Pattern collapse inhibiting composition, method for producing pattern, and method for manufacturing device

Abstract

[Problem] To provide a pattern collapse inhibiting composition and a method for producing a pattern using the pattern collapse inhibiting composition. [Solution] A pattern collapse inhibiting composition comprising a solidifying component (A) and a solvent (B), wherein the solidifying component (A) is dicyclopropylketone oxime, 2,2,4,4-tetramethyl-3-pentanone oxime, or a mixture thereof. The pattern collapse inhibiting composition is a highly functional material that can be used in a semiconductor device production process of a nanotechnology process, for example, a semiconductor device production process for controlling a liquid crystal, quantum dot, or OLED display formed on a substrate.

Description

[DESCRIPTION][Title of Invention]PATTERN COLLAPSE INHIBITING COMPOSITION, METHOD FOR PRODUCING PATTERN, AND METHOD FOR MANUFACTURING DEVICE [Technical Field]

[0001] The present disclosure relates to a pattern collapse inhibiting composition, a method for producing a pattern, and a method for manufacturing a device. [Background Art]

[0002] In recent years, there is an increasing need for highly integrated LSIs, and pattern miniaturization is demanded. In order to meet these needs, lithography processes using short wavelength KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet radiation (EUV; 13 nm), X-rays, electron beams, or the like are being put into practical use. In order to deal with the miniaturization of patterns, a photosensitive resin composition used as a resist in microfabrication is also required to have properties for high resolution. Short-wavelength light exposure can form finer patterns, however, due to creating finer structures, pattern collapse may occur.

[0003] PTL 1 describes a substrate processing method including forming a solidified film from a treatment liquid containing a sublimable material and a solvent, and sublimating the solidified film.

[0004] PTL 2 describes a substrate processing method including forming a solidified film from a treatment liquid containing a first sublimable material and a second sublimable material, and sublimating and removing the solidified film.[Citation List][Patent Literature]

[0005] [PTL 1 ] JP 2022-170681 A [PTL 2] JP 2022-186047 A[Summary of Invention][Technical Problem]

[0006] The inventors believe that there are still one or more problems which need to be improved. Examples of such problems include: many defects occur in a fine pattern; pattern collapse occurs in a fine pattern; when a developer or a rinse liquid between patterns is removed by spin drying, pattern collapse occurs due to surface tension; a pattern cannot be cleaned thoroughly; removal of particles from a pattern is inefficient; a process for removing a film formed in a pattern cleaning process is complicated; a removal agent is required to remove a formed film; a formed film remains in a pattern without being removed; embedding in a fine pattern cannot be performed; precipitation occurs when a developer is replaced with another material; and yield is poor.

[0007] The present invention has been made based on the technical background as described above, and provides a pattern collapse inhibiting composition.[Solution to Problem]

[0008] A pattern collapse inhibiting composition according to one embodiment comprises a solidifying component (A) and a solvent (B): where the solidifying component (A) is dicyclopropylketone oxime, 2, 2,4,4- tetramethyl-3-pentanone oxime, or a mixture thereof; and a content of the solidifying component (A) based on a total mass of the composition is 0.10 to 15.0 mass%.

[0009] A method for producing a pattern according to one embodiment comprises using the aforementioned pattern collapse inhibiting composition.

[0010] A method for manufacturing a device according to one embodiment comprises the aforementioned method for producing a pattern.[Advantageous Effects of Invention]

[0011] By using the pattern collapse inhibiting composition of the present disclosure, the following one or more effects can be provided: occurrence of a defect in a fine pattern can be suppressed; pattern collapse can be suppressed in a fine pattern; pattern collapse can be suppressed when a developer or a rinse liquid between patterns is removed by spin drying; a pattern can be cleaned thoroughly; removal of particles from a pattern is efficient; a process for removing a film from a pattern cleaning process can be simplified; a need for a remover for removing a film can be eliminated; a formed film can be removed from within a pattern; embedding in a fine pattern can be performed; precipitation can be suppressed when a developer is replaced with the composition; and yield can be increased.

[0012] The above description is not to be construed as disclosing all embodiments of the present invention and all advantages related to the present invention. [Brief Description of Drawings]

[0013] [Fig. 1] Fig. 1 is an explanatory view of a method for producing a pattern according to a first embodiment.[Fig. 2] Fig. 2 is an explanatory view of a method for producing a pattern according to a second embodiment.[Description of Embodiments]

[0014] Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments, and various applications can be made within the spirit and scope of the present invention.

