Aqueous solution for manufacturing electronic equipment, method for manufacturing resist pattern, and method for manufacturing device

Abstract

To provide an aqueous solution for manufacturing electronic devices that can suppress defects. The aqueous solution for manufacturing electronic devices comprises a sulfonic acid derivative (A) having a specific structure, a solvent (B) containing water, and a hydroxy derivative (C) having a specific structure.

Description

[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. [Background technology]

[0002] In recent years, the need for higher integration of LSIs has increased, resulting in a demand for finer patterns. To meet these needs, lithography processes using short-wavelength light, such as KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet light (EUV; 13 nm), X-rays, and electron beams, are becoming more practical. To meet this demand for finer resist patterns, photosensitive resin compositions used as resists in 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 patterns.

[0003] Patent Document 1 discloses that a rinse solution containing a sulfonic acid compound and a nonionic surfactant is used to suppress pattern collapse, etc. Patent Document 2 discloses that an aqueous solution for manufacturing electronic devices containing an alkylcarboxylic acid compound is used to suppress pattern collapse and non-uniformity of resist pattern width. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-198456 [Patent Document 2] International Publication No. 2021 / 204651A1 Summary of the Invention [Problem to be solved by the invention]

[0005] The inventors have found that there are still one or more problems that require improvement, such as: reducing defects in fine resist patterns; suppressing the occurrence of bridges in resist patterns; preventing collapse of fine resist patterns; suppressing variations in the film thickness of resist patterns; preventing uneven distribution of solutes in aqueous solutions for manufacturing electronic devices when resist patterns are immersed in the aqueous solutions; reducing residues after removing the aqueous solutions for manufacturing electronic devices; reducing the surface tension of the aqueous solutions for manufacturing electronic devices; providing aqueous solutions for manufacturing electronic devices that are less dangerous to handle; and providing aqueous solutions for manufacturing electronic devices that have excellent storage stability (e.g., long-term storage). The present invention has been made based on the above-mentioned technical background, and provides an aqueous solution for manufacturing electronic devices. [Means for solving the problem]

[0006] The aqueous solution for manufacturing electronic devices according to the present invention comprises: Sulfonic acid derivatives (A), a solvent (B), and Hydroxy derivatives (C), comprising where: The sulfonic acid derivative (A) is represented by formula (a): [ka] (In the formula, A1 is C 3-30 a hydrocarbon group, which may be substituted with halogen; α is 1 or 2, X α+ is H + , NH4 + , or α-valent metal ions) The solvent (B) comprises water, The hydroxy derivative (C) is represented by formula (c). [ka] (In the formula, A2 is C 1-12alkyl, which may be substituted with halogen; n 21 is a number between 0 and 1, and n 22 is an integer from 1 to 4, Y + is H + or NH4 + (It is).

[0007] The method for producing a resist pattern according to the present invention uses the above aqueous solution for manufacturing electronic devices.

[0008] The device manufacturing method according to the present invention comprises the above-described method for manufacturing a resist pattern. [Effects of the Invention]

[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. 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 prevent resist pattern collapse in fine resist patterns. It is possible to suppress fluctuations in film thickness of resist patterns. It is believed that it is possible to prevent uneven distribution of solutes in the aqueous solution when the resist pattern is immersed in the aqueous solution for manufacturing electronic devices. It is possible to prevent the resist pattern from dissolving and reducing the pattern walls. It is possible to suppress swelling of the pattern walls due to the reaction of solutes with the resist pattern walls. It is possible to reduce residues after removing the aqueous solution for manufacturing electronic devices. It is possible to reduce the surface tension of the aqueous solution for manufacturing electronic devices. It is possible to reduce the danger 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. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram showing a state in which the resist wall is being rinsed. DETAILED DESCRIPTION OF THE INVENTION

[0011] The embodiments of the present invention will be described in detail below.

[0012] definition 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." An element of a concept can be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of elements as well as any single element. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "C x-y "," "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to alkyl chains having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. This copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are represented by structural formulas, the n or m in parentheses indicates the repeating number. The temperature unit is Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to the compound itself that has that function (for example, in the case of a base generator, it refers to the compound itself that generates a base). The compound may be dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, such a solvent is preferably contained in the composition of the present invention as solvent (B) or another component.

