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 apparatus which makes it possible to prevent pattern collapse or reduce non-uniformity of resist pattern width.SOLUTION: An aqueous solution for manufacturing electronic apparatus comprises an alkylcarboxylic acid compound (A) and a solvent (B), wherein the alkylcarboxylic acid compound (A) is represented by the formula (a): A1-COOH (a), wherein A1 is C4-12 alkyl, and the solvent (B) comprises water.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] In recent years, the need for higher integration of LSIs has increased, resulting in a demand for finer patterns. To meet these needs, lithography processes using short-wavelength light, such as KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet light (EUV; 13 nm), X-rays, and electron beams, are becoming more practical. To meet this demand for finer resist patterns, photosensitive resin compositions used as resists in fine processing are also required to have high resolution. Although finer patterns can be formed by exposure to short-wavelength light, the creation of extremely fine structures poses yield problems, such as collapse of the fine patterns.

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

[0004] Another attempt is to use a surfactant containing fluorine (Patent Document 2 and Patent Document 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-219577 [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 still one or more problems that require improvement, such as: reducing defects in fine resist patterns; suppressing the occurrence of bridging in resist patterns; preventing resist pattern collapse in fine resist patterns; suppressing non-uniformity in resist pattern width; reducing residues after removal of aqueous solutions for manufacturing electronic devices; reducing the surface tension of aqueous solutions for manufacturing electronic devices; providing aqueous solutions for manufacturing electronic devices that have little environmental impact; providing aqueous solutions for manufacturing electronic devices that are less dangerous to handle; and providing aqueous solutions for manufacturing electronic devices that have excellent storage stability (e.g., long-term storage). The present invention has been made based on the above-mentioned technical background, and provides an aqueous solution for manufacturing electronic devices. [Means for solving the problem]

[0007] The aqueous solution for manufacturing electronic devices according to the present invention comprises: an alkyl carboxylic acid compound (A), and Solvent (B) Contains where: The alkyl carboxylic acid compound (A) is represented by formula (a); A1-COOH formula (a) (Wherein, A1 is C 4-12 Alkyl, preferably linear or branched C 5-10 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 manufacturing electronic devices.

[0009] The device manufacturing method according to the present invention comprises the above-described method for manufacturing a resist pattern. [Effects 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 resist patterns. It is possible to prevent resist pattern collapse in fine resist patterns. It is possible to suppress non-uniformity in resist pattern width. It is possible to reduce residues after removing the aqueous solution used in manufacturing electronic devices. It is possible to reduce the surface tension of the aqueous solution used in manufacturing electronic devices. It is possible to reduce the environmental impact of the aqueous solution used in manufacturing electronic devices. It is possible to reduce the danger of handling the aqueous solution used in manufacturing electronic devices. It is possible to improve the storage stability of the aqueous solution used in manufacturing electronic devices. [Brief explanation of the drawings]

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

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

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

[0014] <Electronic device manufacturing aqueous solution> The aqueous solution for manufacturing electronic devices according to the present invention comprises an alkylcarboxylic acid compound (A) and a solvent (B). The aqueous solution for manufacturing electronic devices is used during the manufacturing process of electronic devices. It is sufficient for the aqueous solution to be used during 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 devices is preferably an aqueous solution for manufacturing semiconductor substrates, more preferably a cleaning solution for semiconductor substrate manufacturing processes, even more preferably a lithography cleaning solution, and even more preferably a resist pattern cleaning solution. The aqueous solution for manufacturing electronic devices that can be used as an aqueous solution for manufacturing semiconductor substrates can also be said to be an aqueous solution for manufacturing semiconductor substrates that consists solely of the aqueous solution for electronic devices of the present invention. In another embodiment of the present invention, the aqueous solution for manufacturing electronic devices can be a rinse composition used to rinse an exposed and developed resist pattern.

[0015] Alkylcarboxylic acid compound (A) The alkylcarboxylic acid compound (A) used in the present invention is represented by the formula (a). A1-COOH formula (a) In the formula, A1 is C 4-12 Alkyl. A1 may be linear, branched or cyclic alkyl. A1 is preferably a linear or branched C 5-10 alkyl; more preferably straight or branched C 6-10 alkyl; more preferably straight or branched C 6-9 alkyl; even more preferably straight or branched C 6-8 It is alkyl.