[0015] [Definitions]In the present disclosure, unless otherwise specifically stated, terms and symbols follow the definitions or examples described in this paragraph.The singular form includes the plural form, and the terms “a” and “the” mean “at least one.” An element of a certain concept can be expressed as a plurality oftypes, and when an amount thereof (for example, mass% or mol%) is described, the amount means a sum of the amounts of the plurality of types.The term “and / or” includes all combinations of elements, and also includes the use of a single element.When a numerical range is expressed using “to” or the range includes values at both ends, and the units are the same. For example, 5 to 25 mol% is 5 mol% or more and 25 mol% or less.Notations such as “Cx-y”, “Cx to Cy” and “Cx” refer to the number of carbon atoms in a molecule or substituent. For example, C1-6 alkyl is an alkyl chain having 1 or more and 6 or less carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).An aromatic hydrocarbon includes a polycyclic aromatic hydrocarbon.When a polymer has a plurality of structural units, monomers that form these structural units are copolymerized in the polymer. The copolymerization may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, and a mixture thereof. When polymers and resins are represented by structural formulae, the symbols n, m and the like in parentheses indicate the number of structural units.Degrees Celsius is used as the temperature unit. For example, 20 degrees is 20 degrees Celsius.The additive is a compound itself that exhibits the function. For example, a base generator is a compound that generates a base. There may also be an embodiment in which the compound is dissolved or dispersed in a solvent and is added to a composition. In one embodiment, such a solvent is preferably contained in the composition of the present disclosure as a solvent (B) or another component.Radiation refers to electromagnetic radiation including light having a wavelength from 10 to 400 nm.

[0016] <Pattern Collapse Inhibiting Composition>A pattern collapse inhibiting composition of the present disclosure (hereinafter, sometimes referred to as “the present composition”) is applied to a pattern such as a resist pattern or a substrate pattern, and for example, by drying asolvent, a pattern embedded film (hereinafter, sometimes referred to as “the embedded film”) is formed between the patterns. The present composition can also be referred to as an embedded film-forming liquid (hereinafter, sometimes referred to as “the embedding liquid”). The present composition is preferably a patterned embedded film-forming composition, more preferably a vaporization removal embedded film-forming composition, and still more preferably a sublimation removal embedded film-forming composition.The present composition is applied to a resist film after development or a substrate on which a pattern is formed. The embedding liquid of the present disclosure is preferably applied to a resist pattern after application of a developer or a cleaning liquid (hereinafter, sometimes referred to as the “rinse liquid”) or a substrate after pattern formation processing, and is more preferably used in order to replace therewith the developer or the cleaning liquid existing between the resist patterns. At this time, it is more preferable that a solute derived from at least one of the developer or the cleaning liquid and the embedding liquid is not precipitated when the developer or the cleaning liquid and the embedding liquid are mixed.

[0017] It is preferable that the embedding liquid of the present disclosure does not substantially vary a film thickness of the pattern when applied to the resist pattern or the substrate on which the pattern is formed.The embedded film of the present disclosure is sublimated at room temperature or by heating, and can be easily removed from between the patterns.

[0018] The pattern collapse inhibiting composition according to an embodiment comprises a solidifying component (A) and a solvent (B).

[0019] Solidifying component (A)The solidifying component (A) (hereinafter, sometimes referred to as the component (A); the same applies to other components) is dicyclopropylketone oxime (Formula (1 )), 2,2,4,4-tetramethyl-3-pentanone oxime (Formula (2)), or a mixture thereof. [Chem. 1]Formula (1 )Formula (2)When the component (A) is a mixture, a mass ratio of dicyclopropylketone oxime to 2,2,4,4-tetramethyl-3-pentanone oxime (mass of dicyclopropylketone oxime: mass of 2,2,4, 4-tetramethyl-3-pentanone oxime) is preferably from 99:1 to 1 :99, more preferably from 95:5 to 5:95, and still more preferably from 90:10 to 10:90.

[0021] Without being bound by theory, dicyclopropylketone oxime and 2, 2,4,4- tetramethyl-3-pentanone oxime as the component (A) easily penetrate between fine patterns during formation of a solidified film. It is believed that pattern collapse can be prevented by sublimation of the penetrated component (A).

[0022] The content of the component (A) is 0.10 to 15.0 mass%, preferably 0.20 to 12.0 mass%, and more preferably 0.30 to 10.0 mass%, based on a total mass of the composition. Without being bound by theory, it is believed that when the content of the component (A) is less than 0.10 mass%, pattern collapse occurs in a step of forming a solid phase due to insufficient filling of the component (A) between the patterns, and when the content is more than 15.0 mass%, drying of the solvent becomes insufficient in the step of forming a solid phase due to a large film thickness, and evaporation of the solvent occurs in a step of removing the film bysublimation, so that the pattern collapse occurs. Although the present composition may comprise a solidifying component other than the component (A), an embodiment in which the solidifying component other than the component (A) is not contained is a preferred embodiment.