[0013] <Electronic device manufacturing aqueous solution> The aqueous solution for manufacturing electronic devices according to the present invention comprises a sulfonic acid derivative (A) (hereinafter sometimes referred to as component (A), the same applies to other components), a solvent (B), and a hydroxy derivative (C). The aqueous solution for manufacturing electronic devices is used in the manufacturing process of electronic devices. It is sufficient for the aqueous solution to be used in the manufacturing process of electronic devices, and it may be removed or lost during the process. Examples of electronic devices include display devices, LEDs, and semiconductor devices. The aqueous solution for manufacturing electronic devices is preferably an aqueous solution for manufacturing semiconductor substrates (more preferably a cleaning solution for semiconductor substrate manufacturing processes; even more preferably a lithography cleaning solution; and even more preferably a resist pattern cleaning solution). The aqueous solution for manufacturing electronic devices that is an aqueous solution for manufacturing semiconductor substrates can also be referred to as an aqueous solution for manufacturing semiconductor substrates that consists solely of the aqueous solution for manufacturing electronic devices of the present invention. In another embodiment of the present invention, the aqueous solution for manufacturing electronic devices is a rinse composition used to rinse an exposed and developed resist pattern.

[0014] Sulfonic acid derivatives (A) The sulfonic acid derivative (A) used in the present invention is represented by the formula (a). [ka] During the ceremony, A1 is C 3-30 A hydrocarbon group (preferably C 8-28 ; more preferably C 12-28 ; more preferably C 15-25 ; even more preferably C 12-20). The hydrocarbon group may be substituted or unsubstituted with a halogen (preferably unsubstituted). A1 is preferably alkyl, phenyl-substituted alkyl, or alkyl-substituted phenyl (more preferably alkyl or alkyl-substituted phenyl; even more preferably alkyl). The alkyl contained in A1 may be linear, branched, or cyclic (preferably linear or branched; more preferably linear). a is 1 or 2 (preferably 1). X α+ is H + , NH4 + , or an α-valent metal ion. α+ is preferably H + , NH4 + , lithium ion, sodium ion, potassium ion, magnesium ion (more preferably, H + or NH4 + ; more preferably, H + ). For example, X α+ However, Mg 2+ When α is written in parentheses, there are two groups in which A1 and a sulfo group are bonded, and Mg 2+ These are ionically bonded to the water. In aqueous solution, they are partially or completely ionized.

[0015] The component (A) is preferably represented by formula (a-1) or (a-2): In one preferred embodiment, the component (A) is represented by formula (a-2).

[0016] Equation (a-1) is as follows: [ka] In the formula, α, X α+ is as above, na is 1 or 2, preferably 1. R a1 is C 1-20 alkyl (preferably C 3-20 ; more preferably C 10-20 ) However, if na is 2, R a1may be the same or different, but the total number of carbon atoms is 20 or less. a1 The alkyl is preferably linear, branched or cyclic (more preferably linear or branched; even more preferably linear). In another preferred embodiment of the present invention, the component (A) is represented by formula (a-1).

[0017] Examples of the compound represented by formula (a-1) include decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, heptadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, nonadecylbenzenesulfonic acid, and the following compounds: [ka]

[0018] Equation (a-2) is as follows: [ka] In the formula, α, X α+ is as above, R a2 is C 3-20 alkyl (preferably C 8-20 ; more preferably C 10-20 ; more preferably C 10-19 ; even more preferably C 13-19 ). R a2 The alkyl is preferably linear, branched or cyclic (more preferably linear or branched; even more preferably linear).

[0019] Examples of compounds represented by formula (a-2) include decane sulfonic acid, undecane sulfonic acid, dodecane sulfonic acid, tridecane sulfonic acid, tetradecane sulfonic acid, pentadecane sulfonic acid, hexadecanesulfonic acid, heptadecane sulfonic acid, octadecane sulfonic acid, nonadecanesulfonic acid, and the following compounds: [ka]

[0020] One of the effects of the aqueous solution for manufacturing electronic devices according to the present invention is the suppression of defects in resist patterns after development. Without being bound by theory, it is believed that the sulfonic acid-derived moiety of component (A) ensures dispersibility in the aqueous solution, while the presence of other moieties reduces surface tension. Because component (A) has a high affinity with water in the aqueous solution for manufacturing electronic devices and is often present in the water, it is believed that this can reduce the risk of defects occurring in the photosensitive resin pattern, not just in the pattern.

[0021] The component (A) may be one type or a mixture of two or more types. The content of component (A) is preferably 0.001 to 10 mass % (more preferably 0.01 to 5 mass %; even more preferably 0.01 to 1 mass %; still more preferably 0.02 to 0.4 mass %) based on the aqueous solution for manufacturing electronic devices.

[0022] Solvent (B) The solvent (B) comprises water, which 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. The impurity concentration of the solvent (B) is preferably 1 ppm or less (more preferably 100 ppb or less; even more preferably 10 ppb or less). The water content based on the solvent (B) is preferably 90 to 100% by mass (more preferably 98 to 100% by mass; even more preferably 99 to 100% by mass; and even more preferably 99.9 to 100% by mass). In a preferred embodiment of the present invention, the solvent (B) consists essentially of water. However, a preferred embodiment of the present invention is one in which an 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 water content in the solvent (B) is 100% by mass.

[0023] Specific examples of the solvent (B) 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, 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.