[0016] Specific examples of the alkylcarboxylic acid compound (A) include 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) is preferably 0.01 to 10 mass %, more preferably 0.02 to 5 mass %, even more preferably 0.02 to 1 mass %, and still more preferably 0.03 to 0.5 mass %, based on the aqueous solution for manufacturing electronic devices.

[0018] One of the effects of the alkyl carboxylic acid compound (A) in the aqueous solution for electronic device manufacturing according to the present invention is that it contributes to preventing 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 increases the contact angle of the aqueous solution for electronic device manufacturing during the rinse drying process. 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 aqueous solution for electronic device manufacturing, thereby achieving a good balance between solubility and low surface tension.

[0019] Solvent (B) The solvent (B) comprises water, which is preferably deionized water. Considering that the solvent (B) is used in the manufacturing process of electronic devices, it is preferable that the solvent (B) has a low impurity content. A preferred solvent (B) has an impurity content of 1 ppm or less, more preferably 100 ppb or less, and even more preferably 10 ppb or less. The content of water based on the solvent (B) is preferably 90 to 100 mass%, more preferably 98 to 100 mass%, even more preferably 99 to 100 mass%, and even more preferably 99.9 to 100 mass%. In a preferred embodiment of the present invention, the solvent (B) consists essentially of water. However, an embodiment in which an additive is dissolved and / or dispersed in a solvent other than water (e.g., a surfactant) and is contained in the aqueous solution for manufacturing electronic devices of the present invention is also acceptable as a preferred embodiment of the present invention.

[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 solvents are preferred in terms of the storage stability of the solution. Two or more of these solvents can also be used as a mixture.

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

[0022] The aqueous solution for manufacturing electronic devices according to the present invention essentially contains the above-described components (A) and (B), but may contain additional compounds as necessary. Details will be described below. The total content of components other than (A) and (B) (if multiple components exist) in the overall composition is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 3% by mass, based on the aqueous solution for manufacturing electronic devices. A preferred embodiment of the present invention is one 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% by mass).

[0023] Hydroxy-containing compounds (C) The aqueous solution for manufacturing electronic devices according to the present invention may further contain a hydroxy-containing compound (C). The hydroxy-containing compound (C) may have one or more hydroxy groups in the compound, but preferably has 1 to 3 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 (C), it is possible to further reduce the limit size at which the particles do not collapse.

[0024] In a preferred embodiment, the hydroxy-containing compound (C) is represented by formula (c): [ka] During the ceremony, R c1 , R c2 , R c3 , and R c4 are each independently hydrogen, fluorine, or C 1ー5 are each independently hydrogen, fluorine, methyl, ethyl, t-butyl, or isopropyl; and more preferably, are each independently hydrogen, methyl, or ethyl. L c1 and L c2 are each independently, C 1-20 Alkylene, C 1-20 Cycloalkylene, C 2-4 Alkenylene, C 2-4 Alkynylene of C 6-20 These groups are arylenes of the formula: 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 c1 and L c2 each independently represents an optionally fluorine-substituted group; 1-5 Alkylene, C 2-4L is an alkynylene, or phenylene (C6 arylene). c1 and L c2 are each independently preferably fluorine-substituted C 2-4 alkylene, acetylene (C alkynylene) or phenylene; even more preferably fluorine-substituted C 2-4 The alkylenes are acetylenes. The effects of the present invention can be achieved without using a fluorine-containing component. c1 and L c2 are each independently, C 1-5 Alkylene, C 2-4 alkynylene, or phenylene; more preferably, each independently represents C 2-4 alkylene, acetylene or phenylene; even more preferably each independently C 2-4 The alkylenes are acetylenes. h is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0025] Specific examples of the hydroxy-containing compound (C) 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.

[0026] The content of the hydroxy-containing compound (C) is preferably 0.001 to 10 mass %, more preferably 0.005 to 5 mass %, and even more preferably 0.01 to 1 mass %, based on the aqueous solution for manufacturing electronic devices.

[0027] Surfactant (D) The aqueous solution for manufacturing electronic devices according to the present invention may further contain a surfactant (D). The surfactant (D) is useful for improving coatability and solubility. Here, the surfactant (D) is different from the alkyl carboxylic acid compound (A) and the hydroxyl-containing compound (C). Examples of surfactants (D) 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 (D) is preferably 0.01 to 5 mass %, more preferably 0.02 to 0.5 mass %, based on the aqueous solution for manufacturing electronic devices.

