Resist pattern forming composition and use thereof

Abstract

To provide a resist pattern forming composition and a method for producing a resist pattern using the same. A resist pattern forming composition is a high-performance material that can be used in a semiconductor device producing step of a nanotechnology process, for example, a step of producing a semiconductor device that controls liquid crystals, quantum dots, or OLED displays formed on a substrate.

Description

[DESCRIPTION][Title of Invention]RESIST PATTERN FORMING COMPOSITION AND USE THEREOF[Technical Field]

[0001] The present invention relates to a resist pattern forming composition and use thereof.[Background Art]

[0002] In recent years, the need for higher integration of LSIs has increased, and pattern miniaturization has been required. To meet such a need, lithography processes using short-wavelength rays, such as KrF excimer lasers, ArF excimer lasers, extreme ultraviolet rays, X-rays, and electron beams, are being increasingly put into practical use. In order to facilitate miniaturization of resist patterns, a photosensitive resin composition used as a resist in microfabrication is also required to have properties for high resolution. Although a finer pattern can be formed by exposure with light having a short wavelength, a resist pattern may collapse due to a finer structure being formed.

[0003] In order to reduce the occurrence of resist pattern collapse, there has been an investigation in which a rinse solution is replaced with a polymer as a reinforcing material (embedding agent), and the polymer is removed by being decomposed (reduced in molecular weight) by plasma or heat (PTL 1 and PTL 2). As a method for suppressing pattern collapse, there exists a method in which a rinse solution used after development is solidified (cooled and solidified) to form a film, and then the film is sublimated under reduced pressure (PTL 3 and PTL 4).There exists a method in which a rinse solution used after development is replaced with carbon dioxide, then solidified to form a film, and the film is subsequently sublimated (PTL 5).[Citation List][Patent Literature]

[0004] [PTL 1] WO 2022 / 039071[PTL 2] Japanese Patent Application Publication No. 2020-129619[PTL 3] Japanese Patent No. 7020637[PTL 4] Japanese Patent No. 6224116 [PTL 5] Japanese Patent No. 7142333 [Summary of Invention] [Technical Problem]

[0005] The inventor found that one or more problems remain for which improvement is still required. The problems include: a high occurrence of defects in a fine resist pattern; resist pattern collapse occurs in a fine resist pattern; when a developing solution or a rinse solution between resist patterns is removed by spin-drying, pattern collapse occurs due to surface tension; the resist pattern cannot be washed cleanly; removal of particles from the resist pattern is not efficient; steps of removing the films formed in the resist pattern cleaning process is complex; a removing agent is required to remove the formed film; the formed film remains in the resist pattern without being removed; embedding into fine resist patterns cannot be performed; when the developing solution is replaced with another material, precipitation occurs; and the yield is poor.[Solution to Problem]

[0006] A resist pattern forming composition according to the present invention comprises a solidifying component (A), and a solvent (B), wherein the component (A) is a crystalline compound that does not contain an oxime and has a melting point at atmospheric pressure of 30°C or higher and 250°C or lower, and the content of the component (A) is 0.10 to 11 .0 mass%, based on the total mass of the composition.

[0007] A method for producing a resist pattern according to the present invention uses the aforementioned resist pattern forming composition, and comprises the following steps of:(1 ) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers interposed between the photosensitive resin composition and the substrate, to form a photosensitive resin layer;(2) exposing the photosensitive resin layer to radiation;(3) applying the resist pattern forming composition;(4) removing at least a portion of the solvent (B) in the resist pattern forming composition to form a solid phase; and(5) removing the solid phase by sublimation.

[0008] A method for producing a device according to the present invention comprises the aforementioned method for producing a resist pattern.[Advantageous Effects of Invention]

[0009] By using the resist pattern forming composition of the present invention, it is possible to achieve one or more of the following effects: occurrence of defects in a fine resist pattern can be reduced; resist pattern collapse in a fine resist pattern can be suppressed; when a developing solution or a rinse solution between resist patterns is removed by spin-drying, pattern collapse can be suppressed; removal of particles from the resist pattern is more efficient; the resist pattern can be washed cleanly; the embedding film can be easily removed; the number of steps of removing the films formed in the resist pattern cleaning process can be reduced; steps of removing the films formed in the resist pattern cleaning process are simplified; the generation of precipitates due to mixing of the embedding solution and the developing solution can be suppressed; the efficiency of the process can be improved; using a removing agent for removing the film is not necessary; embedding into fine resist patterns can be performed; and the time during which the developing solution remains between the resist patterns can be shortened. [Brief Description of Drawings]

[0010] [Fig. 1 ]Fig. 1 is an explanatory view of a resist pattern producing method according to the present invention.[Description of Embodiments]

[0011] Embodiments of the present invention are described in detail below.

[0012] [Definitions]In the present specification, the definitions and examples included in this paragraph are used, unless specifically stated otherwise.The singular shall include the plural, and “a” or “the” means “at least one”. An element of a concept can be expressed by a plurality of types, and when an amount (e.g., mass% or mol%) thereof is described, the amount thereof means a sum of the plurality of types thereof.“And / or” includes all combinations of elements, and also includes use of either one of the elements.When a numerical range is indicated using “to” or both end points are included in the range, and the units are common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.Description such as “Cx-y”, “Cx-Cy”, and “Cx” mean the number of carbons in a molecule or substituent. For example, “C1-6 alkyl” means an alkyl chain having 1 or more and 6 or less carbons (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl). Aromatic hydrocarbons include polycyclic aromatic hydrocarbons.When the polymer includes multiple types of repeating units, these repeating units create a copolymer. The copolymer may be any of an alternating copolymer, a random copolymer, a block copolymer, a graft copolymer, or a mixture thereof. When a polymer or a resin is represented by a structural formula, n, m, or the like in parentheses represents the number of repetitions.The unit of temperature used is Celsius temperature (degrees Celsius). For example, 20 degrees means 20 degrees Celsius.An additive refers to a compound itself that has function (for example, a base generator refers to a compound itself that generates a base). There may also be anembodiment in which the compound is dissolved or dispersed in a solvent and is added to a composition. As an embodiment of the present invention, such a solvent is preferably contained as the solvent (B) or other component in the composition according to the present invention.

[0013] <Resist Pattern Forming Composition>The resist pattern forming composition according to the present invention (hereinafter referred to as “the present composition” in some cases) is applied to a resist pattern to form a resist pattern embedding film (hereinafter referred to as “embedding film” in some cases) between resist patterns by for example, drying a solvent. The present composition can be also referred to as an embedding film forming embedding solution (hereinafter referred to as “embedding solution” in some cases). The present composition is preferably a resist pattern embedding film forming composition; more preferably a volatilization-removable embedding film forming composition; and still more preferably a sublimation-removable embedding film forming composition.The present composition is applied to a resist film after exposure. The embedding solution according to the present invention is preferably applied to resist patterns after application of the developing solution, and more preferably used so as to be replaced with the developing solution present between the resist patterns. At this time, it is more preferable that when the developing solution and the embedding solution are mixed, the solute derived from at least one of them does not precipitate.The embedding solution according to the present invention is applied to a resist film after exposure, and preferably is able to be applied as a developing solution for forming a resist pattern, and also to be applied as an embedding solution between resist patterns after forming the resist pattern.