[0024] The content of the solvent (B) is preferably 80 to 99.999 mass % (more preferably 90 to 99.99 mass %; even more preferably 95 to 99.99 mass %; and still more preferably 98 to 99.99 mass %) based on the aqueous solution for manufacturing electronic devices. The content of water contained in the solvent (B) is preferably 80 to 99.999 mass % (more preferably 90 to 99.99 mass %; even more preferably 95 to 99.99 mass %; and still more preferably 98 to 99.99 mass %) based on the aqueous solution for manufacturing electronic devices.

[0025] Hydroxy derivatives (C) The hydroxy derivative (C) used in the present invention is represented by formula (c). [ka] During the ceremony, A2 is C 1-12 alkyl (preferably C 1-8 Alkyl; more preferably C 1-6 Alkyl; more preferably C 3-6The alkyl may be substituted or unsubstituted (preferably unsubstituted) with halogen (preferably F). The alkyl of A2 is preferably linear, branched, or cyclic (more preferably linear or branched; even more preferably branched). Without being bound by theory, it is preferred that A2 is C 1-6 When the component (C) is an alkyl, it is thought that localization of the component (C) (for example, uneven distribution at the interface of the resist pattern) can be suppressed when the resist pattern is immersed in an aqueous solution for manufacturing electronic devices. n 21 is a number of 0 to 1 (preferably 0 or 1). n 22 is an integer of 1 to 4 (preferably 1, 2, or 3; more preferably 1 or 2; and even more preferably 1). 22 When n is 2 or more, A2 is a linker of divalent or more alkyl. 22 The group enclosed in the parentheses is attached. For example, n 22 When n = 2, A2 is a divalent alkylene. 22 When ≧2, n 21 The number of occurrences of -C(=O)- (carbonyl group) in one compound enclosed in parentheses is n 21 and n 22 is equal to the product of Y + is H + or NH4 + (preferably H + ). Y + is partially or completely ionized in aqueous solution.

[0026] The following compound is a compound represented by formula (c), where A2 is C2 alkyl (ethylene), n 22 = 2, n 21 =0.5, and two Y + Both are H + , can be read as n 21 ×n 22 = 1, and one carbonyl group appears in one compound. [ka]

[0027] The compound on the left below is a compound represented by formula (c), where A2 is C1 alkyl (methylene), n 22 = 2, n 21 = 0, and two Y + Both are H + , can be read as: The compound on the right below is a compound represented by formula (c), where A2 is a C3 alkyl (trivalent n-propylene), n 22 =3, n 21 = 1, and 3 Y + All are H + , can be read as: [ka]

[0028] The component (C) is preferably represented by formula (c-1) or (c-2). In a preferred embodiment, the component (C) is represented by formula (c-1). In formula (c), n 21 = 1, formula (c) is expressed as formula (c-1). In formula (c), n 21 When =0, equation (c) is expressed as equation (c-2).

[0029] Formula (c-1) is as follows: When the component (C) is represented by formula (c-1), the hydroxy derivative (C) may also be called a carboxylic acid derivative (C). [ka] wherein the symbols and subscripts have the same meanings as above.

[0030] Examples of the compound of formula (c-1) include isobutyric acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 3,5,5-trimethylhexanoic acid, malonic acid, 1,2,3-tricarboxylic acid, perfluorooctanoic acid, and the following compounds. [ka]

[0031] Equation (c-2) is as follows: [ka] wherein the symbols and subscripts have the same meanings as above. In another preferred embodiment of the present invention, the component (C) is represented by formula (c-2).

[0032] Examples of the compound of formula (c-2) include tert-butyl alcohol, 2-butanol, 4-methyl-2-pentanol, cyclohexanol, 1,2,3-hexanetriol, and the following compounds. [ka]

[0033] The content of the hydroxy derivative (C) is preferably 0.001 to 10 mass % (more preferably 0.001 to 5 mass %; even more preferably 0.001 to 1 mass %; and still more preferably 0.002 to 0.1 mass %) based on the aqueous solution for manufacturing electronic devices. Without being bound by theory, it is believed that the inclusion of component (C) can suppress aggregation of component (A) during the manufacturing process of electronic devices (e.g., the resist pattern cleaning process). It is believed that aggregation occurs mainly in the highly hydrophobic parts of component (A), and when component (A) is dissociated by the water in solvent (B) (product form), the charge imbalance increases, which is thought to reduce the aggregation. Without being bound by theory, it is believed that component (A) is in equilibrium with the parent form and the product form due to the dissociation, and component (C) stabilizes the product form by hydrogen bonding, which shifts the ratio of the parent form to the product form toward the product form, further reducing the aggregation.