[0028] Additive (E) The aqueous solution for manufacturing electronic devices according to the present invention may further contain an additive (E). In the present invention, the additive (E) comprises an acid (excluding the alkyl carboxylic acid compound (A)), a base, a disinfectant, an antibacterial agent, an antiseptic, or an antifungal agent.

[0029] Acids or bases can be used to adjust the pH value of the processing solution or to improve the solubility of additive components. Examples of acids include aromatic carboxylic acids.

[0030] Preferably, the additive (E) comprises a base. Examples of bases include ammonia, primary amines, secondary amines, tertiary amines, and ammonium compounds. These compounds can be unsubstituted or substituted with a substituent(s). More specifically, they include ammonia, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, ethylenediamine, diethylenetriamine, pentaethylenehexamine, piperidine, piperazine, morpholine, tetramethylammonium hydroxide, and combinations thereof. One embodiment of a suitable base is ammonia. The content of the base is preferably 0.01 to 0.3 mass % based on the aqueous solution for manufacturing electronic devices.

[0031] The additive (E) may optionally contain an antibacterial agent, an antifungal agent, a preservative, or a disinfectant. These chemical substances are used to prevent the growth of bacteria and fungi over time. Examples of these chemical substances are alcohols such as phenoxyethanol and isothiazolones. Bestcide (manufactured by Nippon Soda Co., Ltd.) is a particularly effective antibacterial agent, antifungal agent, and disinfectant. The content of these chemical substances is preferably 0.00005 to 0.1% by mass, more preferably 0.0001 to 0.01% by mass, based on the aqueous solution used in manufacturing electronic devices.

[0032] The content of the additive (E) is preferably 0.0001 to 10 mass %, more preferably 0.0005 to 0.1 mass %, based on the aqueous solution for manufacturing electronic devices.

[0033] After dissolving its components, the electronics manufacturing aqueous solution according to the present invention can be filtered to remove impurities and / or insoluble matter.

[0034] <Method of manufacturing a resist pattern> The present invention also provides a method for producing a resist pattern using the above-mentioned aqueous solution for manufacturing electronic devices. The photosensitive resin composition (resist composition) used in this method may be either positive-type or negative-type; positive-type is more preferred. A typical method for producing a resist pattern using the aqueous solution for manufacturing electronic devices according to the present invention comprises the following steps: (1) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers, to form a photosensitive resin layer; (2) exposing the photosensitive resin layer to radiation; (3) developing the exposed photosensitive resin layer; (4) Washing the developed layer with the above electronics manufacturing aqueous solution.

[0035] Details are explained below. First, a photosensitive resin composition is applied (e.g., laminated) onto a substrate, such as a silicon substrate or a glass substrate, which has been pretreated as needed, to form a photosensitive resin layer. While known techniques can be used for lamination, spin coating or other coating methods are preferred. The photosensitive resin composition can be laminated directly onto the substrate, or via one or more intermediate layers (e.g., BARC). An anti-reflective film (e.g., TARC) may also be laminated above the photosensitive resin layer (on the opposite side from the substrate). Layers other than the photosensitive resin layer will be described later. Forming an anti-reflective film above or below the photosensitive resin film can improve the cross-sectional shape and exposure margin.

[0036] Representative examples of positive or negative photosensitive resin compositions that can be used in the resist pattern production method of the present invention include those containing a quinone diazide photosensitizer and an alkali-soluble resin, and chemically amplified photosensitive resin compositions. From the perspective of forming a high-resolution, fine resist pattern, chemically amplified photosensitive resin compositions are preferred, such as chemically amplified PHS-acrylate hybrid EUV resist compositions. These are more preferably positive photosensitive resin compositions.

[0037] Examples of the quinone diazide photosensitizer used in the positive-type 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, and esters or amides of these sulfonic acids. Examples of the alkali-soluble resin include novolak resins, polyvinylphenols, polyvinyl alcohols, copolymers of acrylic acid or methacrylic acid, etc. Preferred novolak resins include 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.

[0038] Examples of chemically amplified photosensitive resin compositions include positive-type chemically amplified photosensitive resin compositions containing a compound (photoacid generator) that generates acid upon irradiation with radiation and a resin whose polarity increases due to the action of the acid generated from the photoacid generator, and whose solubility in a developer changes between exposed and unexposed areas; and negative-type chemically amplified photosensitive resin compositions that 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, and whose solubility in a developer changes between exposed and unexposed areas.