[0014] It is preferable that the embedding solution according to the present invention not substantially change the film thickness of the resist pattern when applied to the resist pattern.The embedding film according to the present invention is sublimated at normal temperature or by heating, and can be easily removed from between the resist patterns.

[0015] The resist pattern forming composition of the present invention comprises a solidifying component (A) and a solvent (B).

[0016] Solidifying Component (A)The resist pattern forming composition of the present invention comprises a solidifying component (A) (hereinafter referred to as component (A) in some cases. The same applies to other components).The component (A) is a crystalline compound that does not contain an oxime and has a melting point at atmospheric pressure (0.091 to 0.111 MPa) of 30°C or higher and 250°C or lower, preferably 30°C or higher and 240°C or lower, and more preferably 30°C or higher and 220°C or lower. In the present application, the “oxime” refers to a compound having a >C=N-OH partial structure. Furthermore, the component (A) is preferably a crystalline compound that is brought into a gaseous state from a solid state without passing through a liquid state at atmospheric pressure (hereinafter referred to as “sublimable substance” in some cases).

[0017] The present composition more preferably comprises, as the component (A), at least one compound represented by any of Formulae (A-1 ) to (A-5). The compounds represented by Formulae (A-1 ) to (A-5) can be used alone or in combination of two or more compounds of any formula.

[0018] Formula (A-1 ) is as follows.[C1 ]whereinGroups X11are each independently -OH or -NH2, preferably -OH.R11is substituted or unsubstituted C5-C20 alkyl or a substituted or unsubstituted C5-C20 saturated alicyclic hydrocarbon group. The alkyl or saturated alicyclic hydrocarbon group may be substituted with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, or may be unsubstituted. More preferably, it is unsubstituted. The number of carbons includes the number of carbons of the substituent. R11is preferably substituted or unsubstituted C5-C16 alkyl. More preferably, R11is C5-C16 linear alkyl or C5-C16 branched alkyl. Still more preferably, R11is linear alkyl. Suitably, R11is propyl, dimethylpropyl, butyl, dimethylbutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or tridecyl.R11is preferably a substituted or unsubstituted C5-C16 saturated alicyclic hydrocarbon group. More preferably, R11is a monocyclic saturated hydrocarbon group, an alkyl-substituted monocyclic saturated hydrocarbon group, a polycyclic saturated hydrocarbon group, or an alkyl-substituted polycyclic saturated hydrocarbon group. The alkyl may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. Suitably, R11is cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptyl, norbornyl, or adamantyl.One or more -CH2- groups or -CH= groups of R11may be substituted with -0- or -C(= 0)-, or may be unsubstituted. More preferably, it is unsubstituted. R11preferably comprises linear alkyl, branched alkyl, cyclic alkyl, aryl, or any combination thereof. noi is 1 or 2, preferably noi = 1 .When noi = 2, R11is a linker.

[0019] Specific examples of Formula (A-1 ) include tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, norbornan-2-ol, 2-adamantanol, 2,2-dimethylpropanol, 2,2-dimethyl-1 ,3- propanediol, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-ol, DL-pantolactone, hexanediol, octanediol, nonanediol, decanediol, 1 ,3-cyclopentanediol, 1 ,2-cyclohexanediol, 1 ,3- cyclohexanediol, 1 ,4-cyclohexanediol, 4-aminocyclohexanol, 1 -adamantanamine, and 2,2-dimethyl-1 ,3-propanediamine. These compounds can be used alone or two or more thereof can be used in a mixture.Still more preferred examples of Formula (A-1 ) include 2,2-dimethylpropanol, 2,2-dimethyl-1 ,3-propanediol, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-ol, and DL- pantolactone.

[0020] Formula (A-2) is as follows.[C2]whereinCy11is a substituted or unsubstituted C6-C20 hydrocarbon ring. The hydrocarbon ring may be substituted with alkyl, or may be unsubstituted. The alkyl may be linear, branched, or cyclic. The alkyl is more preferably linear or branched, and still more preferably linear. The “linear” includes methyl. The number of carbons includes the number of carbons of the substituent. Cy11is preferably a substituted or unsubstituted Ce-C aromatic hydrocarbon ring. More preferably, Cy11is benzene, alkyl-substituted benzene, naphthalene, alkyl-substituted naphthalene, anthracene, or alkyl-substituted anthracene. Suitably, Cy11is benzene, methylbenzene, dimethylbenzene, trimethylbenzene, naphthalene, or anthracene. Cy11is also preferably a saturated or unsaturated Ce-C alicyclic hydrocarbon. More preferably, Cy11is a monocyclic saturated hydrocarbon, an alkyl-substituted monocyclic saturated hydrocarbon, a polycyclic saturated hydrocarbon, or an alkyl-substituted polycyclic saturated hydrocarbon. Suitably, Cy11is cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptane, norbornane, or adamantane. One or more -CH2- groups or -CH= groups of Cy11may be substituted with -C(=O)-. Cy11preferably comprises one or more -C(=O)- groups, and more preferably comprises one -C(=O)- group.Groups R12are each independently C1-C4 alkyl, preferably methyl or ethyl, more preferably methyl.no2 is 0, 1 , 2, 3, 4, 5 or 6, preferably 0, 1 , 2 or 3. More preferably, no2 is 0 or 2, and still more preferably 0.

[0021] Specific examples of Formula (A-2) include cyclooctanone, 2-adamantanone, norborna-5-ene-2-one, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-one, 1 ,2- cyclohexanedione, 1 ,3-cyclohexanedione, 1 ,4-cyclohexanedione, 2-methyl-1 ,3- cyclohexanedione, 1 ,2-benzoquinone, 1 ,4-benzoquinone, 2-tert-buty 1-1 ,4- benzoquinone, 2-methyl-1 ,4-benzoquinone, 2, 5-dimethyl-1 ,4-benzoquinone, 2,6- dimethyl-1 ,4-benzoquinone, 2,3-dimethyl-1 ,4-benzoquinone, 2, 3, 5-trimethyl-1 ,4- benzoquinone, 2, 3, 5, 6-tetramethyl-1 ,4-benzoquinone, naphthalene, anthracene, triphenylene, phenalene, phenanthrene, pyrene, norbornane, norbornene, and tetrahydrodicyclopentadiene. These compounds can be used alone, or two or more thereof can be used in mixture.Still more preferred examples of Formula (A-2) include 1 ,7,7- trimethylbicyclo[2.2.1 ]heptan-2-one, naphthalene, tetrahydrodicyclopentadiene, and cyclooctanone.