[0034] The aqueous solution for manufacturing electronic devices according to the present invention essentially contains the aforementioned components (A), (B), and (C), but may contain additional compounds as necessary. Details will be described below. The total amount of components other than (A) to (C) (if multiple components are present, their sum total) in the entire composition is preferably 0 to 10% by mass (more preferably 0 to 5% by mass; even more preferably 0 to 3% by mass; and even more preferably 0.0001 to 1% by mass) based on the aqueous solution for manufacturing electronic devices. A preferred embodiment of the present invention is an aqueous solution for manufacturing electronic devices that does not contain any components other than (A) to (C) (0% by mass).

[0035] Nitrogen-containing compounds (D) The aqueous solution for manufacturing electronic devices according to the present invention may further contain a nitrogen-containing compound (D). The nitrogen-containing compound (D) may have one or more nitrogen atoms in the compound. The aqueous solution for manufacturing electronic devices according to the present invention can further suppress pattern collapse by combining with component (D).

[0036] Examples of component (D) include (i) ammonia, (ii) primary aliphatic amines having 1 to 16 carbon atoms and derivatives thereof (e.g., methylamine, ethylamine, isopropylamine, n-butylamine, tert-butylamine, cyclohexylamine, ethylenediamine, tetraethylenediamine, etc.), (iii) secondary aliphatic amines having 2 to 32 carbon atoms and derivatives thereof (e.g., dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, N,N-dimethylmethylenediamine, etc.), (iv) tertiary aliphatic amines having 3 to 48 carbon atoms and derivatives thereof (e.g., trimethylamine, triethylamine, tripropylamine, dimethylethylamine, tricyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, 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 their derivatives (e.g., pyrrole, oxazole, thiazole, imidazole, 4-methylimidazole, pyridine, methylpyridine, butylpyridine, etc.) Examples include:

[0037] Component (D) is 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.

[0038] The molecular weight of the component (D) is preferably 17 to 500 (more preferably 17 to 150; even more preferably 60 to 143).

[0039] The content of component (D) is preferably 0.00 to 1 mass % (more preferably 0.0005 to 0.5 mass %; even more preferably 0.0005 to 0.1 mass %) based on the aqueous solution for manufacturing electronic devices. In one aspect of the present invention, the aqueous solution for manufacturing electronic devices according to the present invention does not contain component (D).

[0040] Surfactant (E) The aqueous solution for manufacturing electronic devices according to the present invention may further contain a surfactant (E). Component (E) is useful for improving coatability and solubility. Component (E) is different from the above-described components (A), (C), and (D). Examples of component (E) 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. Other examples include fluorine-based surfactants such as F-TOP EF301, EF303, and EF352 (Tochem Products), MEGAFACE F171, F173, R-08, R-30, and R-2011 (Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (Sumitomo 3M), and Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.). The content of the component (E) is 0.00 to 5 mass % (more preferably 0.005 to 1 mass %; even more preferably 0.01 to 0.5 mass %) based on the aqueous solution for manufacturing electronic devices. In one preferred embodiment of the present invention, the component (E) is not included.

[0041] Additives (F) The aqueous solution for manufacturing electronic devices according to the present invention may further contain an additive (F). In the present invention, the additive (F) comprises an acid, a base, a bactericide, an antibacterial agent, a preservative, or an antifungal agent. The acid in the additive (F) is different from the component (A). The base in the additive (F) is different from the component (D). The additive (F) more preferably comprises an antibacterial agent (and even more preferably consists of only an antibacterial agent).

[0042] Acids or bases can be used to adjust the pH value of the processing solution or to improve the solubility of additive components. Examples of acids include aromatic carboxylic acids.

[0043] Component (F) can optionally contain an antibacterial agent, antifungal agent, preservative, or disinfectant. These chemicals are used to prevent bacterial and fungal growth over time. Examples of these chemicals are alcohols such as phenoxyethanol and isothiazolones. Bestcide (Nippon Soda) is a more effective antibacterial, antifungal, and disinfectant.

[0044] The content of the additive (F) is preferably 0.00 to 10 mass % (more preferably 0.0001 to 0.1 mass %; even more preferably 0.0002 to 0.001 mass %) based on the aqueous solution for manufacturing electronic devices. In one preferred embodiment of the present invention, the additive (F) is not contained.

[0045] The electronics manufacturing aqueous solution according to the present invention, after dissolving its components, contains impurities and / or The mixture may be filtered to remove insoluble matter.

[0046] <Method of manufacturing a resist pattern> The present invention also provides a method for producing a resist pattern using the above-mentioned aqueous solution for manufacturing electronic devices. The photosensitive resin composition (resist composition) used in this method may be either positive-type or negative-type; positive-type is more preferred. A typical method for producing a resist pattern using the aqueous solution for manufacturing 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) Washing the developed layer with the above electronics manufacturing aqueous solution.

[0047] 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 needed, to form a photosensitive resin layer. While known techniques can be used for lamination, spin coating or other coating methods are 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). Layers other than the photosensitive resin layer will be described later. Forming an anti-reflective film above or below the photosensitive resin film can improve the cross-sectional shape and exposure margin.