[0023] When the composition is applied to the substrate pattern, the content of the component (A) is preferably 0.50 to 15.0 mass%, more preferably 0.70 to 12.0 mass%, and still more preferably 1 .0 to 11 .0 mass%, based on the total mass of the composition. The substrate pattern is often formed deeper than the resist pattern, that is, with a high pattern wall. On the other hand, the substrate pattern tends to have higher pattern rigidity than the resist pattern due to a nature of the material. By setting the content of the component (A) within the above range, it is possible to effectively suppress pattern collapse in a subsequent step by increasing the thickness of the embedded film while suppressing pattern collapse in the application step.

[0024] When the composition is applied to the resist pattern, the content of the component (A) is preferably 0.10 to 10.0 mass%, more preferably 0.20 to 8.0 mass%, and still more preferably 0.25 to 6.0 mass%, based on the total mass of the composition. Since the resist pattern has relatively low pattern rigidity, when a viscosity of the composition to be applied is excessively high, pattern collapse may be induced in the application step. On the other hand, since the resist pattern is often formed to be relatively shallow, that is, to have a relatively low pattern wall, the content of the component (A) can be set to be lower. By setting the content of the component (A) within the above range, pattern collapse in the application step can be suppressed, and the thickness of the embedded film desired for suppressing pattern collapse can be secured.

[0025] Solvent (B)The pattern collapse inhibiting composition of the present disclosure comprises the solvent (B). The component (B) preferably comprises at least oneselected from the group consisting of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, acetic acid esters, lactic acid esters, lactones, and amides.

[0026] Examples of the component (B) include alkanes such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n- propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di- i-propylbenzene, and n-amylnaphthalene; alcohols such as methanol, ethanol, n- propanol, i-propanol (IPA), n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i- pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2- methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2- ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, secundecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1 ,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1 ,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin; ketones such as 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, and fenchone; ethers such as ethyl ether, i-propy I 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-ethyl butyl 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, and 2- methyltetrahydrofuran; acetic acid esters such as methyl acetate, ethyl acetate, 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, and methoxytriglycol acetate; lactic acid esters such as methyl lactate, ethyl lactate (EL), n-butyl lactate, and n-amyl lactate; lactones such as y-butyrolactone and y-valerolactone; amides such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; other esters such as ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; carbonates such as diethyl carbonate; and sulfur compounds such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1 ,3-propane sultone. These solvents can be used alone or in combination of two or more kinds thereof.

[0027] A vapor pressure of the component (B) at 20°C and at 1 atm is preferably 0.20 to 20.0 kPa, more preferably 0.40 to 15.0 kPa, and still more preferably 1.0 to 14.0 kPa. By setting the vapor pressure of the component (B) to 0.20 kPa or more, the embedded film can be formed at a lower temperature or in a shorter time. Bysetting the vapor pressure of the component (B) to 20.0 kPa or less, the handleability of the composition can be improved, and a process window of the application step can be widened.

[0028] The component (B) is preferably nBA, EL, n-butyl lactate, n-pentyl acetate, IPA, n-butanol, PGME, 2-methylpentanol, DBE, ethylene glycol mono-n-butyl ether, PGMEA, cyclopentanone, cyclohexanone, di-i-butyl ketone or a mixture of two or more thereof; more preferably nBA, EL, IPA, n-butanol, PGME, 2-methylpentanol, PGMEA, cyclopentanone, cyclohexanone, or a mixture of two or more thereof; still more preferably nBA, IPA, PGME, PGMEA, cyclopentanone, or a mixture of two or more thereof; and even more preferably IPA. The component (B) preferably includes only one or two types of solvents, and more preferably includes only one type of solvent.

[0029] When the component (B) includes two kinds of solvents, the mass ratio thereof is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

[0030] The content of the component (B) is preferably 85.0 to 99.9 mass%, more preferably 88.0 to 99.8 mass%, still more preferably 90.0 to 99.8 mass%, and even more preferably 90.0 to 99.7 mass%, based on the total mass of the pattern collapse inhibiting composition.

[0031] Additive (C)The pattern collapse inhibiting composition of the present disclosure can further comprise an additive (C). The component (C) is at least one selected from the group consisting of a surfactant, an acid, a base, an antibacterial agent, a disinfectant, a preservative, and an antifungal agent. An example of the acid is acetic acid. The component (C) is preferably a surfactant, an acid, a base, an antibacterial agent, or a combination of two or more thereof, and more preferably a surfactant, an acid, an antibacterial agent, or a combination of two or more thereof.The component (C) is different from the component (A) and the component (B) described above.