[0039] Resins whose polarity increases under the action of an acid and whose solubility in a developer changes between exposed and unexposed areas include resins having groups in the main chain or side chain, or both the main chain and the side chain, that decompose under the action of an acid to generate alkali-soluble groups. Typical examples include polymers in which an acetal group or a ketal group is introduced as a protecting group into a hydroxystyrene polymer (PHS) (e.g., JP-A-2-19847, etc.), and similar polymers in which a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group is introduced as an acid-decomposable group (e.g., JP-A-2-209977, etc.).

[0040] The photoacid generator may be any compound that generates an acid upon irradiation with radiation, and examples thereof include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts, organic halogen compounds, organometallic / organic halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis such as iminosulfonates, disulfone compounds, diazoketosulfones, and diazodisulfone compounds. Compounds in which these photoacid-generating groups or compounds are introduced into the main chain or side chain of a polymer can also be used.

[0041] 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.

[0042] The photosensitive resin composition is applied to a substrate using a suitable application 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 and form 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 90 seconds, when using a hot plate, and for 1 to 30 minutes when using a clean oven.

[0043] The resist pattern manufacturing method of the present invention allows the presence of films or layers other than the photosensitive resin layer. An intermediate layer may be interposed between the substrate and the photosensitive resin layer without direct contact. The intermediate layer is a layer formed between the substrate and the photosensitive resin layer and is also called an underlayer film. Examples of underlayer films include substrate modification films, planarization films, bottom antireflective coatings (BARCs), inorganic hard mask intermediate layers (silicon oxide films, silicon nitride films, and silicon oxide nitrate films), and adhesion films. For the formation of inorganic hard mask intermediate layers, see Japanese Patent No. 5336306. The intermediate layer may be composed of one layer or multiple layers. A top antireflective coating (TARC) may also be formed on the photosensitive resin layer.

[0044] In the resist pattern production process of the present invention, known techniques can be used for the layer structure in accordance with the process conditions, and examples thereof include the following laminated structures. Substrate / 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 / flattening film / BARC / photosensitive resin layer / TARC Substrate / substrate modification layer / flattening film / adhesion film / BARC / photosensitive resin layer / TARC These layers can be cured by heating and / or exposure to light after application, or can be formed using known techniques such as CVD. These layers can be removed by known techniques (such as etching), and each layer can be patterned using the upper layer as a mask.

[0045] The photosensitive resin layer is exposed through a predetermined mask. If other layers are included (such as TARC), they may also be exposed. The wavelength of the radiation (light) used for exposure is not particularly limited, but exposure with light having a wavelength of 13.5 to 248 nm is preferred. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet (wavelength 13.5 nm) can be used, with extreme ultraviolet being more preferred. These wavelengths have a tolerance of ±5%, preferably ±1%. After exposure, post-exposure baking (PEB) can be performed as needed. The post-exposure baking temperature is selected from 70 to 150°C, preferably 80 to 120°C, and the heating time is selected from 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0046] Next, development is carried out using a developer. Preferably, a 2.38% by mass (±1% is 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 appropriately selected generally from 10 to 300 seconds, preferably 20 to 60 seconds. Known development methods such as puddle development can be used. As mentioned above, the resist pattern of the present invention includes not only resist films that have been exposed and developed, but also resist patterns in which walls have been thickened by further covering them with other layers or films.

[0047] The resist pattern (developed photosensitive resin layer) formed through the above steps is in an unwashed state. This resist pattern can be washed with the aqueous solution for manufacturing electronic devices according to the present invention. The time for which the aqueous solution for manufacturing electronic devices is in contact with the resist pattern, i.e., the treatment time, is preferably 1 second or more. The treatment temperature may also be arbitrary. The method for contacting the aqueous solution for manufacturing electronic devices with the resist is also arbitrary, and can be carried out, 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. Cut.

[0048] In the resist pattern manufacturing method according to the present invention, the developed resist pattern can be washed with another cleaning liquid before and / or after the cleaning process with the aqueous solution for manufacturing electronic devices. The other cleaning liquid is preferably water, more preferably pure water (DW, deionized water, etc.). The cleaning before the cleaning process is useful for cleaning the developer adhering to the resist pattern. The cleaning after the cleaning process is useful for cleaning the aqueous solution for manufacturing electronic devices. In one preferred embodiment of the manufacturing method according to the present invention, the developed resist pattern is washed by pouring pure water into it to replace the developer, and then, while the pattern remains immersed in the pure water, the aqueous solution for manufacturing electronic devices is poured in to replace the developer, thereby washing the pattern. The cleaning with the aqueous solution used in the electronics manufacturing process may be carried out by known methods. For example, the resist substrate may be immersed in an electronic device manufacturing solution, or the electronic device manufacturing solution may be dropped onto the surface of a rotating resist substrate. These methods may be used in combination as appropriate.