[0048] 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 photosensitizer and an alkali-soluble resin, and chemically amplified photosensitive resin compositions. From the perspective 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 considered the following. 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.

[0049] Examples of the quinone diazide photosensitizer used in the positive photosensitive resin composition containing the above quinone diazide photosensitizer and an alkali-soluble resin include 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, and esters or amides of these sulfonic acids. Examples of the alkali-soluble resin include polyvinylphenol, polyvinyl alcohol, and copolymers of acrylic acid or methacrylic acid.

[0050] 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 that consist of an alkali-soluble resin, a photoacid generator, and a crosslinking agent, and in which crosslinking of the resin occurs due to the action of the crosslinking agent, and whose solubility in a developer changes between exposed and unexposed areas.

[0051] 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 generate alkali-soluble groups. Typical examples include polymers in which an acetal group or a ketal group is introduced as a protecting group into a hydroxystyrene polymer (PHS) (e.g., JP-A-2-19847, etc.), and similar polymers in which a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group is introduced as an acid-decomposable group (e.g., JP-A-2-209977, etc.).

[0052] 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 an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis such as iminosulfonates, disulfone compounds, diazoketosulfones, and diazodisulfone compounds. Compounds in which these photoacid-generating groups or compounds are introduced into the main chain or side chain of a polymer can also be used.

[0053] 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.

[0054] The photosensitive resin composition is applied onto a substrate using a suitable application device such as a spinner or coater and by a suitable application 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; even more preferably 30 to 120 seconds).

[0055] The resist pattern manufacturing method of the present invention 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 nitride films), and adhesion films. An example of a planarizing film is SOC. For the formation of inorganic hard mask intermediate layers, see Japanese Patent No. 5336306. The intermediate layer may be composed of one layer or multiple layers. Furthermore, an upper layer film may be formed on the photosensitive resin layer. An example of an upper layer film is a top antireflective coating (TARC).

[0056] In the resist pattern production process of the present invention, known techniques can be used for the layer structure in accordance with the process conditions, and examples thereof include the following laminated structures. Substrate / photosensitive resin layer Substrate / lower film / photosensitive resin layer Substrate / flattening film / photosensitive resin layer Substrate / flattening film / photosensitive resin layer / upper layer film Substrate / Planarization film / BARC / Photosensitive resin layer Substrate / flattening film / photosensitive resin layer / upper layer film Substrate / planarization film / inorganic hard mask intermediate layer / photosensitive resin layer Substrate / planarization film / adhesion film / photosensitive resin layer Substrate / substrate modification layer / planarization film / photosensitive resin layer Substrate / substrate modification layer / flattening film / adhesion film / photosensitive resin layer These layers can be cured by heating and / or exposure to light after application, or can be formed using known techniques such as CVD. These layers can be removed by known techniques (such as etching), and each layer can be patterned using the upper layer as a mask. In a preferred embodiment of the present invention, the photosensitive resin composition is applied directly onto the substrate without an intermediate layer, and in another embodiment of the present invention, no TARC is 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 a photosensitive resin layer as in WO2022 / 129015.

[0057] The photosensitive resin layer is exposed through a predetermined mask. If other layers are included (such as TARC), they may also 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 a tolerance of ±5%, preferably ±1%. After exposure, post-exposure baking (PEB) can be performed as needed. 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).

[0058] 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, surfactants and the like can also be added to these developers. The temperature of the developer is preferably 5 to 50°C (more preferably 25 to 40°C), and the development time is preferably 10 to 300 seconds (more preferably 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 resist patterns in which walls have been thickened by further covering them with other layers or films.

[0059] 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 in 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 contacting the aqueous solution for manufacturing electronic devices with the resist is also arbitrary, and can be carried out by, for example, immersing the resist substrate in the aqueous solution for manufacturing electronic devices or dropping the aqueous solution onto the surface of a rotating resist substrate.

[0060] 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.). The cleaning before the cleaning process is useful for cleaning the developer adhering to the resist pattern. The cleaning after the cleaning process is useful for cleaning the aqueous solution for manufacturing electronic devices. In one preferred embodiment of the manufacturing method according to the present invention, the developed resist pattern is washed by pouring pure water into it to replace the developer, and then, while the pattern remains immersed in the pure water, the aqueous solution for manufacturing electronic devices is poured in to replace the developer, thereby washing the pattern. The cleaning with the aqueous solution used in the electronics manufacturing process may be carried out by known methods. For example, the resist substrate may be immersed in an electronic device manufacturing solution, or the electronic device manufacturing solution may be dropped onto the surface of a rotating resist substrate. These methods may be used in combination as appropriate.

[0061] 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 becomes severe when the walls of the resist pattern are parallel. In this specification, the minimum space size is defined as the distance between the smallest spacings 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 spacings between walls is low, the frequency of defects will decrease, and therefore the frequency of defective products will 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.