[0032] The content (the sum in the case of a plurality of components) of the component (C) is preferably 0 to 10 parts by mass, more preferably 0.001 to 5.00 parts by mass, and still more preferably 0.001 to 1.00 parts by mass, based on 100 parts by mass of the component (A). It is also a preferred embodiment of the present disclosure that the present composition does not contain the component (C) (0 parts by mass).

[0033] <Method for Producing Pattern>A method for producing a pattern of the present disclosure uses the pattern collapse inhibiting composition described above.

[0034] The method for producing a pattern according to the first embodiment comprises the following steps. An explanatory view of this embodiment is presented in Fig. 1 .(1 ) Applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers interposed therebetween, to form a photosensitive resin layer;(2) exposing the photosensitive resin layer to radiation;(3) developing the exposed photosensitive resin layer using a developer;(4) processing the substrate using the developed photosensitive resin layer as a mask;(5) applying the pattern collapse inhibiting composition to the processed substrate;(6) removing at least a part of the solvent (B) in the pattern collapse inhibiting composition to form a solid phase; and(7) removing the solid phase by sublimation.

[0035] A method for producing a pattern according to the second embodiment comprises the following steps. An explanatory view of this embodiment is presented in Fig. 2.(1 A) Applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers interposed therebetween, to form a photosensitive resin layer;(2A) exposing the photosensitive resin layer to radiation;(3A) developing the exposed photosensitive resin layer using a developer; (4A) applying the pattern collapse inhibiting composition to the developed photosensitive resin layer;(5A) removing at least a part of the solvent (B) in the pattern collapse inhibiting composition to form a solid phase; and(6A) removing the solid phase by sublimation.

[0036] Steps (1 ) and (1A)A photosensitive resin layer is formed above a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, or the like) by applying a photosensitive resin composition.In the present disclosure, the term “above” includes a case of being formed immediately above and a case of being formed with another layer interposed therebetween. For example, one or more intermediate layers (for example, a planarization film or an underlayer antireflection film) may be formed immediately above the substrate, and the photosensitive resin composition may be applied immediately above the intermediate layers. In a preferred embodiment of the present disclosure, the photosensitive resin composition is applied immediately above the substrate to form a photosensitive resin layer (resist film). The application method is not particularly limited, and examples thereof include a method by coating with a spinner or a coater. Among them, spin coating is suitable. After the application, a photosensitive resin layer (resist film) is formed by drying and the like.

[0037] A method for forming the photosensitive resin layer is not particularly limited. The photosensitive resin composition is preferably a metal oxide-containing resist composition, a chemically amplified acrylic / methacrylic resist composition, a chemically amplified hydroxystyrene resist composition, a chemically amplifiedepoxy resist composition, or a chemically amplified hydroxystyrene-acrylate hybrid resist composition, and more preferably an organometallic oxide hydroxide- containing resist composition. The composition described in JP 2021-73367 A 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, the photosensitive resin composition is a negative resist. The solvent of the metal oxide-containing resist composition is preferably selected from an aromatic solvent (for example, xylene, toluene), an ether solvent (for example, anisole, tetrahydrofuran), an ester solvent (for example, PGMEA, ethyl acetate, nBA, ethyl lactate), an alcohol solvent (for example, 4- methyl-2-propanol, 1 -butanol, methanol, isopropyl alcohol, 1 -propanol), a ketone solvent (for example, methyl ethyl ketone, 2-heptanone), or a combination of two or more thereof.

[0038] The photosensitive resin composition is applied to the substrate and then preferably heated to form a photosensitive resin layer (resist film). 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 air 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.

[0039] Steps (2) and (2A)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), an extreme ultraviolet ray (EUV, 13.5 nm in wavelength), or the like can be used, and the extreme ultraviolet ray is preferable. These wavelengths have an allowable range of ± 1 %.After the exposure, a post-exposure bake (PEB) can also be performed, as necessary. The temperature of the PEB is preferably 80 to 200°C, more preferably90 to 190°C, and the heating time is preferably 30 to 240 seconds, more preferably 90 to 180 seconds.

[0040] Steps (3) and (3A)In a development step, the exposed photosensitive resin layer (resist film) is developed using a developer, thereby forming a resist pattern. Examples of the development include alkali development and organic solvent development. In the case of alkali development, examples of the developer include a tetramethylammonium hydroxide (TMAH) aqueous solution, a sodium carbonate aqueous solution, a sodium hydroxide aqueous solution, and a potassium hydroxide aqueous solution, a TMAH aqueous solution is preferable, and a 2.38% TMAH aqueous solution is more preferable. In the case of organic solvent development, examples of the developer include a hydrocarbon-based solvent, a carboxylic acidbased solvent, an ether-based solvent, an ester-based solvent, a ketone-based solvent, and an alcohol-based solvent. A carboxylic acid-based solvent, an ester- based solvent, or a ketone-based solvent is preferable, and a carboxylic acid-based solvent or an ester-based solvent is more preferable. Specifically, for example, 2- heptanone, cyclopentanone, nBA, PGMEA, and acetic acid are suitable as the developer.