[0049] One of the conditions that makes pattern collapse likely is the location where the spacing between the walls of the resist pattern is narrowest. This condition becomes severe when the walls of the resist pattern are parallel. In this specification, the minimum space size is defined as the distance between the smallest spacings on one circuit unit. Preferably, one circuit unit will become one semiconductor in a subsequent process. Also, it is preferable that one semiconductor includes one circuit unit in the horizontal direction and multiple circuit units in the vertical direction. Of course, unlike the test sample, if the frequency of narrow spacings between walls is low, the frequency of defects will decrease, and therefore the frequency of defective products will decrease. In the present invention, the minimum space size of the resist pattern in one circuit unit is preferably 10 to 30 nm, more preferably 10 to 20 nm, and even more preferably 10 to 17 nm.

[0050] <Device manufacturing method> The device manufacturing method of the present invention comprises a method for manufacturing a resist pattern using an aqueous solution for manufacturing electronic devices. Preferably, the device manufacturing method of the present invention comprises etching a substrate using the resist pattern manufactured by the above method as a mask. After processing, the resist film is stripped as necessary. Preferably, the device is a semiconductor. In the manufacturing method of the present invention, the intermediate layer and / or the substrate can be processed by etching using the resist pattern as a mask. Known etching techniques such as dry etching and wet etching can be used for the etching, with dry etching being more preferred. For example, the substrate can be processed by etching the intermediate layer using the resist pattern as an etching mask, and then etching the substrate using the resulting intermediate layer pattern as an etching mask. Alternatively, the resist pattern can be used as an etching mask to etch the layers below the resist layer (e.g., the intermediate layer) while also etching the substrate as is. The processed substrate becomes, for example, a patterned substrate. The formed pattern can be used to form wiring on the substrate. These layers can be removed by dry etching, preferably with O2, CF4, CHF3, Cl2 or BCl3, preferably with O2 or CF4. In one preferred embodiment, the method for manufacturing a device according to the present invention further comprises forming wiring on the processed substrate.

[0051] <Stress on the resist wall> As described in Namatsu et al. Appl. Phys. Lett. 1995(66) pp. 2655-2657 and shown diagrammatically in FIG. 1, the stress on the wall during rinsing can be expressed by the following equation: σ max =(6γcosθ / D)x(H / W) 2 σ max : Maximum stress applied to the resist, γ: Surface tension of the rinse θ: contact angle, D: distance between walls H: Wall height, W: Wall width These lengths can be measured by known methods, for example, SEM photography.

[0052] As can be seen from the above formula, a shorter D or a shorter W causes more stress. In this specification, the "pitch size" means one unit of the resist pattern unit array having W and D as shown in FIG. This means that the finer (narrower pitch size) the resist pattern is required to be, the greater the stress on the resist pattern will be. As the pattern becomes finer, the more stringent the conditions become, and the more improvements are required in aqueous solutions (e.g., rinse compositions) used in the manufacture of electronic devices.

[0053] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0054] <Preparation Example of Example 101> Add n-hexanoic acid as alkyl carboxylic acid compound (A) to deionized water to a concentration of 0.2% by mass, and stir. Visually confirm complete dissolution. Filter (pore size = 10 nm) to obtain an aqueous solution of Example 101.