[0062] <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. After processing, the resist film is stripped 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. Known etching techniques such as dry etching and wet etching can be used for the etching, with dry etching being more preferred. For example, the substrate can be processed by etching the intermediate layer using the resist pattern as an etching mask, and then etching the substrate using the resulting intermediate layer pattern as an etching mask. Alternatively, the resist pattern can be used as an etching mask to etch the layers below the resist layer (e.g., the intermediate layer) while also etching the substrate as is. The processed substrate becomes, for example, a patterned substrate. The formed pattern can be used to form wiring on the substrate. These layers can be removed by dry etching, preferably with O2, CF4, CHF3, Cl2 or BCl3, preferably with O2 or CF4. In one preferred embodiment, the method for manufacturing a device according to the present invention further comprises forming wiring on the processed substrate.

[0063] <Stress on the resist wall> As described in Namatsu et al. Appl. Phys. Lett. 1995(66) pp. 2655-2657 and shown diagrammatically in FIG. 1, the stress on the wall during rinsing can be expressed by the following equation: σ max =(6γcosθ / D)x(H / W) 2 σ max : Maximum stress applied to the resist, γ: Surface tension of the rinse θ: contact angle, D: distance between walls H: Wall height, W: Wall width These lengths can be measured by known methods, for example, SEM photography.

[0064] As can be seen from the above formula, a shorter D or a shorter W causes more stress. In this specification, the "pitch size" means one unit of the resist pattern unit array having W and D as shown in FIG. This means that the finer (narrower pitch size) the resist pattern is required to be, the greater the stress on the resist pattern will be. As the pattern becomes finer, the more stringent the conditions become, and the more improvements are required in aqueous solutions (e.g., rinse compositions) used in the manufacture of electronic devices.

[0065] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0066] <Preparation Example of Example 11> Add decane sulfonic acid (as the sulfonic acid derivative (A)) and isobutyric acid (as the hydroxy derivative (C)) to deionized water to a concentration of 2,000 ppm and stir. Visually confirm complete dissolution. Filter (pore size = 10 nm) the resulting solution to obtain the aqueous solution of Example 11.

[0067] <Preparation Examples of Examples 12 to 19, Comparative Examples 11 to 13, and Reference Example 11> Aqueous solutions of Examples 12 to 19, Comparative Examples 11 to 13, and Reference Example 11 are prepared in the same manner as in the preparation example of Example 11 above, using the sulfonic acid derivative (A), hydroxy derivative (C), and nitrogen-containing compound (D) as shown in Table 1, so as to have the concentrations shown in Table 1. Comparative Example 13 was filtered deionized water with no additives. [Table 1] In Tables 1 to 3, A1: decane sulfonic acid, [ka] A2: tetradecanesulfonic acid, [ka] A3: Dodecylbenzenesulfonic acid, [ka] A4: alkylsulfonic acid mixture (a mixture of alkylsulfonic acids having the following structure and 13 to 18 carbon atoms), [ka] A5: Alkylbenzenesulfonic acid mixture (structure shown below. Mixture of alkyl chains with 13 to 18 carbon atoms) [ka] C1: isobutyric acid, C2: 2-methylpentanoic acid, · C3: 2-methylhexanoic acid, C4: 3,5,5-trimethylhexanoic acid, C5: malonic acid, C6: Perfluorooctanoic acid, Comp. C7: The following structure, R a1 is a methyl group, R a2 a compound in which r11, s11, r21, and s21 are integers that satisfy r11+r21=3.5 and s11+s21=0, respectively; [ka] Comp. C8: The above structure, R a1 is a methyl group, R a2 a compound in which r11, s11, r21, and s21 are integers that satisfy r11+r21=5 and s11+s21=2, respectively; is.

[0068] <Defect evaluation (1)> A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist is then spin-coated onto the substrate and heated on a hot plate at 110°C for 60 seconds to obtain a 35 nm thick resist film. A 2.38% by mass TMAH aqueous solution is then poured into the substrate and held for 30 seconds (puddling). While the developer is puddling, water is started to flow, and the developer is replaced with water while rotating the substrate, and the process is stopped while the substrate is puddling with water. While the substrate is puddling with water, the aqueous solution of Example 11 is poured into the substrate while rotating at a low speed for 30 seconds, and the water is replaced with the aqueous solution of Example 11. The substrate is then spun at a high speed and dried to obtain a cleaned resist film. The surface of the cleaned resist film was observed using a defect inspection system LS9110 (Hitachi High-Technologies), and the number of foreign particles adhering to the surface of the resist film was counted. The results obtained are shown in Table 1. Using each of the aqueous solutions of Examples 11 to 19, Comparative Examples 11 to 13, and Reference Example 11, evaluation substrates are prepared in the same manner as above, and the number of foreign particles is counted. Comparative Example 13 differs from Example 11 above in that the substrate is spin-dried immediately after being puddled with water, but is otherwise similar.

