Aqueous solution for manufacturing electronic equipment, method for manufacturing resist patterns, and method for manufacturing devices.

Abstract

To provide an aqueous solution for manufacturing electronic equipment that can prevent pattern collapse or suppress non-uniformity of resist pattern width. [Solution] An aqueous solution for manufacturing electronic equipment comprising an alkylcarboxylic acid compound (A) and a solvent (B): where the alkylcarboxylic acid compound (A) is represented by formula (a); A1-COOH formula (a) (In the formula, A1 is C 3-12 (It is alkyl) and Solvent (B) consists of water.

Description

[Technical Field]

[0001] This invention relates to an aqueous solution for manufacturing electronic equipment, a method for manufacturing resist patterns, and a method for manufacturing devices. [Background technology]

[0002] In recent years, there has been a growing need for higher integration in LSIs, requiring miniaturization of 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 (EUV; 13 nm), X-rays, and electron beams are being put into practical use. To accommodate this miniaturization of resist patterns, high-resolution photosensitive resin compositions used as resists during microfabrication are also required. While exposure with short-wavelength light can form finer patterns, creating extremely fine structures raises concerns about yield, such as the deformation of the fine patterns.

[0003] In this context, Patent Document 1 investigates a lithography rinse solution that exhibits excellent performance in areas such as pattern collapse margin, defects, and LWR, similar to conventional systems containing surfactants, and also possesses superior melting properties.

[0004] Another approach involves considering the use of surfactants containing fluorine (Patent Documents 2 and 3). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2014-219577 [Patent Document 2] International Publication No. 2018 / 095885 [Patent Document 3] International Publication No. 2017 / 220479 [Overview of the Initiative] Problems to be Solved by the Invention

[0006] The inventors have recognized that there are one or more problems for which improvement is still needed. Examples of these problems include the following: reducing defects in fine resist patterns; suppressing the occurrence of bridges in resist patterns; preventing collapse of fine resist patterns; suppressing non-uniformity of resist pattern width; reducing residue after removing an aqueous solution for electronic device manufacturing; reducing the surface tension of an aqueous solution for electronic device manufacturing; providing an aqueous solution for electronic device manufacturing that has low environmental impact; providing an aqueous solution for electronic device manufacturing that has low handling risk; providing an aqueous solution for electronic device manufacturing that is excellent in storage stability (e.g., long-term storage); providing an aqueous solution for electronic device manufacturing that has little influence on resist patterns. The present invention has been made based on the above technical background, and provides an aqueous solution for electronic device manufacturing. Means for Solving the Problems

[0007] The aqueous solution for electronic device manufacturing according to the present invention is an alkyl carboxylic acid compound (A), and a solvent (B) comprising the same wherein the alkyl carboxylic acid compound (A) is represented by formula (a); A1-COOH formula (a) (wherein A1 is C 3-12 alkyl) and the solvent (B) comprises water.

[0008] The method for producing a resist pattern according to the present invention uses the above aqueous solution for electronic device manufacturing.

[0009] The method for producing a device according to the present invention comprises the above method for producing a resist pattern. Effect of the Invention

[0010] By using the aqueous solution for manufacturing electronic equipment according to the present invention, it is possible to achieve one or more of the following effects. It is possible to reduce defects in fine resist patterns. It is possible to suppress the occurrence of bridging in resist patterns. It is possible to prevent resist pattern collapse in fine resist patterns. It is possible to reduce the non-uniformity of resist pattern width. It is possible to reduce residue after removing the electronic equipment manufacturing aqueous solution. It is possible to lower the surface tension of the electronic equipment manufacturing aqueous solution. It is possible to reduce the environmental impact of the electronic equipment manufacturing aqueous solution. It is possible to reduce the handling risks of the electronic equipment manufacturing aqueous solution. It is possible to improve the storage stability of the electronic equipment manufacturing aqueous solution. It is possible to reduce the impact of the electronic equipment manufacturing aqueous solution on resist patterns. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a schematic diagram showing the state of rinsing the resist wall. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described in detail as follows.

[0013] definition In this specification, unless otherwise specified, the definitions and examples set forth in this paragraph shall prevail. The singular form includes the plural form, and "one" or "that" means "at least one." An element of a certain concept can be expressed by multiple types, and when a quantity (e.g., mass %) is given, that quantity represents the sum of those multiple types. "and / or" includes all combinations of elements, as well as their use individually. When a numerical range is indicated using "~" or "-", it includes both endpoints and has the same unit. For example, 5~25 mol% means between 5 mol% and 25 mol%. "Cx-y "C x ~C y " and "C x The notation, such as "," refers to the number of carbon atoms in the molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having between 1 and 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl). When a polymer has multiple types of repeating units, these repeating units copolymerize. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers and resins are shown in structural formulas, the n, m, etc., in parentheses indicate the number of repeating units. The unit of temperature used is Celsius. For example, 20 degrees means 20 degrees Celsius. An 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 also be added to the composition in the form of being dissolved or dispersed in a solvent. In one embodiment of the present invention, it is preferable that such a solvent is included in the composition according to the present invention as solvent (B) or other component.