[0055] <Preparation Examples of Examples 102 to 112 and Comparative Preparation Examples of Comparative Examples 101 to 103> Aqueous solutions of Examples 102 to 112 and Comparative Examples 101 to 103 are prepared in the same manner as in the preparation example of Example 101 above, using alkylcarboxylic acid compounds (A) and basic compounds (C) as shown in Table 1, so as to have the concentrations shown in Table 1. The aqueous solution of Comparative Example 101 is obtained by filtering deionized water to which nothing has been added. [Table 1]

[0056] <Creating an evaluation board 1> A base anti-reflective coating composition (AZ Kr-F17B, Merck Performance Materials, Inc. (hereinafter referred to as MPM)) is applied to a silicon substrate by spin coating and heated on a hot plate at 180°C for 60 seconds to obtain a bottom anti-reflective coating with a thickness of 80 nm. A PHS-acrylate chemically amplified resist (DX6270P, MPM) 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 through a mask (250 nm line / space 1:1) using a KrF exposure system (FPA3000 EX5, Canon). The exposure dose is 25 mJ / cm. 2 ~40mJ / cm 2 and the resulting line width is changed. Then, post-exposure baking (PEB) was performed on a hot plate at 100°C for 60 seconds, and a 2.38% by weight aqueous TMAH developer was poured in and held for 60 seconds (puddling). While the developer was puddling, water was started to flow, and while rotating the substrate, the developer was replaced with water. The puddling was stopped and the substrate was left standing for 60 seconds. Then, while the substrate was puddling with water, the aqueous solution of Example 101 prepared above was poured in, the water was replaced with the aqueous solution of Example 101, the puddling was stopped and the substrate was left standing for 10 seconds. The substrate was then spin-dried for 30 seconds to dry the substrate. For Examples 102 to 112 and Comparative Examples 101 to 103, evaluation substrates were prepared in the same manner as above using the respective aqueous solutions.

[0057] <Evaluation of collapse prevention> The evaluation substrate prepared in Example 1 was used to evaluate the ability to prevent pattern collapse. The resist pattern was observed using an SEM S-9220 (Hitachi High-Technologies) to check for the presence or absence of pattern collapse. The evaluation criteria were as follows: In Comparative Example 101, pattern collapse was observed in the resist pattern with a line width of 187 nm. The results are shown in Table 1. A: No pattern collapse was observed for resist patterns with line widths of 150 nm to 177 nm. B: Pattern collapse was observed in resist patterns with line widths of 150 nm or more and 187 nm or less. C: Pattern collapse was observed in resist patterns with line widths greater than 187 nm.

[0058] <Preparation Example of Example 201> Add 2-methylpentanoic acid and 1,4-butanediol to deionized water to a concentration of 0.2% by mass and 0.1% by mass, respectively, and stir. Visually confirm complete dissolution. Filter (pore size = 10 nm) to obtain an aqueous solution of Example 201.

[0059] <Preparation Examples of Examples 202 to 205 and Comparative Preparation Example of Comparative Example 201> Aqueous solutions of Examples 202 to 205 and Comparative Example 201 are prepared in the same manner as in the preparation example of Example 201 above, using the alkylcarboxylic acid compound (A) and basic compound (C) as shown in Table 2, so as to have the concentrations shown in Table 2. Note that Comparative Example 201 is obtained by filtering deionized water to which nothing has been added. <Preparation Example of Example 206> Add 2-ethylhexanoic acid and ammonia to deionized water to concentrations of 0.1% by mass and 0.05% by mass, respectively, and stir. Visually confirm complete dissolution. Filter (pore size = 10 nm) to obtain an aqueous solution of Example 206. [Table 2]

[0060] <Creating an evaluation board 2> A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist is then spin-coated and heated on a hotplate at 110°C for 60 seconds to obtain a 45nm thick resist film. The substrate is then exposed to light through a mask (18nm line / space 1:1) using an EUV exposure system (NXE:3300B, ASML). The exposure dose is varied to vary the resulting line width. A post-exposure bake (PEB) is then performed on a hotplate at 100°C for 60 seconds. A 2.38% by weight aqueous TMAH developer is then poured in and held for 30 seconds (puddling). While the developer is puddling, water is started, and the developer is replaced with water while the substrate is rotating. The puddling is stopped and the substrate is left to stand for 60 seconds. Thereafter, the aqueous solution of Example 201 is poured into the puddled state with water to replace the water with the aqueous solution of Example 201, and the substrate is stopped for 10 seconds in the puddled 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 201, evaluation substrates are prepared in the same manner as above using each aqueous solution.

[0061] <Evaluation of the Limit Pattern Size> The resist pattern formed on the evaluation substrate of Fabrication 2 is observed for line width and the presence or absence of pattern collapse using a length measurement SEM CG5000 (Hitachi High-Technologies). As the exposure dose increases, the line width decreases. The minimum line width size at which no pattern collapse occurs 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 16.4 nm. On the other hand, since no collapse is confirmed at 17.3 nm, the limit pattern size is taken as 17.3 nm. The results are shown in Table 2.

