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, which can prevent pattern collapse or suppress non-uniformity of resist pattern width. The present invention provides an aqueous solution for manufacturing electronic devices, comprising an alkyl carboxylic acid compound (A) and a solvent (B), 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.

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 high integration of LSIs has been increasing, and finer patterns are being demanded. In order to meet such needs, lithography processes using short-wavelength light such as KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet light (EUV; 13 nm), X-rays, electron beams, etc. are being put to practical use. In order to meet such 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 light with a short wavelength, the production yield, such as collapse of the fine pattern, becomes a problem because a very fine structure is created.

[0003] In this situation, Patent Document 1 discusses a rinse solution for lithography that is excellent in performance such as pattern collapse margin, defects, and LWR, similar to conventional systems containing surfactants, and also has excellent melting properties.

[0004] As another attempt, the use of a surfactant containing fluorine has been investigated (Patent Document 2 and Patent Document 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-219577 A [Patent Document 2] International Publication No. 2018 / 095885 [Patent Document 3] International Publication No. 2017 / 220479 Summary of the Invention [Problem to be solved by the invention]

[0006] The inventors have found that there are one or more problems that still require improvement, such as the following: reducing defects in a fine resist pattern; suppressing the occurrence of bridges in a resist pattern; preventing the collapse of a fine resist pattern; suppressing non-uniformity in the resist pattern width; reducing residues after removal of the aqueous solution for manufacturing electronic devices; reducing the surface tension of the aqueous solution for manufacturing electronic devices; providing an aqueous solution for manufacturing electronic devices with little environmental impact; providing an aqueous solution for manufacturing electronic devices with little risk of handling; providing an aqueous solution for manufacturing electronic devices with excellent storage stability (e.g., long-term storage); providing an aqueous solution for manufacturing electronic devices with little effect on the resist pattern. 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]

[0007] The electronic device manufacturing aqueous solution according to the present invention comprises: An alkyl carboxylic acid compound (A), and Solvent (B) It comprises Where: The alkyl carboxylic acid compound (A) is represented by the 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-mentioned aqueous solution for manufacturing electronic devices.

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

[0010] 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 the resist pattern. It is possible to prevent the resist pattern from collapsing in a fine resist pattern. It is possible to suppress non-uniformity in the width of the resist pattern. 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 environmental impact 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. It is possible to reduce the impact of the aqueous solution for manufacturing electronic devices on the resist pattern. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram showing a state in which a resist wall is being rinsed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The embodiment of the present invention will be described in detail below.

[0013] definition In this specification, unless otherwise specifically stated, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "a" or "the" means "at least one." An element of a concept may be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of the elements as well as its use alone. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "Cx-y ", "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown by structural formulas, the n or m in parentheses indicates the number of repeats. Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to a compound having that function (for example, in the case of a base generator, it is a compound 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 according to the present invention as the solvent (B) or another component.

[0014] <Electronic device manufacturing aqueous solution> The aqueous solution for manufacturing electronic devices according to the present invention comprises an alkyl carboxylic acid compound (A) and a solvent (B). Here, the electronic device manufacturing aqueous solution is used during the process of manufacturing 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 electronic equipment manufacture is preferably an aqueous solution for semiconductor substrate manufacture, more preferably a cleaning solution for semiconductor substrate manufacture process, even more preferably a lithography cleaning solution, and even more preferably a resist pattern cleaning solution. The aqueous solution for electronic equipment manufacture which is an aqueous solution for semiconductor substrate manufacture can also be said to be an aqueous solution for semiconductor substrate manufacture consisting of only the aqueous solution for electronic equipment of the present invention. In another embodiment of the present invention, the aqueous solution for manufacturing electronic devices may be a rinse composition used for rinsing a resist pattern that has been exposed and developed.

[0015] Alkyl carboxylic acid compound (A) The alkyl carboxylic acid compound (A) used in the present invention is represented by the formula (a). A1-COOH formula (a) Where: 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; more preferably linear or branched C 3-9 alkyl; even more preferably linear or branched C 3-8 It is an alkyl. In one preferred embodiment of the invention, A1 is a straight or branched C3 alkyl.

