse and limit pattern size

Claims

36 Claim An aqueous solution for manufacturing electronic devices comprising a compound (A) and a solvent (B): the compound (A) comprises a monovalent anion moiety (A a) and a monovalent cation moiety, the anion moiety (A a) being represented by the formula (A a - a), [C1] — J 711 (Ah-ah) Formerly ZF Y-Tech (In the formula, X and X" are each independently -s (=0) 2- or -C (= 〇) - and Z and Z" are each independently a C-16 hydrocarbon group; One or more H in Z 11 is 〇 H, SH, COOH, CO NH 2S may be substituted with N H2 or 0 C H3, One or more Hs in Z 12 are 〇 H, SH, COO H s CO NH 2S may be substituted with N H2 or 0 C H3, one or more non-adjacent methylenes in Z may be substituted by oxy; one or more non-adjacent methylenes in Z" may be substituted with oxy; Y" is H or OH, n12, m12 and n12 are each independently 0 or 1, and when m12 = 1, 012 = 0, and when m12 = 0, 012 = 1. The solvent (B) contains water (B-1). 37

2. The aqueous solution for manufacturing electronic devices according to claim 1, wherein the number of carbon atoms in Z1 and Z2 is different.

3. The aqueous solution for manufacturing electronic devices according to claim 1 or 2, wherein XI \ X" or both are -S (= 0) 2 -.

4. The aqueous solution for manufacturing electronic devices according to any one of claims 1 to 3, wherein Z is a linear alkyl, a branched alkyl, a cyclic alkyl, or any combination thereof, and Z" includes a linear alkylene, a branched alkylene, a cyclic alkylene, or any combination thereof. 〇

5. 2 i or 2 " is one or more aromatic hydrocarbon groups, one or more The aqueous solution for manufacturing electronic devices according to claim 1 , comprising CH═CH— or one or more —C═C— groups.

6. The monovalent cation moiety is H+ or a monovalent cation moiety (Ac), The aqueous solution for manufacturing electronic devices according to claim 1 , wherein the monovalent cation moiety (Ac) is represented by the formula (Ac-a). + N H P R%_ P Formula (A c — a) (In the formula, Each Ra is independently a C-3 alkyl, one or more H of said C-3 alkyl may be replaced with OH, and p is O, 1, 2, 3, or 4.

7. The aqueous solution for producing electronic devices according to any one of claims 1 to 6, wherein the content of compound (A) is 0.001 to 10% by mass, based on the total mass of the aqueous solution for producing electronic devices; optionally, the content of solvent (B) is 80-99.999% by mass, based on the total mass of the aqueous solution for producing electronic devices; and optionally, the content of water (B-1) contained in solvent (B) is 80-99.999% by mass, based on the total mass of the aqueous solution for producing electronic devices.

8. The aqueous solution for manufacturing electronic devices according to any one of claims 1 to 7, wherein the molecular weight of compound (A) is 100 to 450.

9. The aqueous solution for manufacturing electronic devices according to any one of claims 1 to 8, wherein the surface tension of an aqueous solution prepared by adding compound (A) to water at a concentration of 500 ppm is 0 to 30% lower than the surface tension of water; wherein the surface tension is measured using a capillary rise type surface tensiometer.

10. The aqueous solution for manufacturing electronic devices according to any one of claims 1 to 9, further comprising a diol compound (C) represented by formula (C-a): [Chemistry 2] (In the formula, Rc1, Rc2, Rc3, and Rc4 are each independently hydrogen, fluorine, or C1-5 alkyl; L" and L C2 are each independently a C-20 alkylene, a C-20 cycloalkylene, a C-4 alkenylene, a C-4 alkynylene, or a C-20 arylene, which may be substituted with fluorine, C-5 alkyl, or hydroxy; and nC is 0, 1, or 2; optionally, the content of the diol compound (C) is 0.001 to 10% by mass, based on the total mass of the aqueous solution for manufacturing an electronic device.

11. The aqueous solution for manufacturing electronic devices according to any one of claims 1 to 10, further comprising a resin (D): optionally, the content of the resin (D) is 0 to 10 mass % based on the total mass of the aqueous solution for manufacturing electronic devices.

12. The aqueous solution for manufacturing electronic devices according to any one of claims 1 to 11, further comprising an additive (E): optionally, the additive (E) comprises one or more other nitrogen-containing compounds, one or more other surfactants, one or more other acids, one or more other bases, a disinfectant, an antibacterial agent, an antiseptic, or an antifungal agent; and optionally, the content of the additive (E) is 0.0001 to 10 mass% based on the total mass of the aqueous solution for manufacturing electronic devices.

13. The aqueous solution for manufacturing electronic devices according to any one of claims 1 to 12, which is an aqueous solution for manufacturing semiconductor devices; optionally, the aqueous solution for manufacturing electronic devices is an aqueous solution for manufacturing semiconductor substrates; optionally, the aqueous solution for manufacturing electronic devices is a cleaning solution for semiconductor substrate manufacturing processes; optionally, the aqueous solution for manufacturing electronic devices is a lithography cleaning solution; or optionally, the aqueous solution for manufacturing electronic devices is a cleaning solution for resist patterns.

14. A method for producing a resist pattern, using the aqueous solution for manufacturing electronic devices according to any one of claims 1 to 13.

15. A method for producing a resist pattern according to claim 14, comprising the following steps: (1) A photosensitive resin layer is formed by applying a photosensitive resin composition to a substrate with or without one or more intermediate layers therebetween; (2) exposing the photosensitive resin layer to radiation; (3) developing the exposed photosensitive resin layer; (4) The developed layer is washed with the aqueous solution for manufacturing electronic devices according to any one of claims 1 to 13.

16. The photosensitive resin composition is a chemically amplified photosensitive resin composition, and optionally, The method for producing a resist pattern according to claim 14 or 15, wherein the light is extreme ultraviolet light.

17. A method for producing a resist pattern according to any one of claims 14 to 16, which produces a resist pattern having a minimum space size of 5 to 30 nm.

18. A method for manufacturing a device, comprising the method for manufacturing a resist pattern according to any one of claims 14 to 17.

19. A method for manufacturing a device according to claim 18, further comprising: etching a substrate using a resist pattern produced by the method according to any one of claims 14 to 17 as a mask; or ion doping a substrate or an underlying film using a resist pattern produced by the method according to any one of claims 14 to 17 as a mask.

20. A method for manufacturing a device as described in claim 18 or 19, further comprising forming wiring on the processed substrate.

21. A compound (A) consisting of a monovalent anionic portion (Aa) and a monovalent cationic portion; The monovalent cation moiety is H+ or a monovalent cation moiety (Ac) The anion part (A a) is represented by the formula (A a — a): [Chemistry 3] (In the formula, X and X" are each independently -S (= 0) 2 - or -C (= 0) -, Z and Z" are each independently a C-16 hydrocarbon group; 41 One or more H in Z 11 is OH, SH, COO H s C0NH 2s may be substituted with N H2 or 00 H3; One or more H in Z 12 is OH, SH, 000 H s C0NH2, may be substituted with N H2 or 00 H3; one or more non-adjacent methylenes in Z may be substituted by oxy; one or more non-adjacent methylenes in Z" may be substituted with oxy; Y" is H or OH, n12, m12 and n12 are each independently 0 or 1, and when m12 = 1, 012 = 0, and when m12 = 0, 012 = 1.

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