[0014] <Electronic device manufacturing aqueous solution> The aqueous solution for manufacturing electronic equipment according to the present invention comprises an alkylcarboxylic acid compound (A) and a solvent (B). Here, the electronic device manufacturing aqueous solution is one used during the manufacturing process of electronic devices. It is sufficient that it is used in the manufacturing process of electronic devices, and it may be removed or lost during the process. Examples of electronic devices include display elements, LEDs, and semiconductor elements. The aqueous solution for manufacturing electronic equipment 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 equipment that is an aqueous solution for manufacturing semiconductor substrates can also be said to be an aqueous solution for manufacturing semiconductor substrates consisting only of the aqueous solution for manufacturing electronic equipment of the present invention. In another aspect of the present invention, the aqueous solution for electronic device manufacturing may be a rinse composition used for rinsing an exposed and developed resist pattern.

[0015] Alkylcarboxylic acid compound (A) The alkylcarboxylic acid compound (A) used in the present invention is represented by formula (a). A1-COOH Formula (a) Here, A1 is C 3-12 alkyl. A1 may be linear, branched or cyclic alkyl. A1 is preferably linear or branched C 3-11 alkyl; more preferably linear or branched C 3-10 alkyl; still more preferably linear or branched C 3-9 alkyl; even more preferably linear or branched C 3-8 alkyl. In a preferred embodiment of the present invention, A1 is linear or branched C3 alkyl.

[0016] Specific examples of the alkylcarboxylic acid compound (A) include 2-methylpropanoic acid, n-butanoic acid, 2-methylbutanoic acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 5-methylhexanoic acid, 2-methylheptanoic acid, 4-methyl-n-octanoic acid, 2-ethylhexanoic acid, 2-propylpentanoic acid, 2,2-dimethylpentanoic acid, and 3,5,5-trimethylhexanoic acid.

[0017] The content of the alkylcarboxylic acid compound (A), based on the aqueous solution for electronic device manufacturing, is preferably 0.01 to 10% by mass (more preferably 0.02 to 5% by mass; still more preferably 0.02 to 1% by mass).

[0018] One of the effects of the alkylcarboxylic acid compound (A) in the aqueous solution for manufacturing electronic equipment according to the present invention is that it contributes to preventing pattern collapse after development of the resist pattern. Although not bound by theory, it is thought that the low affinity between the alkylcarboxylic acid compound of the present invention and the resist wall can increase the contact angle of the aqueous solution for manufacturing electronic equipment during the rinsing drying process. Specifically, it is thought that the alkyl in formula (a) can lower the surface tension of the composition, and the carboxyl can improve the solubility of the aqueous solution for manufacturing electronic equipment, thereby improving the balance between solubility and low surface tension.

[0019] Solvent (B) The solvent (B) comprises water. The water is preferably deionized water. Considering its use in the manufacturing process of electronic devices, solvent (B) is preferably one with few impurities. Solvent (B) preferably has an impurity concentration of 1 ppm or less (more preferably 100 ppb or less; even more preferably 10 ppb or less). The water content relative to solvent (B) 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). In a preferred embodiment of the present invention, solvent (B) consists substantially of water alone. However, a form in which additives are dissolved and / or dispersed in a solvent other than water (e.g., a surfactant) and contained in the aqueous solution for manufacturing electronic equipment of the present invention is also acceptable as a preferred embodiment of the present invention. In a further preferred embodiment of the present invention, the water content in solvent (B) is 100% by mass.

[0020] Specific examples of solvents (B) other than water include, for example, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, or mixtures thereof. These are preferred in terms of the storage stability of the solution. Two or more of these solvents can also be used in mixture form.

[0021] The content of solvent (B) is preferably 80 to 99.99% by mass (more preferably 90 to 99.99% by mass; even more preferably 95 to 99.99% by mass; and even more preferably 98 to 99.99% by mass), based on the aqueous solution for electronic equipment manufacturing. Furthermore, the water content in solvent (B) is preferably 80 to 99.99% by mass (more preferably 90 to 99.99% by mass; even more preferably 95 to 99.99% by mass; and even more preferably 98 to 99.99% by mass), based on the aqueous solution used for manufacturing electronic equipment.

[0022] The aqueous solution for manufacturing electronic equipment according to the present invention is essential for the above-mentioned components (A) and (B), but may contain further compounds as needed. These will be described in detail below. The total amount of components other than (A) and (B) in the overall composition (if there are multiple components, their sum) is preferably 0 to 10% by mass (more preferably 0 to 5% by mass; even more preferably 0 to 3% by mass) based on the aqueous solution for manufacturing electronic equipment. A form in which the aqueous solution for manufacturing electronic equipment according to the present invention does not contain components other than (A) and (B) (0% by mass) is also a preferred form of the present invention.