[0062] <Evaluation of LWR> The LWR of the resist pattern formed on the evaluation substrate of Fabrication 2 is evaluated. Using a SEM CG5000 (Hitachi High-Technologies), 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. Some aspects of the present invention are set out below. [Aspect 1] an alkyl carboxylic acid compound (A), and Solvent (B) A resist pattern cleaning solution comprising: [[ID=2*]] where: The alkyl carboxylic acid compound (A) is represented by formula (a); <00*0394>1 -COOH Formula (a) <00003*7> (In the formula, A 1 is C 4-12 alkyl) and The solvent (B) comprises water. [Aspect 2] The resist pattern cleaning liquid according to embodiment 1, further comprising a hydroxy-containing compound (C). [Aspect 3] 3. The resist pattern cleaning liquid according to embodiment 2, wherein the hydroxy-containing compound (C) comprises a compound represented by formula (c):

Chemical Formula

Claims

1. an alkylcarboxylic acid compound (A), and Solvent (B) A resist pattern cleaning solution comprising: where: The alkylcarboxylic acid compound (A) is represented by formula (a): A １ -COOH formula (a) (In the formula, A １ is C ４－１２ alkyl) and The solvent (B) comprises water.

2. 2. The resist pattern cleaning solution according to claim 1, further comprising a hydroxy-containing compound (C).

3. The resist pattern cleaning liquid according to claim 2 , wherein the hydroxy-containing compound (C) comprises a compound represented by formula (c): 【Chemical 1】 (In the formula, R ｃ１ , R ｃ２ , R ｃ３ , and R ｃ４ are each independently hydrogen, fluorine, or C １－５ is an alkyl of L ｃ１ and L ｃ２ are each independently C １－２０ Alkylene, C １－２０ Cycloalkylene of C ２－４ Alkenylene of C ２－４ Alkynylene of C ６－２０ These groups are arylenes of the formula: １－５ optionally substituted with alkyl or hydroxy; h is 0, 1, or 2.

4. The content of the alkylcarboxylic acid compound (A) is 0.01 to 10 mass% based on the resist pattern cleaning solution; The content of the solvent (B) is 80 to 99.99 mass% based on the resist pattern cleaning solution; The content of water contained in the solvent (B) is 80 to 99.99 mass% based on the resist pattern cleaning solution; or 4. The resist pattern cleaning solution according to claim 1, wherein the content of the hydroxy-containing compound (C) is 0.001 to 10 mass % based on the resist pattern cleaning solution.

5. The resist pattern cleaning solution according to any one of claims 1 to 4, further comprising a surfactant (D).

6. 6. The resist pattern cleaning solution according to claim 5, wherein the content of the surfactant (D) is 0.01 to 5 mass % based on the resist pattern cleaning solution.

7. The resist pattern cleaning solution according to any one of claims 1 to 6, further comprising an additive (E); where: The additive (E) comprises an acid, a base, a disinfectant, an antibacterial agent, a preservative, or an antifungal agent.

8. 8. The resist pattern cleaning solution according to claim 7, wherein the content of the additive (E) is 0.0001 to 10 mass % based on the resist pattern cleaning solution.

9. 9. The resist pattern cleaning solution according to claim 1, for cleaning a resist pattern having a minimum space size of 10 to 30 nm in one circuit unit.

10. A method for producing a resist pattern, which uses the resist pattern cleaning solution according to any one of claims 1 to 9.

11. A method for producing a resist pattern, comprising the following steps: (1) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers, to form a photosensitive resin layer; (2) exposing the photosensitive resin layer to radiation; (3) developing the exposed photosensitive resin layer; (4) The developed layer is washed with the resist pattern washing solution according to any one of claims 1 to 9.

12. The method for producing a resist pattern according to claim 11, wherein the exposure is carried out using extreme ultraviolet light.

13. 13. The method for producing a resist pattern according to claim 10, wherein the minimum space size of the resist pattern in one circuit unit is 10 to 30 nm.

14. A method for manufacturing a device, comprising the method for manufacturing a resist pattern according to any one of claims 10 to 13.

15. The method for producing a device according to claim 14, further comprising etching a substrate using the resist pattern produced by the method according to any one of claims 10 to 13 as a mask.

16. The method for manufacturing a device according to claim 14 or 15, further comprising forming wiring on the processed substrate.

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