[0041] The method for producing a pattern according to the present disclosure may further comprise a cleaning treatment using a cleaning liquid after step (3) or (3A).The cleaning liquid used in the cleaning treatment is preferably water, and more preferably pure water (DIW, deionized water, etc.). The cleaning treatment is useful for cleaning the developer attached to the resist pattern. The cleaning treatment may be performed by a known method, and for example, can be performed by dropping pure water on the surface of the resist pattern of the rotating substrate.A preferred embodiment of a method for producing a pattern according to the second embodiment is a method in which a cleaning liquid is poured into a developed resist pattern to clean the pattern while replacing a developer with the cleaning liquid, the pattern collapse inhibiting composition is poured while the resistpattern is immersed in the cleaning liquid to replace the cleaning liquid with the present composition, and then the pattern is cleaned by steps (4A) to (6A).

[0042] Step (4)In the first embodiment, the resist pattern formed in the developed photosensitive resin layer is preferably used for processing a resist underlayer or a substrate (more preferably a substrate). Specifically, using the resist pattern as a mask, the resist underlayer or various substrates to be underlying layers can be processed using known means such as dry etching and wet etching.A resist underlayer pattern may be formed using the resist pattern as a mask, and the substrate may be processed using the resist underlayer pattern as a mask. The resist underlayer and the substrate may be simultaneously processed using the resist pattern as a mask.The processed substrate is, for example, a patterned substrate. The wiring can be formed on the substrate using the formed pattern.

[0043] After the processing, the resist pattern is removed, as necessary. The resist pattern on the substrate can be removed by dry etching using O2, CF4, CHF3, CI2, or BCI3. As the dry etching gas, O2 or CF4 is preferably used. The resist pattern may be removed before step (5) or after step (7).

[0044] The method for producing a pattern according to the first embodiment may further comprise a cleaning treatment using a cleaning liquid after step (4).The cleaning liquid used for the cleaning treatment is pure water (DIW, deionized water, etc.), sulfuric acid, hydrofluoric acid, ammonia water, SPM (a mixed liquid of sulfuric acid, hydrogen peroxide, and water), SC1 (a mixed liquid of ammonia, hydrogen peroxide, and water), SC2 (a mixed liquid of hydrogen chloride, hydrogen peroxide, and water), or IPA, preferably pure water, hydrofluoric acid, SC1 , DIW, or IPA, and more preferably pure water, SC1 , or IPA. The cleaning treatment is useful for cleaning and removing processing residues and the like attached to the substrate pattern. The cleaning treatment may be performed by a known method, and for example, can be performed by dropping pure water on thesurface of the substrate pattern of the rotating substrate. A preferred embodiment of the method for producing a pattern according to the first embodiment is a method in which the pattern collapse inhibiting composition is poured while the substrate pattern is immersed in the cleaning liquid to replace the cleaning liquid with the present composition, and then the pattern is cleaned by steps (5) to (7).

[0045] Steps (5) and (4A)The pattern collapse inhibiting composition according to the present disclosure is applied to the substrate pattern or the resist pattern. The pattern collapse inhibiting composition can be introduced into these patterns by any known method. For example, the method can be performed by immersing the substrate having the substrate pattern or the substrate having the resist pattern in the pattern collapse inhibiting composition, or dropping the pattern collapse inhibiting composition on the rotating substrate surface. These methods may be appropriately combined.The state in which the substrate pattern or the resist pattern is immersed in the pattern collapse inhibiting composition is maintained for preferably 0.5 to 30 seconds, more preferably 0.5 to 25 seconds, and still more preferably 1 to 20 seconds. The temperature at which the present composition is applied 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.

[0046] In the second embodiment, the pattern collapse inhibiting composition is preferably applied to the resist pattern to which the developer has been applied, and more preferably used for the purpose of replacing the developer present between the resist patterns. By pouring the pattern collapse inhibiting composition into the developed resist pattern, the developer is replaced with the present composition.

[0047] Steps (6) and (5A)After the pattern collapse inhibiting composition is applied between the patterns, at least a part of the component (B) is removed by heating, nitrogen gasspraying, or spin dry heating, preferably by heating or nitrogen gas spraying, and dried to form a solid phase (embedded film containing the component (A)) between the patterns.