[0016] Specific examples of the alkyl carboxylic 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 alkyl carboxylic acid compound (A) is preferably 0.01 to 10 mass % (more preferably 0.02 to 5 mass %; further preferably 0.02 to 1 mass %) based on the aqueous solution for manufacturing electronic devices.

[0018] One of the effects of the alkyl carboxylic acid compound (A) in the electronics manufacturing aqueous solution according to the present invention is that it contributes to preventing the pattern collapse after development of the resist pattern. Without being bound by theory, it is believed that the low affinity between the alkyl carboxylic acid compound of the present invention and the resist wall can increase the contact angle of the electronics manufacturing aqueous solution in the rinse drying step. Specifically, it is believed that the alkyl in formula (a) can reduce the surface tension of the composition, and the carboxyl can improve the solubility of the electronics manufacturing aqueous solution, thereby improving the balance between solubility and low surface tension.

[0019] Solvent (B) The solvent (B) comprises water, which is preferably deionized water. Considering that it is used in the manufacturing process of electronic devices, it is preferable that the solvent (B) has a small amount of impurities. The impurity concentration of the solvent (B) is preferably 1 ppm or less (more preferably 100 ppb or less; further preferably 10 ppb or less). The content of water 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; still 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 content of water in the solvent (B) is 100% by mass.

[0020] 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 are preferred in terms of the storage stability of the solution. Two or more of these solvents can also be mixed and used.

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

[0022] The aqueous solution for manufacturing electronic devices according to the present invention essentially contains the above-mentioned components (A) and (B), but may contain further compounds as necessary. This will be described in detail below. The components other than (A) and (B) (when there are multiple components, the sum of the components) in the entire composition is preferably 0 to 10 mass % (more preferably 0 to 5 mass %; further preferably 0 to 3 mass %) based on the aqueous solution for manufacturing electronic devices. A form in which the aqueous solution for manufacturing electronic devices according to the present invention does not contain any components other than (A) and (B) (0 mass %) is also a preferred form of the present invention.

[0023] Nitrogen-containing compounds (C) The aqueous solution for manufacturing electronic devices according to the present invention contains a nitrogen-containing compound (C). The nitrogen-containing compound (C) may have one or more nitrogen atoms in the compound. As described above, the aqueous solution for manufacturing electronic devices according to the present invention contains the alkyl carboxylic acid compound (A) to suppress pattern collapse, but by combining it with the nitrogen-containing compound (C), pattern collapse can be further suppressed, and other defects such as pattern melting and resist residue can also be suppressed. Without being bound by theory, it is believed that the inclusion of the nitrogen-containing compound (C) makes it possible to reduce the effect of the alkyl carboxylic acid compound (A) on the resist pattern.

[0024] Examples of the nitrogen-containing compound (C) 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 their derivatives (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:

[0025] The nitrogen-containing compound (C) 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.

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

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

[0028] Hydroxy-Containing Compounds (D) The aqueous solution for manufacturing electronic devices according to the present invention may further contain a hydroxy-containing compound (D). The hydroxy-containing compound (D) may have one or more hydroxy groups in the compound, and preferably has one to three hydroxy groups, and may be substituted with fluorine. 3-30 Here, the fluorine substitution replaces the H in the compound with F, but this substitution does not replace the H in the hydroxy. It is believed that by further containing this hydroxy-containing compound (D), it becomes possible to further reduce the limit size at which the particles do not collapse.