[0069] <Preparation Examples of Examples 21 to 29 and Comparative Example 21> Aqueous solutions of Examples 21 to 29 and Comparative Example 21 are prepared in the same manner as in the preparation example of Example 11 above, using the sulfonic acid derivative (A), hydroxy derivative (C), and nitrogen-containing compound (D) as shown in Table 2, so as to have the concentrations shown in Table 2. Comparative Example 21 was filtered deionized water with no additives. [Table 2]

[0070] <Defect evaluation (2)> A silicon substrate was treated with HMDS at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist was then applied onto the substrate by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a 35 nm thick resist film. This substrate was then exposed through a mask (18 nm line / space 1:1) using an EUV exposure system (NXE:3400, ASML). PEB was then performed on a hot plate at 110°C for 60 seconds, and a 2.38 wt% TMAH aqueous developer solution was poured in and held for 30 seconds. While the developer was puddling, water was started to flow, and the developer was replaced with water while rotating the substrate, and the process was stopped while the substrate was puddling with water. Then, while the substrate was puddling with water, the aqueous solution of Example 21 was poured in while rotating at a low speed for 30 seconds, and the water was replaced with the aqueous solution of Example 21. The substrate was then rotated at a high speed and dried to obtain a cleaned resist pattern. The number of foreign particles adhering to the surface of the cleaned resist pattern was counted using a defect inspection system UVision4 (Applied Materials), and the shape of the foreign particles was observed using a defect observation system eDR7280 (KLA Tencor). Evaluation was based on the following criteria. The results obtained are shown in Table 2. A: The number of defects is less than 30% of the number of foreign matters in Comparative Example 21. B: The number of defects is 30% or more and less than 100% of the number of foreign matters in Comparative Example 21. C: The number of defects is 100% or more and less than 300% of the number of foreign matters in Comparative Example 21. D: All patterns are dissolved. For each of the aqueous solutions of Examples 22 to 29, an evaluation substrate is prepared in the same manner as above, and evaluated according to the above criteria. Comparative Example 21 differs from Example 21 above in that the substrate is spin-dried immediately after being puddled with water, but is otherwise similar.

[0071] <Number of pattern failures> A cleaned resist pattern is obtained in the same manner as in defect evaluation (2). The number of collapsed patterns was counted for the cleaned resist patterns using the defect inspection system UVision4 and defect review system eDR7280. The results are shown in Table 2.

[0072] <Limit pattern size> A silicon substrate is treated with HMDS for 30 seconds at 90°C. An EUV PHS-acrylate chemically amplified resist is then applied by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a 50 nm thick resist film. This substrate is then exposed through a mask (16 nm line / space 1:1) using an EUV exposure system (NXE:3400). The exposure dose is varied to vary the resulting line width. PEB is then performed on a hot plate at 110°C for 60 seconds, followed by pouring in a 2.38 wt% TMAH aqueous developer solution and holding for 30 seconds. While the developer is puddling, water is started to flow, and the developer is replaced with water while rotating the substrate, stopping the puddling with water. Then, while the substrate is puddling with water, the aqueous solution of Example 21 is poured in and the substrate is washed while rotating at low speed for 30 seconds, replacing the water with the aqueous solution of Example 21. The substrate is rotated at high speed and dried to obtain a cleaned resist pattern. The cleaned resist pattern was observed using a SEM CG6300 (Hitachi High-Technologies) to check the line width and whether or not pattern collapse occurred. The minimum line width at which pattern collapse did not occur was defined as the "critical pattern size." The results obtained are shown in Table 2. For each of the aqueous solutions of Examples 22 to 29, the "critical pattern size" is obtained in the same manner as above. Comparative Example 21 is similar to Example 21 except that the substrate is spin-dried immediately after being puddled with water. In this case, pattern collapse was observed at a line width of 16.4 nm, but not at a line width of 16.8 nm, so the critical pattern size was set to 16.8 nm.

[0073] <Preparation Examples of Examples 31 to 39, Comparative Examples 31 and 32, and Reference Example 31> Aqueous solutions of Examples 31 to 39, Comparative Examples 31 and 32, and Reference Example 31 are prepared in the same manner as in the preparation example of Example 11 above, using the sulfonic acid derivative (A), hydroxy derivative (C), and nitrogen-containing compound (D) as shown in Table 3, so as to have the concentrations shown in Table 3. Comparative Example 31 was filtered deionized water with no additives. [Table 3]