[0048] The heating temperature in the case of forming a solid phase by heating is preferably 50 to 200°C, more preferably 50 to 160°C, and still more preferably 50 to 120°C. The heating time is preferably 30 to 240 seconds, and more preferably 30 to 120 seconds. The heating is preferably performed in the air or a nitrogen gas atmosphere.

[0049] When a solid phase is formed by nitrogen gas spraying, a flow rate of the nitrogen gas is preferably 1 to 100 L / min, more preferably 10 to 80 L / min, and still more preferably 20 to 70 L / min. The temperature of the substrate is preferably 10 to 50°C, more preferably 20 to 50°C, and still more preferably 20 to 40°C. The nitrogen gas spraying time is preferably 10 to 200 seconds, and more preferably 30 to 100 seconds.

[0050] A rotation speed of the substrate in the case of forming a solid phase by spin drying is preferably 100 to 4000 rpm, more preferably 500 to 3000 rpm, and still more preferably 1000 to 3000 rpm. The temperature of the substrate is preferably 10 to 50°C, more preferably 20 to 50°C, and still more preferably 20 to 40°C. The rotation time is preferably 10 to 200 seconds, more preferably 10 to 180 seconds, and still more preferably 20 to 150 seconds. The spin drying is preferably performed in the air or a nitrogen gas atmosphere.

[0051] Steps (7) and (6A)The solid phase formed between the patterns is sublimated by heating and removed from between the resist patterns. The heating temperature to sublimate 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 air or a nitrogen gas atmosphere.There is no intention to limit the scope of the invention, and there is no intention to be bound by theory; however, since the component (A) is a crystalline compound, a condensation reaction by heating does not occur, and a material in which the molecular weight is increased does not adhere to the resist pattern and become difficult to be removed.It is also possible to combine heating and gas spraying. The gas to be sprayed is not particularly limited. Although a gas such as air can be used, it is preferable to use an inert gas such as argon gas or nitrogen gas. The gas flow rate is not particularly limited, and the conditions are suitably selected. 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.

[0052] Figs. 1(i) and 2(i) illustrate a state in which a photosensitive resin layer (resist film) 2 is formed immediately above a substrate 1 , and exposed through a predetermined mask, and then a developer 3 is applied. In this state, an exposed portion in a positive resist and an unexposed portion in a negative resist are dissolved in the developer 3 and developed.

[0053] Figs. 1(ii) and 2(ii) illustrate a state in which a resist pattern 2A is formed immediately above the substrate 1 and the developer 3 remains between the resist patterns 2A. In the second embodiment, the pattern collapse inhibiting composition (embedding liquid) can be applied in this state.

[0054] Fig. 1(iii) illustrates a state in which the resist pattern 2A is formed immediately above the substrate 1 . Fig. 2(iii) illustrates a state in which the resist pattern 2A is formed immediately above the substrate 1 , and the developer 3 between the resist patterns 2A is replaced with the pattern collapse inhibiting composition 4.

[0055] Fig. 1 (iv) illustrates a state in which the substrate 1 is processed using the resist pattern 2A as a mask to form a substrate pattern 1A. Fig. 1 (v) illustrates astate in which the pattern collapse inhibiting composition 4 is disposed between the substrate pattern 1A and the resist pattern 2A.

[0056] Figs. 1 (vi) and 2(iv) illustrate a state in which the component (B) of the pattern collapse inhibiting composition (embedding liquid) is removed to form a solid phase (embedded film containing the component (A)) 4A between the substrate patterns 1A or the resist patterns 2A. Although Figs. 1 (vi) and 2(iv) are diagrams in which the solid phase 4A partially fills a space between the substrate patterns 1 A or the resist patterns 2A, the solid phase 4A may completely fill the space. Even in a case where the solid phase (embedded film) 4A is formed only at a bottom portion between the substrate patterns 1 A or the resist patterns 2A, the effect of preventing pattern collapse can be exhibited.

[0057] Figs. 1 (vii) and 2(v) illustrate a state in which the solid phase (embedded film containing the component (A)) 4A between the substrate pattern 1 A or the resist pattern 2A is removed by sublimation. Thus, in the second embodiment, the substrate 1 having the resist pattern 2A is produced.

[0058] Fig. 1 (viii) illustrates a state in which the resist pattern 2A is removed. Thus, in the first embodiment, the substrate 1 having the substrate pattern 1 A is produced.