[0029] In a preferred embodiment, the hydroxy-containing compound (D) is represented by formula (d). [ka] During the ceremony, R d1 , R d2 , R d3 , and R d4 are each independently hydrogen, fluorine, or C 1-5 (preferably, each independently, hydrogen, fluorine, methyl, ethyl, t-butyl, or isopropyl; more preferably, each independently, hydrogen, methyl, or ethyl). L d1 and L d2 are each independently 1-20 Alkylene, C 1-20 Cycloalkylene, C 2-4 Alkenylene, C 2-4 Alkynylene of C 6-20 These groups are fluorine, C 1-5 It may be substituted with alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon group having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. Preferably, L d1 and L d2 each independently represents an optionally fluorinated group; 1-5 Alkylene, C 2-4 or phenylene (C6 arylene). d1 and L d2 Each independently is preferably a fluorine-substituted C 2-4 alkylene, acetylene (C alkynylene) or phenylene; even more preferably fluorine-substituted C 2-4 The alkylenes are acetylene and acetylene. It is possible to obtain the effects of the present invention without using a fluorine-containing component. d1 and L d2 are each independently, C 1-5 Alkylene, C 2-4 or phenylene (more preferably each independently represents C 2-4 alkylene, acetylene or phenylene; more preferably each independently C 2-4of alkylenes, acetylenes). h is 0, 1, or 2 (preferably 0 or 1; more preferably 0).

[0030] Specific examples of the hydroxy-containing compound (D) include 3-hexyne-2,5-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 1,4-butynediol, 2,4-hexadiyne-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 the hydroxy-containing compound (D) is preferably 0.001 to 10 mass % (more preferably 0.005 to 5 mass %; further preferably 0.01 to 1 mass %) based on the aqueous solution for manufacturing electronic devices. In one preferred embodiment of the present invention, the hydroxy-containing compound (D) is not contained.

[0032] Surfactant (E) The aqueous solution for manufacturing electronic devices according to the present invention may further include a surfactant (E). The surfactant (E) is useful for improving the coating property and solubility. Here, the surfactant (E) is different from the alkyl carboxylic acid compound (A) and the hydroxy-containing compound (D). Examples of the surfactant (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 (manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-08, R-30, and R-2011 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited), and Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The content of the surfactant (E) is preferably from 0.01 to 5 mass %, and more preferably from 0.02 to 0.5 mass %, based on the aqueous solution for manufacturing electronic devices. In one preferred embodiment of the present invention, the surfactant (E) is not included.

[0033] 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 alkyl carboxylic acid compound (A). The base in the additive (F) is different from the nitrogen-containing compound (C).

[0034] The acid or base can be used to adjust the pH value of the processing solution or to improve the solubility of the additive components. Examples of the acid include aromatic carboxylic acids.

[0035] Additives (F) may optionally include antibacterial, antifungal, preservative or bactericides. These chemicals are used to prevent bacteria and fungi from growing over time. Examples of these chemicals are alcohols such as phenoxyethanol, and isothiazolones. Bestcide (Nippon Soda Co.) is a particularly effective antibacterial, antifungal and bactericide.

[0036] The content of the additive (F) is preferably 0.0001 to 10 mass % (more preferably 0.0005 to 0.1 mass %) based on the aqueous solution for manufacturing electronic devices. In one preferred embodiment of the present invention, no additive (F) is contained.

[0037] The aqueous electronics manufacturing solution according to the present invention may be filtered, after its components have been dissolved, to remove impurities and / or insoluble matter.

[0038] <Method of manufacturing resist pattern> The present invention also provides a method for producing a resist pattern using the above-mentioned aqueous solution for electronic device manufacture. The photosensitive resin composition (resist composition) used in this method may be either positive or negative; positive is more preferred. A representative method for producing a resist pattern using the aqueous solution for electronic device manufacture 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) Rinse the developed layer with the above aqueous electronics manufacturing solution.

[0039] The details are explained below. First, a photosensitive resin composition is applied (for example, laminated) above a substrate such as a silicon substrate or a glass substrate, which has been pretreated as necessary, to form a photosensitive resin layer. A known method can be used for lamination, but a coating method such as spin coating is preferable. The photosensitive resin composition can be laminated directly on the substrate, or can be laminated via one or more intermediate layers (for example, BARC). An anti-reflective film (for example, TARC) may be laminated above the photosensitive resin layer (opposite side to 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] Representative examples of the positive or negative photosensitive resin composition used in the resist pattern production method of the present invention include, for example, those containing a quinone diazide-based photosensitizer and an alkali-soluble resin, and chemically amplified photosensitive resin compositions. From the viewpoint of forming a high-resolution fine resist pattern, chemically amplified photosensitive resin compositions are preferred, such as chemically amplified PHS-acrylate hybrid EUV resist compositions. These are more preferably positive photosensitive resin compositions.