[0022] Formula (A-3) is as follows.[C3]whereinY11is NH or N.Y12to Y16are each independently CR13or N, and at least one of Y12to Y16is N.Groups R13are each independently H or C1-C3 alkyl, preferably H or methyl, more preferably H. nos is 0 or 1 , preferably 1 .

[0023] Specific examples of Formula (A-3) include pyrazole, imidazole, 1 ,2,4-triazol, tetrazole, pyrazine, 1 ,2,4-triazine, and 1 ,3,5-triazine. These compounds can be used alone, or two or more thereof can be used in mixture.Still more preferred examples of Formula (A-3) include imidazole, pyrazine, and 1 ,3,5-triazine.

[0024] Formula (A-4) is as follows.[C4]whereinR14is a single bond or a substituted or unsubstituted C1-C20 hydrocarbon group. The hydrocarbon group may be substituted with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, or may be unsubstituted. More preferably, it is unsubstituted. The number of carbons includes the number of carbons of the substituent. R14is preferably a single bond, substituted or unsubstituted C1-C16 alkyl, or a substituted or unsubstituted Ce-C cyclic hydrocarbon group. More preferably, R14is a single bond, substituted or unsubstituted C1-C16 linear alkyl, substituted or unsubstituted C3-C16 branched alkyl, substituted or unsubstituted Ce- C16 aryl, or a substituted or unsubstituted Ce-C saturated alicyclic hydrocarbon group. Still more preferably, R14is a single bond, C1-C16 linear alkyl, phenyl, alkylsubstituted phenyl, naphthyl, alkyl-substituted naphthyl, a monocyclic saturated hydrocarbon group, an alkyl-substituted monocyclic saturated hydrocarbon group, a polycyclic saturated hydrocarbon group, or an alkyl-substituted polycyclic saturated hydrocarbon group. The alkyl substituent may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. The linear alkyl includes methyl. Suitably, R14is a single bond, methyl, ethyl, propyl, dimethylpropyl, butyl, decyl, dodecyl, phenyl, naphthyl, cyclopentyl, cyclohexyl, or decahydronaphthyl. In a case where R14is a single bond, Formula (A-4) represents oxalic acid or oxalic acid ester.Groups R15are each independently H or C1-C3 alkyl, preferably H, methyl or ethyl. More preferably, R15is H or methyl, and still more preferably H. no4 is 1 , 2, or 3, preferably 1 or 2, and more preferably 1 . An embodiment in which no4 = 2 is also a preferred embodiment.When no4 = 2 or 3, R14is a linker.

[0025] Specific examples of Formula (A-4) include decanoic acid, dodecanoic acid, tetradecanoic acid, benzoic acid, acetylsalicylic acid, 2,2-dimethylpropionic acid, 1- adamantane carboxylic acid, 1-methyl-1 -cyclohexane carboxylic acid, 2- methylcyclohexane carboxylic acid, 3-methylcyclohexane carboxylic acid, 1 ,3- cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, decahydro-1 ,4- naphthalenedicarboxylic acid, 1 ,3-adamantanedicarboxylic acid, 2,3- norbornanedicarboxylic acid, 4-cyclohexene-1 ,2-dicarboxylic acid, 5-norbornene- 2,3-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1 ,4- naphthalenedicarboxylic acid, dipropylmalonic acid, cyclopentane-1 ,1 -dicarboxylic acid, cyclopentane-1 ,2-dicarboxylic acid, cyclopentane-1 ,3-dicarboxylic acid, oxalic acid, dimethyl oxalate, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1 ,9-nonanedicarboxylic acid, dodecanedioic acid, trimellitic acid, propane tricarboxylic acid, and 1 ,3,5- benzenetricarboxylic acid. These compounds can be used alone, or two or more thereof can be used in mixture.Still more preferred examples of Formula (A-4) include dimethyl oxalate, succinic acid, benzoic acid, acetylsalicylic acid, and 2,2-dimethylpropionic acid.

[0026] Formula (A-5) is as follows.[C5]whereinR16is a substituted or unsubstituted C1-C20 hydrocarbon group. The hydrocarbon group may be substituted with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, or may be unsubstituted. More preferably, it is unsubstituted. The number of carbons includes the number of carbons of the substituent. R16is preferably substituted or unsubstituted C1-C16 alkyl, or a substituted or unsubstituted C3-C16 cyclic hydrocarbon group. More preferably, R16is substituted or unsubstituted C1-C16 linear alkyl, substituted or unsubstituted C3- C16 branched alkyl, substituted or unsubstituted Ce-Cie aryl, or a substituted or unsubstituted Ce-Cie saturated alicyclic hydrocarbon group. Still more preferably, R16is C1-C16 linear alkyl, phenyl, alkyl-substituted phenyl, naphthyl, alkylsubstituted naphthyl, a monocyclic saturated hydrocarbon group, an alkylsubstituted monocyclic saturated hydrocarbon group, a polycyclic saturated hydrocarbon group, or an alkyl-substituted polycyclic saturated hydrocarbon group. The alkyl substituent may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. The linear alkyl includes methyl. Suitably, R16is methyl, ethyl, propyl, butyl, phenyl, naphthyl, cyclopentyl, cyclohexyl, or adamantyl. nos is 1 , 2, 3, or 4, preferably 1 , 2, or 3, and more preferably 2. When 2 < nos, R16is a linker.

[0027] Specific examples of Formula (A-5) include 1 -cyanoadamantane, 2- cyanoadamantane, dicyanomethane, dicyanoethane, 1 ,2-dicyanobenzene, 1 ,3- dicyanobenzene, and 1 ,4-dicyanobenzene. These compounds can be used alone, or two or more thereof can be used in mixture.Still more preferred examples of Formula (A-5) include dicyanomethane, dicyanoethane, and 1 ,3-dicyanobenzene.

[0028] The molecular weight of the component (A) (hereinafter referred to as Mw in some cases) is preferably 70 or more and 200 or less, more preferably 70 or more and 190 or less, and still more preferably 70 or more and 180 or less.Without intending to limit the scope of the claims, and without being bound by theory, the molecular weight of the component (A) is within the range, so that the component (A) easily penetrates between the particle and the resist pattern. It is considered that the particles adhered to the resist pattern can be easily removed by sublimation of the component (A) that has penetrated. Without being bound bytheory, it is believed that when the molecular weight of the component (A) exceeds 200, embedding the resist pattern forming composition between fine resist patterns is difficult, and the effects of the present invention are difficult to obtain.In the present invention, Mw can be determined by mass spectrometry (MS). For the measurement, it is a preferred example to use electrospray ionization (ESI) as the ionization method.