[0023] Nitrogen-containing compounds (C) The aqueous solution for manufacturing electronic equipment according to the present invention comprises a nitrogen-containing compound (C). The nitrogen-containing compound (C) only needs to contain one or more nitrogen atoms. As described above, the aqueous solution for manufacturing electronic equipment according to the present invention contains an alkyl carboxylic acid compound (A), which suppresses pattern deformation. However, by combining it with a nitrogen-containing compound (C), pattern deformation can be further suppressed, and other defects such as pattern melting and resist residue can also be suppressed. Although not bound by theory, it is considered possible to reduce the influence of the alkyl carboxylic acid compound (A) on the resist pattern by including the nitrogen-containing compound (C).

[0024] Examples of nitrogen-containing compounds (C) 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, tert-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''-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.), (vi) Heterocyclic amines having 5 to 30 carbon atoms and their derivatives (e.g., pyrrole, oxazole, thiazole, imidazole, 4-methylimidazole, pyridine, methylpyridine, butylpyridine, etc.) These are some examples.

[0025] The nitrogen-containing compound (C) is preferably selected from the group consisting of (i), (ii), and (iv), and more preferably from the group consisting of ammonia, n-butylamine, ethylenediamine, triethylamine, tripropylamine, and N,N,N',N'-tetraethylethylenediamine.

[0026] The molecular weight of the nitrogen-containing compound (C) is preferably 17 to 500 (more preferably 17 to 150; even more preferably 60 to 143).

[0027] The content of nitrogen-containing compound (C) is preferably 0.0001 to 10% by mass (more preferably 0.0005 to 0.5% by mass; even more preferably 0.0005 to 0.05% by mass; and even more preferably 0.0005 to 0.01% by mass) based on the aqueous solution used for manufacturing electronic equipment.

[0028] Hydroxy-containing compounds (D) The aqueous solution for manufacturing electronic equipment according to the present invention may further contain a hydroxyl-containing compound (D). The hydroxyl-containing compound (D) only needs to have one or more hydroxyls in the compound, but preferably has 1 to 3 hydroxyls and may be fluorine-substituted. 3-30 This is a compound. In this case, fluorine substitution replaces the H atoms in the compound with F, but this substitution does not replace the H atoms in the hydroxyl group. It is believed that by further including this hydroxyl-containing compound (D), it will be possible to further reduce the minimum size at which it will not tip over.

[0029] A preferred form of the hydroxyl-containing compound (D) is represented by formula (d). [ka] During the ceremony, R d1 , R d2 , R d3 , and R d4 These are, independently, hydrogen, fluorine, or C 1-5 The alkyl group is preferably hydrogen, fluorine, methyl, ethyl, t-butyl, or isopropyl, each independently; more preferably hydrogen, methyl, or ethyl, each independently. L d1 and L d2 Each of them is independent of C 1-20 Alkylene, C 1-20 Cycloalkylene, C 2-4 Alkenylene, C 2-4 Alkynylene, or C 6-20 These are arylenes. These groups are fluorine, C 1-5 It may be substituted with alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon having one or more double bonds, and alkylylene means a divalent hydrocarbon group having one or more triple bonds. Preferably L d1 and L d2 Each of these may be fluorine-substituted, C 1-5 Alkylene, C 2-4 It is alkynylene or phenylene (C6 arylene). d1 and L d2 Each is independently, more preferably fluorine-substituted C 2-4 The alkylene, acetylene (C2 alkylene) or phenylene; more preferably fluorine-substituted C 2-4 These are alkylenes and acetylenes. The effects of the present invention can be obtained even without using fluorine-containing components. One such form is L d1 and L d2 Each is independent of C 1-5 Alkylene, C 2-4 The alkynylene or phenylene (more preferably each independently of C) 2-4 Alkylene, acetylene, or phenylene; more preferably each independently of C 2-4(Alkylene, acetylene). h is 0, 1, or 2 (preferably 0 or 1; more preferably 0).

[0030] Specific examples of hydroxyl-containing compounds (D) include 3-hexyn-2,5-diol, 2,5-dimethyl-3-hexyn-2,5-diol, 3,6-dimethyl-4-octin-3,6-diol, 1,4-butyndiol, 2,4-hexadiin-1,6-diol, 1,4-butanediol, 2,2,3,3-tetrafluoro-1,4-butanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, cis-1,4-dihydroxy-2-butene, 1,4-benzenedimethanol, and combinations thereof.

[0031] The content of hydroxyl-containing compound (D) is preferably 0.001 to 10% by mass (more preferably 0.005 to 5% by mass; even more preferably 0.01 to 1% by mass) based on the aqueous solution used for manufacturing electronic equipment. A preferred embodiment of the present invention is one in which the hydroxyl-containing compound (D) is not included.