[0041] Examples of the quinone diazide photosensitizer used in the positive photosensitive resin composition containing the quinone diazide photosensitizer and the 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 the alkali-soluble resin include novolak resins, polyvinylphenols, polyvinyl alcohols, copolymers of acrylic acid or methacrylic acid, etc. Preferable examples of the novolak resin include those produced from one or more phenols such as phenol, o-cresol, m-cresol, p-cresol, xylenol, etc., and one or more aldehydes such as formaldehyde, paraformaldehyde, etc.

[0042] Examples of chemically amplified photosensitive resin compositions include positive-type chemically amplified photosensitive resin compositions containing a compound that generates an acid when irradiated with radiation (photoacid generator) 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 which are composed 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 acid, so that the solubility in a developer changes between exposed and unexposed areas.

[0043] The 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 or side chains of the resin, or both the main and side chains, which decompose under the action of an acid to generate an alkali-soluble group.Typical examples of such resins include polymers in which an acetal or ketal group is introduced as a protective 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.).

[0044] The photoacid generator may be any compound that generates an acid upon irradiation with radiation, and examples of such compounds 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 groups or compounds that generate an acid upon exposure to light 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 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.

[0046] The photosensitive resin composition is applied on a substrate by a suitable application device and application method such as a spinner or coater, and is heated on a hot plate to remove the solvent in the photosensitive resin composition, 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, for 10 to 180 seconds, preferably 30 to 120 seconds, when using a hot plate, and for 1 to 30 minutes when using a clean oven.

[0047] In the resist pattern manufacturing method of the present invention, the presence of a film or layer other than the photosensitive resin layer is also permitted. The substrate and the photosensitive resin layer may not be in direct contact with each other, and an intermediate layer may be interposed. The intermediate layer is a layer formed between the substrate and the photosensitive resin layer, and is also called an underlayer film. Examples of the underlayer film include a substrate modification film, a planarization film, a bottom antireflective film (BARC), an inorganic hard mask intermediate layer (a silicon oxide film, a silicon nitride film, and a silicon oxide nitrogen film), and an adhesion film. For the formation of the inorganic hard mask intermediate layer, reference can be made to Japanese Patent No. 5336306. The intermediate layer may be composed of one layer or multiple layers. Also, a top antireflective film (TARC) may be formed on the photosensitive resin layer.

[0048] In the resist pattern production process of the present invention, the layer structure can be formed by a known method in accordance with the process conditions. For example, the following laminate structure can be mentioned. 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 / flattening 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 formed by known techniques such as curing by heating and / or exposure to light after application, or by CVD, etc. These layers can be removed by known techniques (such as etching), and each layer can be patterned using the upper layer as a mask.

[0049] The photosensitive resin layer is exposed through a predetermined mask. When 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 it is preferable to expose with light having a wavelength of 13.5 to 248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet ray (wavelength 13.5 nm) can be used, and extreme ultraviolet ray is more preferable. These wavelengths allow a range of ±5%, preferably ±1%. After exposure, post-exposure baking (PEB) can be performed as necessary. The temperature of post-exposure baking is appropriately selected from 70 to 150°C, preferably 80 to 120°C, and the heating time is appropriately selected from 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0050] Then, development is carried out with 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 generally 5 to 50°C, preferably 25 to 40°C, and the development time is generally appropriately selected from 10 to 300 seconds, preferably 20 to 60 seconds. As the development method, a known technique such as paddle development can be used. As described 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 the walls have been thickened by covering them with other layers or films.

[0051] The resist pattern (developed photosensitive resin layer) created by 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, for example, by immersing the resist substrate in the aqueous solution for manufacturing electronic devices, or by dropping the aqueous solution for manufacturing electronic devices onto the surface of a rotating resist substrate.