[0029] The content of the component (A) is preferably 0.10 to 11.0 mass%, more preferably 0.20 to 9.0 mass%, still more preferably 0.30 to 7.0 mass%, and even more preferably 0.40 to 5.0 mass%, based on the total mass of the resist pattern forming composition. Without being bound by theory, it is considered that when the content of the component (A) is less than 0.10 mass%, pattern collapse may occur during the solid phase formation step due to insufficient filling of the component (A) between the resist patterns, and when it exceeds 11 .0 mass%, pattern collapse may occur during the application step of the resist pattern forming composition to the resist patterns due to high viscosity.The present composition may comprise a solidifying component other than the component (A). An embodiment in which no solidifying component other than the component (A) is contained is also a preferred embodiment.

[0030] Solvent (B)The resist pattern forming composition according to the present invention comprises a solvent (B).The solvent (B) preferably comprises at least one selected from the group consisting of water, alcohols, alkanes, ethers, lactic acid esters, acetic acid esters, aromatic hydrocarbons, ketones, amides, and lactones.

[0031] Specific examples of the solvent (B) include water, n-pentane, i-pentane, n- hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene, methanol, ethanol, n-propanol, i-propanol, n- butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sechexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, secoctanol, n-nonyl alcohol, 2,6-dimethylheptan-4-ol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1 ,3-butylene glycol, 2,4-pentanediol, 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4- heptanediol, 2-ethylhexane-1 ,3-diol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, 2- heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4- pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchone, ethyl ether, i-propyl ether, n-butyl ether (di-n-butyl ether, DBE), n-hexyl ether, 2- ethylhexyl ether, ethylene oxide, 1 ,2-propylene oxide, dioxolane, 4- methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2- methyltetrahydrofuran, diethyl carbonate, methyl acetate, ethyl acetate, y- butyrolactone, y-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate (normal butyl acetate, nBA), i-butyl acetate, sec-butyl acetate, n-pentyl acetate,sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2 -ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), n- butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N- methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N- methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1 ,3-propanesultone. These solvents can be used alone, or two or more thereof can be used in mixture.

[0032] The component (B) is preferably DIW, nBA, EL, n-butyl lactate, n-pentyl acetate, IPA, n-butanol, PGME, 2-methylpentanol, DBE, ethylene glycol mono-n- butyl ether, PGMEA, cyclopentanone, cyclohexanone, d-i-butyl ketone, or a mixture of any thereof; more preferably DIW, nBA, EL, IPA, n-butanol, PGME, 2- methylpentanol, PGMEA, cyclopentanone, cyclohexanone, or a mixture of any thereof; still more preferably DIW, nBA, IPA, PGME, PGMEA, cyclopentanone, or a mixture of any thereof; and even more preferably DIW or nBA. The component (B) suitably consists of only one or two solvents, and more suitably consists of only one.When the component (B) consists of two solvents, their mass ratio is preferably 5:95 to 95:5, more preferably 10:90 to 90:10; and still more preferably 20:80 to 80:20.

[0033] The content of the component (B) is preferably 85.0 to 99.9 mass%, more preferably 86.0 to 99.9 mass%, and still more preferably 87.0 to 99.9 mass%, based on the total mass of the resist pattern forming composition.

[0034] Developing Component (C)The resist pattern forming composition according to the present invention may further comprise a developing component (C).In one embodiment of the present invention, development is performed by applying a resist pattern forming composition comprising the component (C) to an exposed resist film. Examples of development include alkali development of a positive type resist, and organic solvent development of a negative type resist and a positive type resist negative development. The component (C) comprises an alkali or an organic solvent.In the case of alkaline development, examples of the component (C) include tetramethylammonium hydroxide (TMAH), sodium carbonate, sodium hydroxide, and potassium hydroxide, and TMAH is preferable.In the case of the organic solvent development, examples of the component (C) include hydrocarbon-based solvents, carboxylic acid-based solvents, ether- based solvents, ester-based solvents, ketone-based solvents, and alcohol-based solvents, preferably, a carboxylic acid-based solvent, an alcohol-based solvent, an ester-based solvent, or a ketone-based solvent, and more preferably, a ketone- based solvent, a carboxylic acid-based solvent, or an ester-based solvent. Specific examples of the component (C) include n-octane, methylcyclohexane, n-butanol, n- pentanol, PGME, DBE, ethylene glycol mono-n-butyl ether, 2-heptanone, cyclopentanone, cyclohexanone, nBA, EL, PGMEA, acetic acid, and propionic acid. Preferably, the component (C) is PGME, cyclopentanone, nBA, EL, PGMEA, or acetic acid. More preferably, the component (C) is PGME, cyclopentanone, EL, PGMEA, or acetic acid.Preferably, the component (C) is different from the above-described component (A) and component (B). When the resist pattern forming composition according to the present invention contains a compound that serves both as asolvent and as a developing component during development, such compound is classified as the component (C).

[0035] The content of the component (C) is preferably 0.30 to 15.0 mass%, more preferably 0.50 to 12.0 mass%, still more preferably 0.80 to 10.0 mass%, and even more preferably 1 .0 to 8.0 mass%, based on the total mass of the resist pattern forming composition.

[0036] Additive (D)The resist pattern forming composition according to the present invention may further comprise an additive (D). The component (D) comprises at least one selected from the group consisting of a surfactant, an acid, a basic compound, an antimicrobial agent, a disinfectant, a preservative, and an antifungal agent. An example of the acid is acetic acid. Preferably, the component (D) is a surfactant, an antimicrobial agent, an acid, a basic compound, or a combination thereof, and more preferably a surfactant, an antimicrobial agent, an acid, or a combination thereof. The component (D) is different from the above-described component (A), component (B), and component (C).

[0037] The content of the component (D) (in the case of a plurality, the total thereof) is preferably 0.00 to 10.0 mass%, more preferably 0.00 to 5.00 mass%, and still more preferably 0.00100 to 1.00 mass%, based on the total mass of the component (A). An embodiment in which no component (D) is contained (0 mass%) in the resist pattern forming composition according to the present invention is also a preferred embodiment of the present invention.

[0038] <Method for Producing Resist Pattern>The method for producing a resist pattern according to the present invention uses the aforementioned resist pattern forming composition, and comprises the following steps of:(1 ) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers interposed between the photosensitive resin composition and the substrate, to form a photosensitive resin layer;(2) exposing the photosensitive resin layer to radiation;(3) applying the resist pattern forming composition;(4) removing at least a portion of the component (B) in the resist pattern forming composition to form a solid phase; and(5) removing the solid phase by sublimation.

[0039] Step (1 )A photosensitive resin composition is applied onto a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, and the like), to form a photosensitive resin layer.In the present invention, the term “onto” includes both a case where a layer is formed directly on another and a case where it is formed with another layer interposed. For example, one or more intermediate layers (such as a planarization film or a bottom anti-reflective coating) may be formed directly on the substrate, and the photosensitive resin composition may be directly applied on the intermediate layer. In a preferred embodiment of the present invention, the photosensitive resin composition is directly applied on the substrate to form a photosensitive resin layer (resist film). The method for application is not particularly limited, and examples thereof include a method by application with a spinner or a coater. Among them, spin coating is preferable. After application, the photosensitive resin layer (resist film) is formed by drying or the like.