[0032] Surfactants (E) The aqueous solution for manufacturing electronic equipment according to the present invention may further contain a surfactant (E). The surfactant (E) is useful for improving the coatability and solubility. Here, the surfactant (E) may be different from alkylcarboxylic acid compounds (A) or hydroxyl-containing compounds (D). Examples of surfactants (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 octyl phenol ether and polyoxyethylene nonyl phenol 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. Furthermore, examples include fluorine-based surfactants such as product names F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), product names Megafac F171, F173, R-08, R-30, R-2011 (manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), product names Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The surfactant (E) content is preferably 0.01 to 5% by mass, and more preferably 0.02 to 0.5% by mass, based on the aqueous solution used for manufacturing electronic equipment. A preferred embodiment of the present invention is one in which the surfactant (E) is not included.

[0033] Additive (F) The aqueous solution for manufacturing electronic equipment according to the present invention may further contain additive (F). In the present invention, additive (F) comprises an acid, a base, a disinfectant, an antibacterial agent, a preservative, or an antifungal agent. The acid in additive (F) is different from alkylcarboxylic acid compound (A). The base in additive (F) is different from nitrogen-containing compound (C).

[0034] Acids or bases can be used to adjust the pH of the treatment solution or to improve the solubility of additive components. Examples of acids include aromatic carboxylic acids.

[0035] Additive (F) may include antibacterial, antifungal, preservative, or fungicide agents as needed. These chemicals are used to prevent the growth of bacteria and fungi over time. Examples of these chemicals include alcohols such as phenoxyethanol and isothiazolone. Bestcide (manufactured by Nippon Soda Co., Ltd.) is a particularly effective antibacterial, antifungal, and fungicide.

[0036] The content of additive (F) is preferably 0.0001 to 10% by mass (more preferably 0.0005 to 0.1% by mass) based on the aqueous solution used for manufacturing electronic equipment. The absence of additive (F) is also a preferred embodiment of the present invention.

[0037] The aqueous solution used for manufacturing electronic equipment according to the present invention can be filtered after its components have been dissolved to remove impurities and / or insoluble matter.

[0038] <Method for manufacturing resist patterns> The present invention also provides a method for manufacturing a resist pattern using the above-described aqueous solution for manufacturing electronic equipment. The photosensitive resin composition (resist composition) used in this method may be either positive or negative type; the positive type is more preferred. A typical resist pattern manufacturing method to which the aqueous solution for manufacturing electronic equipment according to the present invention is applied comprises the following steps. (1) Applying a photosensitive resin composition to a substrate with or without an intermediate layer to form a photosensitive resin layer, (2) Expose the photosensitive resin layer to radiation, (3) Develop the exposed photosensitive resin layer. (4) Wash the developed layer with the above-mentioned electronic equipment manufacturing aqueous solution.

[0039] The details are explained below. First, a photosensitive resin composition is applied (e.g., laminated) to a substrate such as a silicon substrate or glass substrate, which has been pre-treated as necessary, to form a photosensitive resin layer. While known lamination methods can be used, coating methods such as spin coating are preferred. The photosensitive resin composition can be directly laminated onto the substrate, or it can be laminated via one or more intermediate layers (e.g., BARC). Furthermore, an anti-reflective film (e.g., TARC) may be laminated above the photosensitive resin layer (on the side opposite the substrate). Layers other than the photosensitive resin layer will be described later. By forming an anti-reflective film above or below the photosensitive resin film, the cross-sectional shape and exposure margin can be improved.

[0040] Typical examples of positive or negative photosensitive resin compositions used in the resist pattern manufacturing method of the present invention include, for example, those comprising a quinone diazide-based photosensitive agent and an alkali-soluble resin, and chemically amplified photosensitive resin compositions. From the viewpoint of forming high-resolution fine resist patterns, chemically amplified photosensitive resin compositions are preferred, such as chemically amplified PHS-acrylate hybrid EUV resist compositions. These are more preferably positive-type photosensitive resin compositions.

[0041] Examples of quinone diazide-based photosensitive resins used in a positive-type photosensitive resin composition comprising the above-mentioned quinone diazide-based photosensitive agent 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, esters or amides of these sulfonic acids, and examples of alkali-soluble resins include novolac resins, polyvinylphenol, polyvinyl alcohol, copolymers of acrylic acid or methacrylic acid. Preferred novolac resins are those produced from one or more phenols such as phenol, o-cresol, m-cresol, p-cresol, and xylenol, and one or more aldehydes such as formaldehyde and paraformaldehyde.

[0042] Furthermore, examples of chemically amplified photosensitive resin compositions include a positive-type chemically amplified photosensitive resin composition containing a compound that generates acid upon irradiation with radiation (photoacid generator) and a resin whose polarity increases due to the action of the acid generated from the photoacid generator, resulting in a change in solubility in the developer between the exposed and unexposed areas; and a negative-type chemically amplified photosensitive resin composition consisting of an alkali-soluble resin, a photoacid generator, and a crosslinking agent, in which crosslinking of the resin occurs by the crosslinking agent due to the action of the acid, resulting in a change in solubility in the developer between the exposed and unexposed areas.