[0059] The first embodiment and the second embodiment can be combined. For example, a method for producing a pattern according to a third embodiment comprises the following steps:(1 B) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers interposed therebetween, to form a photosensitive resin layer;(2B) exposing the photosensitive resin layer to radiation;(3B) developing the exposed photosensitive resin layer using a developer; (4B) applying the pattern collapse inhibiting composition to the developed photosensitive resin layer;(5B) removing at least a part of the solvent (B) in the pattern collapse inhibiting composition to form a solid phase;(6B) removing the solid phase by sublimation;(7B) processing the substrate using the developed photosensitive resin layer as a mask;(8B) applying the pattern collapse inhibiting composition to the processed substrate; (9B) removing at least a part of the solvent (B) in the pattern collapse inhibiting composition to form a solid phase; and(10B) removing the solid phase by sublimation.Each step is as described in the first embodiment and the second embodiment.

[0060] <Method for Manufacturing Device>A method for manufacturing a device according to the present disclosure comprises forming a pattern by the method described above.

[0061] In the method for manufacturing a device, ion-doping can be performed on the substrate or the resist underlayer using the resist pattern produced by the aforementioned method as a mask. Ion-doping is performed on the substrate or the resist underlayer using the formed resist pattern as a mask, or the underlayer of the resist pattern is processed using the formed resist pattern as a mask to form a resist underlayer pattern, and ion-doping is performed on the substrate using the resist underlayer pattern as a mask. Ion-doping can be performed by a known method using a known ion-doping apparatus. Generally, in the manufacturing of semiconductor devices, display devices, and the like, an impurity diffusion layer is formed on the surface of a substrate. The impurity diffusion layer is usually formed in two steps of impurity introduction and diffusion. One of the methods of impurity introduction is ion-doping in which impurities such as phosphorus and boron are ionized in vacuum and accelerated at a high electric field to be implanted into the surface of the substrate or the layer. The ion acceleration energy during ion-doping is generally 10 to 200 keV. Examples of ion sources (impurity elements) includeions such as boron, phosphorus, arsenic, and argon. Examples of a thin film on the substrate include a thin film of silicon, silicon dioxide, silicon nitride, or aluminum.

[0062] The method for manufacturing a device preferably further comprises a step of forming wiring on the processed substrate. Known methods can be applied to these processes. The substrate is then optionally cut into chips, connected to a lead frame, and packaged in resin. In the present disclosure, the packaged product is referred to as a device. The device is preferably a semiconductor device. [Examples]

[0063] The present invention will be described below using various examples. Note that the aspects of the present invention are not limited to these examples.

[0064] Preparation Example of Pattern Collapse Inhibiting Composition> The components are shown in Table 1 .

[0065] [Table 1]Table 1

[0066] A sublimable material shown in Table 1 as the component (A) and 2-propanol (IPA) as the component (B) are provided, and the component (A) is added to the component (B) so that the content of the component (A) has the numerical values shown in Tables 2 and 3. 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 pattern collapse inhibiting composition.

[0067] <Si Pattern (substrate pattern)>Examples 1 to 7 and Comparative Examples 1 to 320 mL of the composition of Example 1 is applied to a 300 mm wafer (hereinafter, referred to as a patterned wafer) on which a pillar pattern is formed using Lithius ProZ (Tokyo Electron), and spin-coated at 1000 rpm for 20 seconds. In the patterned wafer, a pillar pattern having a top diameter of a cylinder of about 30 nm, a bottom diameter of about 65 nm, and a height of about 600 nm is formed on a silicon wafer (provided by Interuniversity Microelectronics Centre (imec)). The sublimable material is embedded in the pattern by spin coating.The sublimable material is removed by sublimation by blowing nitrogen gas to the substrate at 50 L / min or heating the substrate on a hot plate at 60°C for 120 seconds.The pattern formed on the evaluation substrate is observed for the presence of pattern collapse using a length-measuring SEM CG7300 (Hitachi High-Technologies). A collapse rate of less than 1 % is evaluated as A, and the collapse rate of 1 % or more is evaluated as B. The results are shown in Table 2-1 and Table 2-2.

[0068] <Resist Pattern>Examples 11 to 17, Comparative Examples 11 to 12A silicon wafer is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. A negative resist is applied thereon by spin coating, and heated on a hot plate at 110°C for 60 seconds to obtain 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 / cm2, and the line width to be obtained is set to 12.0 nm.Thereafter, a post exposure bake (PEB) is performed on the hot plate at 100°C for 60 seconds, butyl acetate is poured as a developer, and then the mixture is held for 30 seconds (paddle). With the developer paddled, the composition of Example 11 is poured in so that butyl acetate is replaced with the composition of Example 11 , and the substrate is stopped for 10 seconds in a state of being paddled with the composition. The substrate is spin-dried (1000 rpm, 20 seconds), and the sublimable material in the composition of Example 11 is embedded between the resist patterns.The sublimable material is removed by sublimation by blowing nitrogen gas to the substrate at 50 L / min or heating the substrate on a hot plate at 60°C for 120 seconds.The pattern formed on the evaluation substrate is observed for the presence of pattern collapse using CG7300. The collapse rate of less than 1 % is evaluated as A, and the collapse rate of 1 % or more is evaluated as B. The results are shown in Table 3-1 and Table 3-2.