[0040] The method for forming the photosensitive resin layer is not particularly limited. Preferably, the photosensitive resin composition is a metal oxide-containing resist composition, a chemically amplified acrylic / methacrylic resist composition, a chemically amplified hydroxystyrene-based resist composition, a chemically amplified hydroxystyrene-acrylate hybrid resist composition, or a chemically amplified epoxy-based resist composition, and more preferably an organometallicoxide hydroxide-containing resist composition. The composition described in Japanese Patent Application Publication No. 2021-73367 can be used as the organometallic oxide hydroxide-containing resist composition. The photosensitive resin composition is preferably an EUV metal oxide-containing resist composition, and in a preferred embodiment, is a negative type resist. The solvent used in the metal oxide-containing resist composition is preferably selected from aromatic solvents (for example, xylene and toluene); ether solvents (for example, anisole and tetrahydrofuran); ester solvents (for example, PGMEA, ethyl acetate, nBA, and ethyl lactate); alcohol solvents (for example, 4-methyl-2-propanol, 1 -butanol, methanol, isopropyl alcohol, and 1 -propanol); ketone solvents (for example, methyl ethyl ketone, 2-heptanone); or a combination thereof.

[0041] After being applied to the substrate, the photosensitive resin composition forms a photosensitive resin layer (resist film) preferably by heating. The heating temperature is preferably 75 to 140°C, more preferably 80 to 130°C, and still more preferably 80 to 120°C. The heating time is preferably 30 to 240 seconds, and more preferably 90 to 180 seconds. The heating is preferably performed in the atmosphere or a nitrogen gas atmosphere. The film thickness of the photosensitive resin layer (resist film) is preferably 10 to 80 nm, and more preferably 15 to 60 nm.

[0042] Step (2)The photosensitive resin layer is exposed through a predetermined mask using radiation. The wavelength of light (radiation) used for exposure is not particularly limited. Exposure with light having a wavelength of 13.5 to 248 nm is preferable. Specifically, a KrF excimer laser (248 nm in wavelength), an ArF excimer laser (193 nm in wavelength), extreme ultraviolet radiation (13.5 nm in wavelength), or the like can be used, and the extreme ultraviolet radiation is preferable. These wavelengths have an allowable range of ±1 %.After exposure, a post-exposure bake (PEB) can also be performed as necessary. The temperature of the PEB is preferably 80 to 200°C, more preferably 90 to 190°C, and the heating time is preferably 30 to 240 seconds, and more preferably 90 to 180 seconds.

[0043] Step (2-2)The method for producing a resist pattern according to the present invention may further comprise a development step (2-2) using a developing solution after step (2).In the development step, the exposed photosensitive resin layer (resist film) is developed using a developing solution to form a resist pattern. Examples of development include alkali development, organic solvent development, and the like. In the case of alkali development, examples of the developing solution include a TMAH aqueous solution, a sodium carbonate aqueous solution, a sodium hydroxide aqueous solution, and potassium hydroxide aqueous solutions. The developing solution is preferably TMAH aqueous solutions, and more preferably 2.38 mass% TMAH aqueous solutions. In the case of organic solvent development, examples of the developing solution include hydrocarbon-based solvents, carboxylic acid-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, and alcohol-based solvents. The developing solution is preferably carboxylic acid-based solvents, ester-based solvents, or ketone-based solvents, and more preferably carboxylic acid-based solvents or ester-based solvents. Preferred examples of the developing solution include 2-heptanone, cyclopentanone, nBA, PGMEA, and acetic acid.

[0044] Fig. 1(i) illustrates a state where a photosensitive resin layer (resist film) 2 is formed directly on a substrate 1 , exposed through a predetermined mask, and then a developing solution 3 is applied. In this state, the exposed portion of the positive type resist and the unexposed portion of the negative type resist are dissolved in the developing solution 3 and developed.

[0045] The method for producing a resist pattern according to the present invention may further comprise cleaning processing using a cleaning liquid after step (2-2).The cleaning liquid used for the cleaning processing is preferably water, and more preferably pure water (DIW, deionized water, or the like). The cleaning processing is useful for cleaning the developing solution attached to the resistpattern. The cleaning processing may be performed by a known method. For example, pure water may be dropped onto the surface of a rotating resist substrate. A preferred embodiment of the producing method according to the present invention is a method in which pure water is poured into a developed resist pattern to clean the pattern while replacing a developing solution with pure water, and the resist pattern forming composition is poured into the resist pattern, while the resist pattern is immersed in pure water, to replace pure water with the resist pattern forming composition, followed by cleaning the pattern through steps (3) to (5).

[0046] Step (3)The resist pattern forming composition according to the present invention is applied to a photosensitive resin layer (resist film), and preferably applied to a resist pattern after application of a developing solution, and more preferably, the resist pattern forming composition is used so as to be replaced with a developing solution present between resist patterns.The resist pattern forming composition is poured into the developed resist pattern to replace a developing solution with the resist pattern forming composition. The method of pouring the resist pattern forming composition into the resist pattern may be performed by a known method. For example, the pouring can be performed by immersing a resist substrate in the resist pattern forming composition or by dropping the resist pattern forming composition onto the surface of a rotating resist substrate. These methods may be appropriately combined and carried out. In order to replace the developing solution with the resist pattern forming composition, the resist pattern may be kept immersed in the resist pattern forming composition for 0.5 to 30 seconds, preferably 0.5 to 25 seconds, and more preferably 1 to 20 seconds. The temperature to be kept is not particularly limited, and is preferably 15 to 40°C, more preferably 20 to 35°C, and still more preferably 25 to 30°C.

[0047] In one embodiment of the present invention, in a case where the photosensitive resin layer is a positive type resist and alkali development is performed, an aqueous sublimable substance is preferably used as the component (A) in the resist pattern forming composition. Here, examples of the aqueoussublimable substance include 2, 2-dimethylpropanol, 2,2-dimethyl-1 ,3-propanediol, DL-pantolactone, 1 ,2-cyclohexanediol, 1 ,3-cyclohexanediol, cyclooctanone, 1 ,2- cyclohexanedione, 1 ,3-cyclohexanedione, pyrazole, imidazole, 1 ,2,4-triazole, tetrazole, pyrazine, 2,2-dimethylpropionic acid, oxalic acid, dimethyl oxalate, malonic acid, succinic acid, glutaric acid, dicyanomethane, and dicyanoethane. These compounds can be used alone, or two or more thereof can be used in mixture. Preferably, the aqueous sublimable substance is 2, 2-dimethylpropanol,2.2-dimethyl-1 ,3-propanediol, DL-pantolactone, dimethyl oxalate, cyclooctanone, or pyrazine.