[0043] Examples of resins whose polarity increases due to the action of the aforementioned acid, resulting in a change in solubility in the developer between the exposed and unexposed areas, include resins having groups in the main chain or side chains, or both the main chain and side chains, that decompose under the action of the acid to produce alkali-soluble groups. Representative examples include polymers in which acetal groups or ketal groups are introduced as protecting groups to hydroxystyrene polymers (PHS) (e.g., Japanese Patent Publication No. 2-19847), and similar polymers in which t-butoxycarbonyloxy groups or p-tetrahydropyranyloxy groups are introduced as acid-decomposing groups (e.g., Japanese Patent Publication No. 2-209977).

[0044] Furthermore, any compound that generates acid upon irradiation with radiation can be used as the photoacid generator. Examples include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arusonium salts, organic halogen compounds, organometallic / organohalides, photoacid generators having o-nitrobenzyl type protecting groups, compounds that decompose to generate sulfonic acid through photodecomposition, such as iminosulfonates, disulfone compounds, diazoketosulfones, and diazodisulfone compounds. Compounds in which these light-activated acid-generating groups or compounds are introduced into the main chain or side chain of a polymer can also be used.

[0045] Furthermore, the chemically amplified photosensitive resin composition may optionally contain acid-degradable dissolution inhibitors, dyes, plasticizers, surfactants, photosensitizers, organic basic compounds, and compounds that promote solubility in developing solutions.

[0046] The above-mentioned photosensitive resin composition is applied to a substrate, for example, using a suitable coating device and method such as a spinner or coater, and then heated on a hot plate to remove the solvent in the photosensitive resin composition, thereby forming a photosensitive resin layer. The heating temperature varies depending on the solvent or resist composition used, but is generally 70 to 150°C, preferably 90 to 150°C, and can be carried out for 10 to 180 seconds, preferably 30 to 120 seconds, when using a hot plate, or for 1 to 30 minutes when using a clean oven.

[0047] In the resist pattern manufacturing method of the present invention, the presence of films and layers other than the photosensitive resin layer is also permitted. An intermediate layer may be interposed so that the substrate and the photosensitive resin layer do not come into direct contact. An intermediate layer is a layer formed between the substrate and the photosensitive resin layer, and is also called a lower layer film. Examples of lower layers include substrate modification films, planarization films, lower layer anti-reflective films (BARC), inorganic hard mask intermediate layers (silicon oxide films, silicon nitride films, and silicon nitrogen oxide films), and adhesion films. For information on the formation of inorganic hard mask intermediate layers, please refer to Japanese Patent No. 5336306. The intermediate layer may consist of one layer or multiple layers. In addition, an upper layer anti-reflective film (TARC) may be formed on the photosensitive resin layer.

[0048] In the resist pattern manufacturing process of the present invention, known methods can be used for the layer configuration according to the process conditions, but examples of such layer configurations include the following. Substrate / lower film / photosensitive resin layer Substrate / Planarization film / BARC / Photosensitive resin layer Substrate / Planarization film / BARC / Photosensitive resin layer / TARC Substrate / Planarization film / Inorganic hard mask intermediate layer / Photosensitive resin layer / TARC Substrate / Planarization film / Inorganic hard mask intermediate layer / BARC / Photosensitive resin layer / TARC Substrate / Planarization film / Adhesion film / BARC / Photosensitive resin layer / TARC Substrate / Substrate modification layer / Planarization film / BARC / Photosensitive resin layer / TARC Substrate / Substrate modification layer / Planarization film / Adhesion film / BARC / Photosensitive resin layer / TARC These layers can be cured by heating and / or exposure after coating, or deposited using known methods such as CVD. These layers can be removed by known methods (such as etching), and each can be patterned using the layer above it as a mask.

[0049] The photosensitive resin layer is exposed through a predetermined mask. If other layers are included (such as TARC), they may be exposed together. 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 lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and extreme ultraviolet light (wavelength 13.5 nm) can be used, with extreme ultraviolet light being more preferred. These wavelengths are allowed within a range of ±5%, preferably within a range of ±1%. After exposure, post-exposure heating (PEB) may be performed as needed. The temperature for post-exposure heating is appropriately selected from 70 to 150°C, preferably 80 to 120°C, and the heating time is 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0050] Next, development is carried out using a developer. For development in the resist pattern manufacturing method of the present invention, preferably, a 2.38% by mass (±1% acceptable) aqueous solution of tetramethylammonium hydroxide (TMAH) is used. Furthermore, surfactants and the like can be added to these developers. The temperature of the developer is generally 5 to 50°C, preferably 25 to 40°C, and the development time is generally 10 to 300 seconds, preferably 20 to 60 seconds, which can be appropriately selected. Known methods such as paddle development can be used for development. As mentioned above, the resist patterns of the present invention include not only those obtained by exposing and developing a resist film, but also those in which the walls are thickened by further covering them with other layers or films.