[0052] In the resist pattern manufacturing method according to the present invention, the developed resist pattern can be washed with another washing liquid before and / or after the washing process with the aqueous solution for manufacturing electronic devices. The other washing liquid is preferably water, more preferably pure water (DW, deionized water, etc.). Washing before the washing process is useful for washing the developing solution attached to the resist pattern. Washing after the washing process is useful for washing the aqueous solution for manufacturing electronic devices. A preferred embodiment of the manufacturing method according to the present invention is a method in which pure water is poured into the resist pattern after development to replace the developing solution, and the pattern is washed while the aqueous solution for manufacturing electronic devices is poured in while the pattern is kept immersed in the pure water. The cleaning with the aqueous solution of the electronics manufacturing process may be carried out by known methods. For example, the resist substrate may be immersed in the aqueous solution for manufacturing electronic devices, or the aqueous solution for manufacturing electronic devices may be dropped onto the surface of a rotating resist substrate. These methods may be used in combination as appropriate.

[0053] One of the conditions that easily cause pattern collapse is the location where the spacing between the walls of the resist pattern is the narrowest. This is a severe condition when the walls of the resist pattern are parallel to each other. In this specification, the minimum space size is the distance between the locations where the spacing is the smallest on one circuit unit. It is preferable that one circuit unit becomes one semiconductor in a later process. It is also 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 occurrence of locations where the spacing between the walls is narrow is low, the frequency of occurrence of defects will decrease, and the frequency of occurrence of defective products will decrease. In the present invention, the minimum space size of the resist pattern in one circuit unit is preferably from 10 to 30 nm, more preferably from 10 to 20 nm, and even more preferably from 10 to 17 nm.

[0054] <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 processing a substrate by etching 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 the substrate can be processed by etching using the resist pattern as a mask. The etching can be performed by known techniques such as dry etching and wet etching, and dry etching is more preferable. For example, the intermediate layer can be etched using the resist pattern as an etching mask, and the substrate can be etched using the obtained intermediate layer pattern as an etching mask to process the substrate. In addition, the resist pattern can be used as an etching mask to etch the layer below the resist layer (e.g., the intermediate layer), while etching the substrate as it 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.

[0055] <Stress on the resist wall> As described in Namatsu et al. Appl. Phys. Lett. 1995(66) p2655-2657 and shown diagrammatically in FIG. 1, the stress on the wall during rinse drying 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.

[0056] As can be seen from the above formula, a short D or a short W causes more stress. In this specification, "pitch size" means one unit of a 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 is. Thus, the finer the pattern, the more stringent the conditions, and the more improvements are required for electronics manufacturing aqueous solutions (e.g., rinse compositions).

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

[0058] <Preparation Example of Example 101> Add 2-methylpropanoic acid as an alkyl carboxylic acid compound (A) to a concentration of 1.0 mass% and n-butylamine as a nitrogen-containing compound (C) to a concentration of 0.01 mass% to deionized water, and stir. Confirm complete dissolution by visual observation. Filter (pore size = 10 nm) to obtain the aqueous solution of Example 101.

[0059] <Preparation Examples of Examples 102 to 112 and Comparative Preparation Examples of Comparative Examples 101 to 104> Using the alkyl carboxylic acid compound (A) and the nitrogen-containing compound (C) as shown in Table 1, the aqueous solutions of Examples 102 to 112 and Comparative Examples 101 to 104 are prepared in the same manner as in the preparation example of Example 101 above, so as to have the concentrations shown in Table 1. In addition, Comparative Example 101 was obtained by filtering deionized water to which nothing was added. [Table 1]