[0048] In a case where the photosensitive resin layer is a positive type resist and organic solvent development is performed, and in a case where the photosensitive resin layer is a negative type resist, an organic solvent-based sublimable substance is preferably used as the component (A) in the resist pattern forming composition. Here, examples of the organic solvent-based sublimable substance include tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, norbornan-2-ol, 2-adamantanol, 2, 2-dimethylpropanol, 2,2- dimethyl-1 ,3-propanediol, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-ol, DL-pantolactone, 2-methylphenol, 4-methylphenol, 4-ethylphenol, 2,3-dimethylphenol, 2,5- dimethylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 3-tert-butylphenol, 4-tert-butylphenol,2.4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 1 ,2- benzenediol, 1 ,3-benzenediol, 1 ,4-benzenediol, 4-methyl-1 ,2-benzenediol, 1 ,2- cyclohexanediol, 1 ,3-cyclohexanediol, 1 ,4-cyclohexanediol, cyclooctanone, 1 ,7,7- trimethylbicyclo[2,2,1 ]heptan-2-one, 1 ,2-cyclohexanedione, 1 ,3-cyclohexanedione,1 .4-cyclohexanedione, 1 ,2-benzoquinone, 1 ,4-benzoquinone, 2-methyl-1 ,4- benzoquinone, 2,5-dimethyl-1 ,4-benzoquinone, 2,6-dimethyl-1 ,4-benzoquinone,2.3-dimethyl-1 ,4-benzoquinone, 2, 3, 5-trimethyl-1 ,4-benzoquinone, 2, 3,5,6- tetramethyl-1 ,4-benzoquinone, naphthalene, anthracene, triphenylene, phenalene, phenanthrene, pyrene, norbornane, norbornene, tetrahydrodicyclopentadiene, pyrazole, imidazole, 1 ,2,4-triazole, tetrazole, pyrazine, 1 ,3,5-triazine, decanoic acid, dodecanoic acid, tetradecanoic acid, benzoic acid, acetylsalicylic acid, 2,2-dimethylpropionic acid, 1 -methyl-1 -cyclohexanecarboxylic acid, 2- methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, 1 ,3- cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1 .2-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, dimethyl oxalate, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1 ,9-nonanedicarboxylic acid, dodecanedioic acid, trimellitic acid, propanetricarboxylic acid, 1 ,3,5- benzenetricarboxylic acid, dicyanomethane, dicyanoethane, and 1 ,3- dicyanobenzene. These compounds can be used alone, or two or more thereof can be used in mixture. Preferred examples thereof include 2,2-dimethylpropanol, 2,2- dimethyl-1 ,3-propanediol, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-ol, DL-pantolactone, naphthalene, dimethyl oxalate, succinic acid, tetrahydrodicyclopentadiene, pyrazine, 1 ,3,5-triazine, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-one, cyclooctanone, imidazole, benzoic acid, 1 ,4-benzoquinone, 1 ,2-cyclohexanedione, 1 ,3- cyclohexanedione, 1 ,4-cyclohexanedione, 1 ,2-cyclohexanediol, 1 ,3- cyclohexanediol, 1 ,4-cyclohexanediol, acetylsalicylic acid, 2,6-dimethylphenol, 4- tert-butylphenol, 2,2-dimethylpropionic acid, dicyanomethane, dicyanoethane, and1 .3-dicyanobenzene.

[0049] Fig. 1 (ii) illustrates a state where resist patterns 2A are formed directly onto the substrate 1 and the developing solution 3 remains between the resist patterns 2A. In this state, the resist pattern forming composition (embedding solution) according to the present invention can be applied. Fig. 1 (iii) illustrates a state where resist patterns 2A are formed directly onto the substrate 1 and the developing solution 3 between the resist patterns 2A is replaced with the resist pattern forming composition 4.

[0050] Step (4)After application of the resist pattern forming composition between the resist patterns, the component (B) may be removed by spin-drying or heating, preferably by spin-drying, and dried to form a solid phase (an embedding film composed of the component (A)) between the resist patterns. The heating temperature in the case offorming a solid phase by heating is preferably 25 to 100°C, more preferably 25 to 80°C, and still more preferably 25 to 50°C. The heating time is preferably 30 to 240 seconds, more preferably 30 to 120 seconds. The heating is preferably performed in the atmosphere or a nitrogen gas atmosphere.

[0051] Fig. 1 (iv) illustrates a state where the resist pattern forming composition (embedding solution) is applied so as to be replaced with a developing solution and the component (B) is removed to form a solid phase (embedding film composed of the component (A)) 4A between the resist patterns 2A. Fig. 1 (iv) is a view in which the solid phase 4A partially fills between the resist patterns 2A, but the resist patterns 2A may be fully filled. Even in a case where a solid phase (embedding film) 4A is formed only at the bottom between the resist patterns 2A, the effect of preventing pattern collapse can be exhibited.

[0052] Step (5)The solid phase formed between the resist patterns may be sublimated by heating and removed from between the resist patterns. The heating temperature in the case of sublimating the solid phase by heating is preferably 50 to 200°C, more preferably 50 to 150°C, and still more preferably 50 to 100°C. The heating is preferably performed in the atmosphere or a nitrogen gas atmosphere.Without intending to limit the scope of the claims, and without being bound by theory, the condensation reaction by heating does not occur because the component (A) is a crystalline compound so that the adhesion of a material having a high molecular weight, which is difficult to remove, to the resist pattern is suppressed.It is also possible to combine heating and gas blowing. The gas to be blown is not particularly limited. While a gas such as air can also be used, an inert gas such as argon or nitrogen gases are preferably used. The flow rate of the airflow is not particularly limited, and the conditions are selected appropriately. The humidity of the gas is 10% or less, preferably 5% or less, more preferably 1 % or less, and particularly preferably 0.1 % or less.Fig. 1 (v) illustrates a state where the solid phase (embedding film composed of the component (A)) 4A between the resist patterns 2A has been removed by sublimation.

[0053] In the method for producing a resist pattern according to the present invention, in a case where the resist pattern forming composition comprises the component (C), development is performed by applying the resist pattern forming composition to the exposed photosensitive resin layer (resist film), to form a resist pattern. In such an embodiment, the above development step (2-2) may be omitted.

[0054] <Method for Producing Device>The method for producing a device according to the present invention comprises a method for producing a resist pattern using the resist pattern forming composition. Preferably, the method for producing a device according to the present invention comprises producing a resist pattern by the aforementioned method, and comprises the following step.(6) performing a processing treatment with the resist pattern as a mask.