[0051] The resist pattern (developed photosensitive resin layer) created up to the above-described step is in an unwashed state. This resist pattern can be washed with the electronic equipment manufacturing aqueous solution according to the present invention. The time for which the electronic equipment manufacturing aqueous solution is in contact with the resist pattern, i.e., the processing time, is preferably 1 second or longer. The processing temperature can also be arbitrary. The method of bringing the electronic equipment manufacturing aqueous solution into contact with the resist is also arbitrary; for example, it can be done by immersing the resist substrate in the electronic equipment manufacturing aqueous solution or by dropping the electronic equipment manufacturing aqueous solution onto the surface of a rotating resist substrate.

[0052] In the resist pattern manufacturing method according to the present invention, the developed resist pattern can be washed with another cleaning solution before and / or after the cleaning treatment with the electronic equipment manufacturing aqueous solution. The other cleaning solution is preferably water, and more preferably pure water (DW, deionized water, etc.). The cleaning before the treatment is useful for washing off the developer adhering to the resist pattern. The cleaning after the treatment is useful for washing off the electronic equipment manufacturing aqueous solution. A preferred embodiment of the manufacturing method according to the present invention is a method in which the developed resist pattern is washed by pouring pure water into it to replace the developer, and then, while maintaining the state in which the pattern is immersed in pure water, the pattern is washed again by pouring in the electronic equipment manufacturing aqueous solution to replace the pure water. The cleaning of the electronic equipment using water-soluble materials may be carried out by known methods. For example, this can be done by immersing a resist substrate in an electronic equipment manufacturing aqueous solution, or by dropping the electronic equipment manufacturing aqueous solution onto the surface of a rotating resist substrate. These methods may be combined as appropriate.

[0053] One of the conditions that makes pattern collapse likely is where the gap between the walls of the resist pattern is narrowest. This is a particularly severe condition where the walls of the resist pattern are parallel. In this specification, the minimum space size is defined as the distance between the smallest gaps on a single circuit unit. Preferably, a single circuit unit becomes a single semiconductor in a later process. It is also preferable that a single semiconductor contains one circuit unit in the horizontal direction and multiple circuit units in the vertical direction. Of course, unlike test samples, if the frequency of occurrence of areas with narrow gaps between walls is low, the frequency of defects will decrease, and thus 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 10 to 30 nm, more preferably 10 to 20 nm, and even more preferably 10 to 17 nm.

[0054] <Device manufacturing method> The present invention relates to a method for manufacturing a device, comprising a method for manufacturing a resist pattern using an aqueous solution for manufacturing electronic equipment. Preferably, the method for manufacturing a device according to 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 peeled off as necessary. Preferably, the device is a semiconductor. In the manufacturing method of the present invention, the intermediate layer and / or substrate can be processed by etching using a resist pattern as a mask. Known etching methods such as dry etching and wet etching can be used, with dry etching being more preferable. For example, the intermediate layer can be etched using the resist pattern as an etching mask, and the substrate can be processed by etching the resulting intermediate layer pattern using the etching mask. Alternatively, the substrate can be etched while etching the layer below the resist layer (e.g., the intermediate layer) using the resist pattern as an etching mask. The processed substrate becomes, for example, a patterned substrate. Wiring can be formed on the substrate using the formed pattern. These layers can preferably be removed by dry etching with O2, CF4, CHF3, Cl2, or BCl3, with O2 or CF4 being preferred. In a preferred embodiment, the method for manufacturing the device according to the present invention further includes forming wiring on a processed substrate.

[0055] <Stress on the resist wall> As described in Namatsu et al. Appl. Phys. Lett. 1995 (66) pp. 2655-2657, and as schematically shown in Figure 1, the stress on the wall during rinse drying can be expressed by the following formula. 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, such as SEM imaging.

[0056] As can be seen from the above formula, shorter D or shorter W causes more stress. In this specification, “pitch size” means one unit of the resist pattern unit array having W and D, as shown in Figure 1. This means that the finer the required resist pattern (narrower pitch size), the greater the stress on the resist pattern. As the pattern becomes finer, the conditions become more stringent, and more improvements are required in the aqueous solutions used in electronic equipment manufacturing (e.g., rinse compositions).

[0057] The present invention will be described below with reference to various examples. However, the embodiments of the present invention are not limited to these examples.

[0058] <Preparation example of Example 101> To deionized water, 2-methylpropanoic acid is added as the alkyl carboxylic acid compound (A) to a concentration of 1.0% by mass, and n-butylamine is added as the nitrogen-containing compound (C) to a concentration of 0.01% by mass. The mixture is then stirred. Visual confirmation is made that the mixture is completely dissolved. This mixture is filtered (pore size = 10 nm) to obtain the aqueous solution of Example 101.