[0074] <Evaluation of film thickness fluctuation> A silicon substrate is treated with HMDS at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist is then applied thereon by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a 35 nm thick resist film. The aqueous solution of Example 21 is poured onto the resist film, covering the resist film with the aqueous solution of Example 21 and allowing it to stand in this state for 180 seconds. The substrate is then rotated at high speed to remove the aqueous solution of Example 21. The thickness of the resist film after removal is measured using an ellipsometer M-2000 (JA Woollam). (35 nm - (thickness of the resist film after removal)) is calculated, and the absolute value is taken as the film thickness fluctuation width X. Evaluation is made according to the following criteria. The obtained results are shown in Table 3. A:X≦1.0nm B: 1.0 nm <x≦2.0nmC:2.0nm <x≦3.0nmD:3.0nm <x The aqueous solutions of Examples 32 to 39, Comparative Examples 31 and 32, and Reference Example 31 are evaluated in the same manner as above using each aqueous solution.< / x

Claims

1. Sulfonic acid derivative (A), a solvent (B), and Hydroxy derivatives (C), An electronics manufacturing aqueous solution comprising: where: The sulfonic acid derivative (A) is represented by the formula (a): 【Chemistry 1】 (In the formula, A １ is C ３－３０ a hydrocarbon group, which may be substituted with halogen; α is 1 or 2; X α＋ Is, H ＋ , N.H. ４ ＋ , or an α-valent metal ion) The solvent (B) comprises water, The hydroxy derivative (C) is represented by formula (c): 【Chemistry 2】 (In the formula, A ２ is C １－１２ alkyl, which may be substituted with halogen; n ２１ is a number between 0 and 1, and n ２２ is an integer from 1 to 4, Y ＋ Is, H ＋ or NH ４ ＋ (It is).

2. A １ is alkyl, phenyl-substituted alkyl, or alkyl-substituted phenyl. Optionally, A １ The alkyl contained in is a straight chain, branched or cyclic alkyl.

3. A ２ But C １－７ 3. The aqueous solution for manufacturing electronic devices according to claim 1, wherein the alkyl is an alkyl group optionally substituted with a halogen. Optionally, A ２ The alkyl may be linear, branched or cyclic.

4. The aqueous solution for producing electronic devices according to at least one of claims 1 to 3, wherein the content of the sulfonic acid derivative (A) is 0.001 to 10 mass% based on the aqueous solution for producing electronic devices: Optionally, the content of the solvent (B) is 80 to 99.999% by mass based on the aqueous solution for manufacturing electronic devices; Optionally, the content of water contained in the solvent (B) is 80 to 99.999 mass % based on the electronic device manufacturing aqueous solution; or Optionally, the content of the hydroxy derivative (C) is 0.001 to 10% by weight, based on the aqueous solution for manufacturing electronic devices.

5. The aqueous solution for manufacturing electronic devices according to claim 1 , further comprising a nitrogen-containing compound (D): Optionally, the aqueous electronics manufacturing solution further comprises a surfactant (E).

6. The aqueous solution for manufacturing electronic devices according to claim 1 , further comprising an additive (F): where: The additive (F) comprises an acid, a base, a disinfectant, an antibacterial agent, a preservative, or an antifungal agent; Optionally, the content of the nitrogen-containing compound (D) is 0.00 to 1 mass % based on the aqueous solution for manufacturing electronic devices; Optionally, the content of the surfactant (E) is 0.00 to 5% by mass based on the aqueous solution for manufacturing electronic devices; or Optionally, the content of the additive (F) is 0.00 to 10% by mass based on the aqueous solution for manufacturing electronic devices.

7. The aqueous solution for manufacturing electronic devices according to at least one of claims 1 to 6, which is an aqueous solution for manufacturing semiconductors: Optionally, the aqueous electronics manufacturing solution is an aqueous semiconductor substrate manufacturing solution; Optionally, the aqueous electronics manufacturing solution is a semiconductor substrate manufacturing process cleaning solution; Optionally, the aqueous electronics manufacturing solution is a lithography cleaning solution; or Optionally, the electronics manufacturing aqueous solution is a resist pattern cleaning solution.

8. A method for producing a resist pattern, which uses the aqueous solution for producing electronic devices according to at least one of claims 1 to 7.

9. A method for producing a resist pattern, comprising 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) The developed layer is washed with the aqueous solution for manufacturing electronic devices according to at least one of claims 1 to 7.

10. 10. The method for producing a resist pattern according to claim 9, wherein the photosensitive resin composition is a chemically amplified photosensitive resin composition, and the exposure is optionally carried out using extreme ultraviolet rays.

11. 11. The method for producing a resist pattern according to claim 8, wherein the minimum space size of the resist pattern in one circuit unit is 5 to 30 nm.

12. A method for manufacturing a device, comprising the method for manufacturing a resist pattern according to at least one of claims 8 to 11.

13. The method for producing a device according to claim 12, further comprising etching a substrate using the resist pattern produced by the method according to at least one of claims 8 to 11 as a mask.

14. The method for manufacturing a device according to claim 12 or 13, further comprising forming wiring on the processed substrate.

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