[0055] Step (6)The resist pattern is preferably used for processing a resist underlayer or a substrate (more preferably a substrate). Specifically, with the resist pattern as a mask, various substrates to serve as bases can be processed by using a dry etching method, a wet etching method, an ion implantation method, a metal plating method, or the like.The resist underlayer pattern may be formed with the resist pattern as a mask, and the substrate may be processed with the resist underlayer pattern as a mask. With the resist pattern as a mask, the resist underlayer and the substrate may be processed at the same time.Preferably, the method further comprises the step of forming a wiring on the processed substrate. A known method can be applied to these types of processing. Thereafter, if necessary, the substrate is cut into chips, connected to a lead frame,and packaged with a resin. In the present invention, this packaged product is referred to as a device. The device is preferably a semiconductor device.

[0056] The present invention will now be described by way of examples, as follows. The embodiment of the present invention is not limited to these examples.

[0057] Preparation of Resist Pattern Forming Composition> (Example 101 )As the component (A), a sublimable substance S1 having the following structure is prepared, and as the component (B), ultrapure water (DIW; De-ionized Water) is prepared. The component (A) is added to the component (B) such that the content of the component (A) becomes 1 .0 mass%. The mixture is stirred at room temperature for 30 minutes, and it is visually confirmed that the component (A) is dissolved. Thereafter, the mixture is filtered through a filter having a pore size of 0.2 pm to obtain a resist pattern forming composition (embedding solution) of Example 101.■ Sublimable substance S1 : Mw 104.15, melting point 128°C, boiling point 210°C [C6]

[0058] (Examples 102 to 3003, Comparative Example 101 to 301)Except for changing the components (A), (B), and (C), and their respective contents as shown in Table 1 , resist pattern forming compositions (embedding solutions) of Examples 102 to 3003 and Comparative Examples 101 to 301 are obtained in the same manner as the above preparation. The content is expressed as mass% based on the total mass of the resist pattern forming composition being 100.

[0059] [Table 1]Table 1(Continued from Table 1)

[0060] In Table 1 ,■ Sublimable substance S2: Mw 88.15, melting point 54°C, boiling point 114°C[C7J■ Sublimable substance S4: Mw 152.24, melting point 178°C, boiling point 204°C [C9]■ Sublimable substance S5: Mw 128.17, melting point 81 °C, boiling point 218°C[C10]■ Sublimable substance S6: Mw 118.09, melting point 54°C, boiling point 164°C[C11]■ Sublimable substance S7: Mw 136.24, melting point 75°C, boiling point 192°C[C12]■ Sublimable substance S8: Mw 80.09, melting point 54°C, boiling point 118°C[C13]■ Sublimable substance S9: Mw 154.25, melting point 208°C, boiling point 213°C [C14]■ Sublimable substance S10: Mw 126.2, melting point 45°C, boiling point 196°C[C15]

[0061] Preparation of Evaluation Substrate> (Example 101 )A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. A chemically amplified acrylic / methacrylic resist (hereinafter simply referred to as “positive type resist A” and indicated as “positive type A” in Table 2) as a positive type resist is applied thereon by spin coating, followed by heating on a hot plate at 110°C for 60 seconds and thereby giving a resist film having a thickness of 45 nm.This substrate is exposed through a mask (14 nm line / space =1 :1 ) using an electron beam lithography apparatus. The exposure amount at this time is set to 850 pC / cm2so that the resulting line width becomes 12.0 nm.Thereafter, PEB is performed on a hot plate at 100°C for 60 seconds, and a TMAH aqueous solution adjusted to 2.38 mass% is poured thereon as a developing solution, and then held for 30 seconds (puddling). In a state where a puddle of the developing solution is placed thereon, water starts to flow, the developing solution is replaced with water while the substrate is being rotated, the substrate is stopped with a puddle of water placed thereon and the system is left to stand for 60 seconds.Thereafter, in a state where a puddle of water is placed thereon, the resist pattern forming composition of Example 101 is poured thereon, and the water is replaced with the resist pattern forming composition, and the substrate is stopped with a puddle of the resist pattern forming composition for 10 seconds. The substrate is then spin-dried (1000 rpm, 60 seconds) to embed the sublimablesubstance S1 contained in the resist pattern forming composition between the resist patterns.The substrate is heated on a hot plate at 60°C for 120 seconds to remove the sublimable substance S1 by sublimation.

[0062] (Examples 102 and 103)Except that the resist pattern forming composition of Example 101 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 101.

[0063] (Example 201 )A silicon substrate is treated with HMDS at 90°C for 30 seconds. A positive type resist A is applied thereon by spin coating, followed by heating on a hot plate at 110°C for 60 seconds and thereby giving a resist film having a thickness of 45 nm.This substrate is exposed through a mask (14 nm line / space =1 :1 ) using an electron beam lithography apparatus. The exposure amount at this time is set to 850 pC / cm2so that the resulting line width becomes 12.0 nm.Thereafter, PEB is performed on a hot plate at 100°C for 60 seconds, and butyl acetate as a developing solution is poured thereon and then held for 30 seconds (puddling). In a state where a puddle of the developing solution is placed thereon, the resist pattern forming composition of Example 201 (butyl acetate solution) is poured, the butyl acetate of the developing solution is replaced with the resist pattern forming composition, and the substrate is stopped with a puddle of the resist pattern forming composition for 10 seconds.The substrate is then spin-dried (1000 rpm, 60 seconds) to embed the sublimable substance S1 contained in the resist pattern forming composition between the resist patterns. The substrate is heated on a hot plate at 60°C for 120 seconds to remove the sublimable substance S1 by sublimation.

[0064] (Examples 202 to 217)Except that the resist pattern forming composition of Example 201 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 201.

[0065] (Example 301 )A silicon substrate is treated with HMDS at 90°C for 30 seconds. A chemically amplified epoxy-based resist (hereinafter, simply referred to as “negative type resist A”, and indicated as “negative type A” in Table 2) as a negative type resist is applied thereon by spin coating, followed by heating on a hot plate at 110°C for 60 seconds and thereby giving a resist film having a thickness of 45 nm.This substrate is exposed through a mask (14 nm line / space =1 :1 ) using an electron beam lithography apparatus. The exposure amount at this time is set to 850 pC / cm2so that the resulting line width becomes 12.0 nm.Thereafter, PEB is performed on a hot plate at 100°C for 60 seconds, and butyl acetate as a developing solution is poured thereon and then held for 30 seconds (puddling). In a state where a puddle of the developing solution is placed thereon, the resist pattern forming composition of Example 301 (butyl acetate solution) is poured, the butyl acetate of the developing solution is replaced with the resist pattern forming composition, and the substrate is stopped with a puddle of the resist pattern forming composition for 10 seconds.The substrate is then spin-dried (1000 rpm, 60 seconds) to embed the sublimable substance S1 contained in the resist pattern forming composition between the resist patterns. The substrate is heated on a hot plate at 60°C for 120 seconds to remove the sublimable substance S1 by sublimation.

[0066] (Examples 302 and 303)Except that the resist pattern forming composition of Example 301 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 301.