[0059] <Preparation examples of Examples 102-112, comparative preparation examples of Comparative Examples 101-104> Using the alkylcarboxylic acid compound (A) and nitrogen-containing compound (C) as shown in Table 1, aqueous solutions of Examples 102-112 and Comparative Examples 101-104 were prepared in the same manner as the preparation example of Example 101, so that they had the concentrations shown in Table 1. Comparative Example 101 is obtained by filtering deionized water with no additives added. [Table 1]

[0060] <Evaluation board fabrication 1> A BARC composition (AZ Kr-F17B, Merck Electronics Co., Ltd. (hereinafter referred to as ME)) is applied to a silicon substrate by spin coating and heated on a hot plate at 180°C for 60 seconds to obtain a BARC film with a thickness of 80 nm. A PHS-acrylate-based chemically amplified resist (DX6270P, ME) is applied on top of this and heated on a hot plate at 120°C for 90 seconds to obtain a resist film with a thickness of 620 nm. This substrate is exposed using a KrF exposure system (FPA3000 EX5, Canon) through a mask (250 nm line / space 1:1). The exposure dose at this time is 25 mJ / cm². 2 ~40 mJ / cm² 2 This is changed so that the resulting line width changes. Next, perform PEB on a hot plate at 100°C for 60 seconds, pour in a 2.38% by mass TMAH aqueous developer solution, and hold for 60 seconds (paddle). With the developer solution paddled, start pouring in water, and while rotating the substrate, replace the developer solution with water. Stop with the substrate paddled with water and let it stand for 60 seconds. Then, with the substrate paddled with water, pour in the aqueous solution of Example 101 prepared above, and while rotating the substrate, replace the water with the aqueous solution of Example 101. Stop with the substrate paddled with the aqueous solution of Example 101 and let it stand for 10 seconds. Spin dry the substrate for 30 seconds to dry it. For Examples 102-112 and Comparative Examples 102-104, evaluation substrates were prepared using the respective aqueous solutions in the same manner as described above. Comparative Example 101 differs from Example 101 in that the substrate is immediately spin-dried after being paddled with water, but otherwise it is the same.

[0061] <Evaluation of fall prevention> The pattern collapse prevention performance will be evaluated using the evaluation substrate fabricated in 1. The resist pattern will be observed using an SEM device S-9220 (Hitachi High-Technologies) to check for pattern collapse. The evaluation criteria are as follows. In Comparative Example 101, pattern collapse of the resist pattern was observed when the line width became narrower than 190 nm. The results are shown in Table 1. A: No pattern distortion was observed in resist patterns with line widths between 150nm and 177nm. B: Pattern distortion is observed in resist patterns with line widths between 150nm and 197nm. C: Pattern distortion is observed in resist patterns with line widths greater than 200 nm.

[0062] <Preparation examples of Examples 201-206, comparative preparation examples of Comparative Examples 201 and 202> Using the alkylcarboxylic acid compound (A) and nitrogen-containing compound (C) as shown in Table 2, aqueous solutions of Examples 201-206 and Comparative Examples 201 and 202 were prepared in the same manner as the preparation example of Example 101, so as to achieve the concentrations shown in Table 2. Comparative Example 201 is obtained by filtering deionized water with no additives added. [Table 2]

[0063] <Fabrication of evaluation board 2> A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. A PHS-acrylate-based chemically amplified resist for EUV is then applied by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 50 nm. This substrate is exposed using an EUV lithography system (NXE:3300B, ASML) through a mask (18 nm line / space 1:1). The exposure amount is varied to change the resulting line width. Subsequently, PEB is performed on a hot plate at 100°C for 60 seconds, and a 2.38 mass% TMAH aqueous developer solution is poured in and held for 30 seconds (paddle). While the developer is paddled, water is started to flow, and the substrate is rotated to replace the developer with water. The substrate is then stopped with the water paddled and allowed to stand for 60 seconds. Next, with the substrate paddled in water, the aqueous solution of Example 201 is poured in, and the substrate is rotated to replace the water with the aqueous solution of Example 201. The substrate is then stopped for 10 seconds while paddled in the aqueous solution of Example 201. The substrate is then spin-dried to dry it. For the aqueous solutions of Examples 202 to 206 and Comparative Example 202, evaluation substrates were prepared using each aqueous solution in the same manner as described above. Comparative Example 201 differs from Example 201 in that the developer is replaced with water, and after paddled with water, the substrate is immediately spin-dried; otherwise, it is the same.

[0064] <Evaluation of the limit pattern size (18nm line / space)> The resist pattern formed on the evaluation substrate from fabrication 2 is observed for line width and pattern deformation using a length-measuring SEM CG5000 (Hitachi High-Technologies). As the exposure amount increases, the line width decreases. The minimum line width size at which pattern deformation does not occur is defined as the "limit pattern size". In the case of the aqueous solution of Comparative Example 201, pattern collapse is confirmed at a line size of 20.3 nm. On the other hand, no collapse is confirmed at 20.8 nm, so the critical pattern size is defined as 20.8 nm. The results are shown in Table 2.