[0069] <Stability Evaluation>The composition shown in each Table is put in a glass bottle and stored in a thermostatic chamber set at 40°C for 30 days. The composition before and after storage is analyzed using LC-MS (LC-MS2050, Shimadzu Corporation) to evaluate the presence or absence of a new peak due to storage. When no new peak is observed, stability over time is evaluated as A, and when a new peak is observed, the stability over time is evaluated as B. The results are shown in Table 2-1 , Table 2-2, Table 3-1 , and Table 3-2.

[0070] <Comprehensive Evaluation>A case where both the pattern collapse evaluation and the stability evaluation are evaluated as A is evaluated as A, and the others are evaluated as B. The results are shown in Table 2-1 , Table 2-2, Table 3-1 , and Table 3-2.

[0071] [Table 2-1]Table 2-1[Table 2-2]Table 2-2

[0072] [Table 3-1]Tabb 3-1[Table 3-2]Table 3-2Reference Signs List

[0073] 1 . Substrate1A. Substrate pattern 2. Photosensitive resin layer (resist film)2A. Resist pattern3. Developer4. Pattern collapse inhibiting composition (embedding liquid)4A. Solid phase (embedded film containing solidifying component (A))

Claims

[CLAIMS]

1. A pattern collapse inhibiting composition, comprising a solidifying component (A) and a solvent (B), wherein the solidifying component (A) is dicyclopropylketone oxime, 2, 2,4,4- tetramethyl-3-pentanone oxime, or a mixture thereof; and a content of the solidifying component (A) based on a total mass of the composition is 0.10 to 15.0 mass%, and preferably 0.20 to 12.0 mass%.

2. The pattern collapse inhibiting composition according to claim 1 , wherein the solvent (B) comprises at least one selected from the group consisting of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, acetic acid esters, lactic acid esters, lactones, and amides: preferably, a vapor pressure of the solvent (B) at 20°C and at 1 atm is 0.20 to 20.0 kPa, and more preferably 0.40 to 15.0 kPa.

3. The pattern collapse inhibiting composition according to claim 1 or 2, further comprising an additive (C), wherein the additive (C) comprises at least one selected from the group consisting of a surfactant, an acid, a base, an antibacterial agent, a disinfectant, a preservative, and an antifungal agent, and a content of the additive (C) is 0 to 10 parts by mass, based on 100 parts by mass of the solidifying component (A).

4. A method for producing a pattern, wherein the pattern collapse inhibiting composition according to any one of claims 1 to 3 is used.

5. The method for producing a pattern according to claim 4, the method comprising the following steps:(1 ) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers interposed therebetween, to form a photosensitive resin layer;(2) exposing the photosensitive resin layer to radiation;(3) developing the exposed photosensitive resin layer using a developer;(4) processing the substrate using the developed photosensitive resin layer as a mask;(5) applying the pattern collapse inhibiting composition according to any one of claims 1 to 3 to the processed substrate;(6) removing at least a part of the solvent (B) in the pattern collapse inhibiting composition to form a solid phase; and(7) removing the solid phase by sublimation.

6. The method for producing a pattern according to claim 4, the method comprising the following steps:(1A) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers interposed therebetween, to form a photosensitive resin layer;(2A) exposing the photosensitive resin layer to radiation;(3A) developing the exposed photosensitive resin layer using a developer;(4A) applying the pattern collapse inhibiting composition according to any one of claims 1 to 3 to the developed photosensitive resin layer;(5A) removing at least a part of the solvent (B) in the pattern collapse inhibiting composition to form a solid phase; and(6A) removing the solid phase by sublimation.

7. The method for producing a pattern according to claim 5 or 6, wherein the steps (6) and (5A) comprise heating at 50 to 200°C, and preferably 50 to 160°C.

8. The method for producing a pattern according to claim 5 or 6, wherein the steps (6) and (5A) comprise spraying a nitrogen gas onto the pattern at a flow rate of 1 to 100 L / min, and a temperature of 10 to 50°C.

9. The method for producing a pattern according to claim 5 or 6, wherein the steps (6) and (5A) comprise rotating the substrate at a temperature of 10 to 50°C, and 100 to 4000 rpm, for 10 to 200 seconds.

10. A method for manufacturing a device, comprising the method for producing a pattern according to any one of claims 4 to 9.

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