[0067] (Examples 304 to 306)Except that the negative type resist A of Example 301 is changed to a tin oxide resist (hereinafter simply referred to as “negative type resist B”, and indicated as “negative type B” in Table 2), and the resist pattern forming composition of Example 301 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 301 .

[0068] (Example 1001 )To 78.5 g of DIW, 1 .0 g of the sublimable substance S1 as the component (A) is added, and the mixture is stirred at room temperature for 30 minutes, and it is visually confirmed that the component (A) is dissolved. 20.5 g of a 25% TMAH aqueous solution is added thereto, and the mixture is further stirred at room temperature for 30 minutes, and then filtered through a filter having a pore size of 0.2 pm to obtain a resist pattern forming composition of Example 1001. 15.4 g of water from 25% TMAH aqueous solution is component (B). The content of the component (A) is 1 .0 mass%, the content of the component (B) is 93.9 mass%, and the content of the component (C) is 5.1 mass%, based on the total mass of the resist pattern forming composition.Except that the 2.38 mass% of TMAH aqueous solution is not used as the developing solution, and that the resist pattern forming composition of Example 1001 , to which TMAH is added at 5.1 mass% is used instead of the resist pattern forming composition of Example 101 , the processing is performed in the same manner as in Example 101. The resist pattern forming composition of Example 1001 , which comprises TMAH as the component (C), also functions as a developing solution, and a resist pattern is formed.

[0069] (Example 2001 )Except that butyl acetate was not used as a developing solution, the same processing as in Example 201 was performed. In the resist pattern forming composition of Example 201 , ethyl lactate functions as a developing solution as the component (C), and a resist pattern is formed.

[0070] (Examples 2002 and 2003)Except that the resist pattern forming composition of Example 2001 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 2001 .

[0071] (Example 3001 )Except that butyl acetate was not used as a developing solution, the processing is performed in the same manner as in Example 301 . In the resist pattern forming composition of Example 3001 , propylene glycol monomethyl ether functions as a developing solution as the component (C), and a resist pattern is formed.

[0072] (Examples 3002 and 3003)Except that the resist pattern forming composition of Example 3001 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 3001 .

[0073] (Comparative Example 101 )Except that the resist pattern forming composition of Example 101 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 101.

[0074] (Comparative Examples 201 to 203)Except that the resist pattern forming composition of Example 201 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 201.In Comparative Example 201 , no resist pattern embedding film (embedding film) is formed between the resist patterns, and in Comparative Example 202, pattern collapse is observed due to insufficient film thickness of the embedding film.In Comparative Example 203, when butyl acetate of the developing solution is switched to the resist pattern forming composition of Comparative Example 203 (butyl acetate solution containing the sublimable substance S1 ), the sublimablesubstance S1 starts to solidify immediately, and therefore a uniform embedding film is not obtained, and collapse of the resist pattern is observed.

[0075] (Comparative Example 301 ) Except that the resist pattern forming composition of Example 301 is changed to the resist pattern forming composition listed in Table 1 , the processing is performed in the same manner as in Example 301.

[0076] Evaluation of Pattern Collapse> The resist pattern formed on the evaluation substrate is observed whether pattern collapse occurs or not using a length measurement SEM CG7300 (Hitachi High-Tech). An evaluation A is made when no collapse is found, and an evaluation B is made when collapse is found. The results are shown in Table 2 below.

[0077] [Table 2]Table 2(Continued from Table 2)[Reference Signs List]

[0078] 1 Substrate2 Photosensitive resin layer (resist film) 2A Resist pattern3 Developing solution4 Resist pattern forming composition (embedding solution)4A Solid phase (embedding film composed of solidifying component (A))

Claims

[CLAIMS]

1. A resist pattern forming composition comprising: a solidifying component (A); and a solvent (B), wherein the solidifying component (A) is a crystalline compound that does not contain an oxime and has a melting point at atmospheric pressure of 30°C or higher and 250°C or lower, and the content of the solidifying component (A) is 0.10 to 11 .0 mass% based on a total mass of the composition.

2. The resist pattern forming composition according to claim 1 , wherein the solidifying component (A) comprises at least one compound represented by any of Formulae (A-1 ) to (A-5):[C1 ]wherein groups X11are each independently -OH or -NH2,R11is substituted or unsubstituted C5-C20 alkyl or a substituted or unsubstituted C5-C20 saturated alicyclic hydrocarbon group, and one or more -CH2- groups or -CH= groups of R11may be substituted with -0- or -C(=O)- or may be unsubstituted, and noi is 1 or 2;[C2]whereinCy11is a substituted or unsubstituted C6-C20 hydrocarbon ring, and one or more -CH2- groups or -CH= groups of Cy11may be substituted with -C(=O)-, groups R12are each independently C1-C4 alkyl, and no2 is 0, 1 , 2, 3, 4, 5, or 6,[C3]whereinY11is NH or N,Y12to Y16are each independently CR13or N, and at least one of Y12to Y16is N, groups R13are each independently H or C1-C3 alkyl, and nos is 0 or 1 ;[C4]R14— fCOOR15] n04( A - 4 ) whereinR14is a single bond or a substituted or unsubstituted C1-C20 hydrocarbon group, groups R15are each independently H or C1-C3 alkyl, and no4 is 1 , 2, or 3; and[C5]( A - 5 )whereinR16is a substituted or unsubstituted C1-C20 hydrocarbon group, and nos is 1 , 2, 3, or 4.

3. The resist pattern forming composition according to claim 1 or 2, wherein a molecular weight of the solidifying component (A) is 70 or more and 200 or less.

4. The resist pattern forming composition according to claim 2 or 3, wherein R11comprises linear alkyl, branched alkyl, cyclic alkyl, aryl, or any combination thereof.

5. The resist pattern forming composition according to any one of claims 2 to 4, wherein Cy11comprises one or more -C(=O)- groups.

6. The resist pattern forming composition according to any one of claims 1 to 5, wherein the solvent (B) comprises at least one selected from the group consisting of water, alcohols, alkanes, ethers, lactic acid esters, acetic acid esters, aromatic hydrocarbons, ketones, amides, and lactones.

7. The resist pattern forming composition according to any one of claims 1 to 6, further comprising a developing component (C).

8. The resist pattern forming composition according to claim 7, wherein the content of the developing component (C) is 0.30 to 15.0 mass% based on a total mass of the resist pattern forming composition.

9. The resist pattern forming composition according to claim 7 or 8, wherein the developing component (C) is tetramethylammonium hydroxide.

10. The resist pattern forming composition according to any one of claims 1 to 9, further comprising an additive (D), wherein the additive (D) comprises at least one selected from the group consisting of a surfactant, an acid, a basic compound, an antimicrobial agent, a disinfectant, apreservative, and an antifungal agent, and the content of the additive (D) is 0.00 to 10.0 mass% based on a total mass of the solidifying component (A).

11. Use of the resist pattern forming composition according to any one of claims 1 to 10 for forming a resist pattern.

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