[0065] <Preparation of Evaluation Substrate 3> Each evaluation substrate is produced in the same manner as in the above Production of Evaluation Substrate 2, except that the mask is changed to one with a narrower pitch of 17 nm line / space 1:1.

[0066] <Evaluation of Critical Pattern Size (17 nm Line / Space)> The critical pattern size is measured for the resist pattern formed on the evaluation substrate of Production 3 in the same manner as in the above Evaluation of Critical Pattern Size (18 nm Line / Space). The results are shown in Table 2. In Comparative Examples 201 and 202, no pattern was formed in Production 3, so measurement was determined to be impossible.

[0067] <Evaluation of LWR> The LWR of the resist pattern formed on the evaluation substrate of Production 2 is evaluated. The LWR (Line Width Roughness) of the resist pattern having a line width of 18 nm is measured using a length-measuring SEM CG5000. The results are shown in Table 2.

Claims

1. Alkylcarboxylic acid compound (A), and Solvent (B) Aqueous solutions for manufacturing electronic equipment containing: Here, The alkylcarboxylic acid compound (A) is represented by formula (a); A １ -COOH Formula (a) (In the formula, A １ is C ３－１２ It is alkyl, preferably A １ C is a linear or branched C ３－１０ (is alkyl) and Solvent (B) consists of water.

2. The aqueous solution for manufacturing electronic equipment according to claim 1, further comprising a nitrogen-containing compound (C).

3. The aqueous solution for manufacturing electronic equipment according to claim 1 or 2, wherein the content of alkylcarboxylic acid compound (A) is 0.01 to 10% by mass, based on the aqueous solution for manufacturing electronic equipment; Preferably, the solvent (B) content is 80 to 99.99% by mass, based on the aqueous solution used for manufacturing electronic equipment; Preferably, the water content in solvent (B) is 80 to 99.99% by mass, based on the aqueous solution used for manufacturing electronic equipment; or Preferably, the nitrogen-containing compound (C) content is 0.0001 to 10% by mass, based on the aqueous solution used for manufacturing electronic equipment.

4. Aqueous aqueous solution for manufacturing electronic equipment according to at least one of claims 1 to 3, further comprising a hydroxyl-containing compound (D): Preferably, the product further contains a surfactant (E).

5. An aqueous solution for manufacturing electronic equipment according to at least one of claims 1 to 4, further comprising additive (F); Here, Additive (F) comprises acids, bases, disinfectants, antibacterial agents, preservatives, or fungicides; Preferably, the content of the hydroxyl-containing compound (D) is 0.001 to 10% by mass, based on the aqueous solution used for manufacturing electronic equipment; Preferably, the surfactant (E) content is 0.01 to 5% by mass, based on the aqueous solution for manufacturing electronic equipment; or Preferably, the content of additive (F) is 0.0001 to 10% by mass, based on the aqueous solution used for manufacturing electronic equipment.

6. An aqueous solution for semiconductor manufacturing, according to at least one of claims 1 to 5: Preferably, the aqueous solution for manufacturing electronic equipment is an aqueous solution for manufacturing semiconductor substrates; Preferably, the aqueous solution for electronic equipment manufacturing is a cleaning solution for semiconductor substrate manufacturing processes; Preferably, the aqueous solution for manufacturing electronic equipment is a lithography cleaning solution; or Preferably, the aqueous solution used for manufacturing electronic equipment is a resist pattern cleaning solution.

7. A method for manufacturing a resist pattern using an aqueous solution for manufacturing electronic equipment according to at least one of claims 1 to 6.

8. A method for manufacturing a resist pattern comprising the following steps: (1) A photosensitive resin composition is applied to a substrate with or without an intermediate layer to form a photosensitive resin layer. (2) Expose the photosensitive resin layer to radiation, (3) Develop the exposed photosensitive resin layer. (4) Wash the developed layer with the electronic equipment manufacturing aqueous solution according to any one of claims 1 to 6.

9. The method for producing a resist pattern according to claim 8, wherein the photosensitive resin composition is a chemically amplified photosensitive resin composition, and preferably exposure is performed using extreme ultraviolet light.

10. A method for manufacturing a resist pattern according to any one of claims 7 to 9, wherein the minimum space size of the resist pattern in a single circuit unit is 10 to 30 nm.

11. A method for manufacturing a device, comprising a method for manufacturing a resist pattern according to any one of claims 7 to 10.

12. A method for manufacturing a device according to claim 11, further comprising etching a resist pattern manufactured by any one of claims 7 to 10 as a mask to process a substrate.

13. A method for manufacturing a device according to claim 11 or 12, further comprising forming wiring on a processed substrate.

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