[0060] <Preparation of evaluation board 1> A BARC composition (AZ Kr-F17B, Merck Electronics Co., Ltd. (hereinafter referred to as ME)) is applied by spin coating onto a silicon substrate and heated on a hot plate at 180°C for 60 seconds to obtain a BARC with a film 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 film thickness of 620 nm. This substrate is exposed through a mask (250 nm line / space 1:1) using a KrF exposure tool (FPA3000 EX5, Canon). The exposure dose is 25 mJ / cm2. 2 ~40mJ / cm 2 , so that the resulting line width changes. Then, PEB is performed on a hot plate at 100°C for 60 seconds, and a developer of 2.38 mass% TMAH aqueous solution is poured in and then held for 60 seconds (puddle). With the developer puddled, water is started to flow, and while rotating the substrate, the developer is replaced with water, and the puddle is stopped with water, and left to stand for 60 seconds. Then, while puddling with water, the aqueous solution of Example 101 prepared above is poured in, and while rotating the substrate, the water is replaced with the aqueous solution of Example 101, and the puddle is stopped with the aqueous solution of Example 101, and left to stand for 10 seconds. The substrate is spin-dried for 30 seconds to dry the substrate. For Examples 102 to 112 and Comparative Examples 102 to 104, evaluation substrates were prepared in the same manner as above using the respective aqueous solutions. Comparative Example 101 differs from Example 101 above in that the substrate is spin-dried immediately after the water puddle condition, but is otherwise similar.

[0061] <Evaluation of collapse prevention> The evaluation substrate of Preparation 1 is used to evaluate the performance of preventing pattern collapse. The resist pattern is observed using an SEM device S-9220 (Hitachi High-Technologies) to observe the presence or absence of pattern collapse. The evaluation criteria are as follows. In Comparative Example 101, when the line width becomes narrower than 190 nm, the resist pattern collapse is confirmed. The results are shown in Table 1. A: No pattern collapse was observed for resist patterns with line widths of 150 nm or more and 177 nm or less. B: Pattern collapse was observed in resist patterns with line widths of 150 nm to 197 nm. C: Pattern collapse was observed in resist patterns with line widths greater than 200 nm.

[0062] <Preparation Examples of Examples 201 to 206 and Comparative Preparation Examples of Comparative Examples 201 and 202> Using the alkyl carboxylic acid compound (A) and nitrogen-containing compound (C) as shown in Table 2, prepare aqueous solutions of Examples 201 to 206 and Comparative Examples 201 and 202 in the same manner as in the preparation example of Example 101 above, so as to have the concentrations shown in Table 2. In addition, Comparative Example 201 was obtained by filtering deionized water to which nothing was added. [Table 2]

[0063] <Preparation of evaluation board 2> A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. An EUV PHS-acrylate-based chemically amplified resist is applied on top of it 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 through a mask (18 nm line / space 1:1) using an EUV exposure device (NXE:3300B, ASML). The exposure dose is changed so that the resulting line width changes. After that, PEB is performed on a hot plate at 100°C for 60 seconds, and a developer of 2.38 mass% TMAH aqueous solution is poured in and held for 30 seconds (puddle). With the developer puddled, water is started to flow, and the developer is replaced with water while rotating the substrate, and the flow is stopped while puddling with water and left to stand for 60 seconds. Thereafter, the aqueous solution of Example 201 is poured into the water puddle, and the water is replaced with the aqueous solution of Example 201 while rotating the substrate, and the substrate is stopped for 10 seconds in the puddle state with the aqueous solution of Example 201. The substrate is spin-dried to dry it. For the aqueous solutions of Examples 202 to 206 and Comparative Example 202, evaluation substrates are prepared in the same manner as above using each aqueous solution. Comparative Example 201 differs from Example 201 above in that the substrate is spin-dried immediately after the developer is replaced with water and the substrate is puddled with water, but otherwise is similar.

[0064] <Evaluation of critical pattern size (18 nm line / space)> The resist pattern formed on the evaluation substrate of Preparation 2 is observed for line width and the presence or absence of pattern collapse using a critical dimension SEM CG5000 (Hitachi High-Technologies). As the exposure dose increases, the line width decreases. The minimum line width size at which pattern collapse does not occur is defined as the "critical 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, since no collapse is confirmed at 20.8 nm, the critical pattern size is set to 20.8 nm. The results are shown in Table 2.

[0065] <Fabrication of Evaluation Substrate 3> Each evaluation substrate is fabricated in the same manner as Fabrication 2 of the above evaluation substrate, 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 in the same manner as the evaluation of the critical pattern size (18 nm line / space) for the resist pattern formed on the evaluation substrate of Fabrication 3. The results are shown in Table 2. In Comparative Examples 201 and 202, since no pattern was formed in Fabrication 3, measurement was not possible.

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

Claims

1. A method for manufacturing a resist pattern comprising the following steps: (1) Applying a photosensitive resin composition to a substrate, with or without an intermediate layer therebetween, 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 an aqueous solution for electronic device manufacturing; Here, the aqueous solution for electronic device manufacturing comprises an alkyl carboxylic acid compound (A), and a solvent (B) and is composed of: Here, the alkyl carboxylic acid compound (A) is represented by formula (a); A １ -COOH formula (a) (wherein A １ is C ３－１２ alkyl, preferably A １ is linear or branched C ３－１０ alkyl) and the solvent (B) contains water.

2. The method for manufacturing a resist pattern according to Claim 1, wherein the aqueous solution for electronic device manufacturing further comprises a nitrogen-containing compound (C).

3. The method for manufacturing a resist pattern according to Claim 1 or 2, wherein, based on the aqueous solution for electronic device manufacturing, the content of the alkyl carboxylic acid compound (A) is 0.01 to 10% by mass; preferably, based on the aqueous solution for electronic device manufacturing, the content of the solvent (B) is 80 to 99.99% by mass; preferably, based on the aqueous solution for electronic device manufacturing, the content of water contained in the solvent (B) is 80 to 99.99% by mass; or preferably, based on the aqueous solution for electronic device manufacturing, the content of the nitrogen-containing compound (C) is 0.0001 to 10% by mass.

4. The method for manufacturing a resist pattern according to Claim 1 or 2, wherein the aqueous solution for electronic device manufacturing further comprises a hydroxy-containing compound (D): preferably, the aqueous solution for electronic device manufacturing further comprises a surfactant (E).

5. The method for manufacturing a resist pattern according to Claim 1 or 2, wherein the aqueous solution for electronic device manufacturing further comprises an additive (F); here, the additive (F) comprises an acid, a base, a bactericide, an antibacterial agent, a preservative or a fungicide; preferably, based on the aqueous solution for electronic device manufacturing, the content of the hydroxy-containing compound (D) is 0.001 to 10% by mass; preferably, based on the aqueous solution for electronic device manufacturing, the content of the surfactant (E) is 0.01 to 5% by mass; or preferably, based on the aqueous solution for electronic device manufacturing, the content of the additive (F) is 0.0001 to 10% by mass.

6. The method for manufacturing a resist pattern according to Claim 1 or 2, wherein the aqueous solution for electronic device manufacturing is an aqueous solution for semiconductor manufacturing: preferably, the aqueous solution for electronic device manufacturing is an aqueous solution for semiconductor substrate manufacturing; Preferably, the aqueous solution for manufacturing electronic devices is a cleaning solution for semiconductor substrate manufacturing processes; Preferably, the aqueous solution for manufacturing electronic devices is a lithography cleaning solution; or Preferably, the aqueous solution for manufacturing electronic devices is a resist pattern cleaning solution.

7. The method for manufacturing a resist pattern according to claim 1 or 2, wherein the photosensitive resin composition is a chemically amplified photosensitive resin composition, and preferably, exposure is performed using extreme ultraviolet rays.

8. The method for manufacturing a resist pattern according to claim 1 or 2, wherein the minimum space size of the resist pattern in one circuit unit is 10 to 30 nm.

9. A method for manufacturing a device, comprising the method for manufacturing a resist pattern according to claim 1 or 2.

10. The method for manufacturing a device according to claim 9, further comprising etching a substrate using the resist pattern manufactured by the method according to claim 1 or 2 as a mask.

11. The method for manufacturing a device according to claim 9, further comprising forming a wiring on the processed substrate.

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