WO2012132686A1 - パターン反転膜形成用組成物及び反転パターン形成方法 - Google Patents
パターン反転膜形成用組成物及び反転パターン形成方法 Download PDFInfo
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- WO2012132686A1 WO2012132686A1 PCT/JP2012/054587 JP2012054587W WO2012132686A1 WO 2012132686 A1 WO2012132686 A1 WO 2012132686A1 JP 2012054587 W JP2012054587 W JP 2012054587W WO 2012132686 A1 WO2012132686 A1 WO 2012132686A1
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Images
Classifications
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
- G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a composition for forming a pattern reversal film and a method for forming a reversal pattern using the composition. More specifically, the present invention provides a pattern reversal film forming composition capable of forming a reversal pattern removable with an organic solvent.
- a photoresist pattern is formed through photoresist coating, pre-baking, exposure, post-baking, and resist development steps.
- the above-mentioned photoresist pattern is increasingly required to be miniaturized.
- a pattern forming method for high-precision dimensional control a reversal mask pattern forming method and the like A resin composition for pattern reversal to be used has been proposed (Patent Documents 1 and 2).
- ashing oxygen plasma
- chemical solution resist stripping solution
- rework ashing
- the above reversal mask pattern is also required to have reworkability (referring to reworkable or easy properties).
- ashing is performed. Even if it is almost impossible to remove because it is altered and hardened to silicon oxide, and since the pattern has undergone a crosslinking reaction by baking, removal by chemical treatment using a conventional resist stripper becomes difficult. It was.
- An object of this invention is to provide the composition for silicon-containing pattern reversal film formation which can be reworked with the organic solvent normally used for peeling of a resist pattern.
- the present inventors use a special drug by constructing a composition containing a polysiloxane having a specific structural unit and a specific additive.
- the present inventors have found that a composition for forming a pattern reversal film that can remove a reversal pattern by a chemical treatment using an organic solvent is obtained, and the present invention has been completed.
- the present invention provides a pattern reversal film forming composition containing polysiloxane, an additive, and an organic solvent, wherein the polysiloxane is a structural unit and a formula represented by the following formula (1): Having a structural unit represented by (2), (Wherein R 1 represents an alkyl group having 1 to 8 carbon atoms.) (Wherein R 2 represents an acryloyloxy group or a methacryloyloxy group, and n represents an integer of 2 to 4);
- the additive is an organic acid having at least two carboxyl groups and / or hydroxy groups.
- the additive is maleic acid, citric acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, phthalic acid It is related with the composition for pattern inversion film formation as described in a 1st viewpoint which is an organic acid selected from the group which consists of pyromellitic acid and ascorbic acid.
- the present invention relates to the pattern reversal film forming composition according to the first aspect or the second aspect, wherein the organic solvent is selected from alcohols having 2 to 10 carbon atoms.
- the polysiloxane includes the structural unit represented by the formula (1) and the structural unit represented by the formula (2) in a molar ratio of 50:50 to 99: 1.
- the present invention relates to the pattern reversal film forming composition according to any one of the first aspect to the third aspect.
- a pattern reversal film obtained by coating a resist pattern on a substrate to be processed with the pattern reversal film forming composition according to any one of the first to fourth aspects, and heating the pattern reversal film also relates to a method for removing a pattern reversal film that is peeled off together with the resist pattern by an organic solvent.
- the pattern reversal film according to the sixth aspect wherein the organic solvent is composed of one or more selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and cyclohexanone. It is related with the removal method.
- the composition for forming a pattern reversal film of the present invention can form a pattern reversal film that can be removed with an organic solvent.
- the pattern reversal film forming composition of the present invention can form a removable pattern reversal film using a general-purpose organic solvent such as a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
- a general-purpose organic solvent such as a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
- the substrate can be recycled and reused, which contributes to the cost reduction of the semiconductor manufacturing process.
- the composition for forming a pattern reversal film of the present invention can form a film that satisfies the required performance as a pattern reversal film.
- composition for forming a pattern reversal film of the present invention can be used very suitably in the manufacture of LSIs that are expected to be further miniaturized in the future.
- FIG. 1 is a view showing a cross-sectional SEM image of a resist pattern on a silicon substrate on which an organic underlayer film is formed.
- FIG. 2 is a diagram showing a cross-sectional SEM image of a pattern reversal film obtained using the pattern reversal film forming composition obtained in Example 1.
- FIG. 3 is a view showing a cross-sectional SEM image of the resist pattern and the pattern reversal film in which the upper part of the resist pattern is exposed.
- FIG. 4 is a view showing a cross-sectional SEM image of a reversal pattern obtained using the composition for forming a pattern reversal film of Example 1.
- FIG. 1 is a view showing a cross-sectional SEM image of a resist pattern on a silicon substrate on which an organic underlayer film is formed.
- FIG. 2 is a diagram showing a cross-sectional SEM image of a pattern reversal film obtained using the pattern reversal film forming composition obtained in Example 1.
- FIG. 5 is a view showing a cross-sectional SEM image as a result of patterning the organic underlayer film using the obtained inverted pattern as an etching mask.
- FIG. 6 is a view showing a cross-sectional SEM image of a resist pattern on a silicon substrate on which an organic underlayer film is formed.
- FIG. 7 shows a cross-sectional SEM image of the resist pattern and the pattern reversal film in which the upper part of the resist pattern is exposed after forming the pattern reversal film using the pattern reversal film forming composition obtained in Example 18
- FIG. FIG. 8 is a view showing a cross-sectional SEM image as a result of patterning the organic underlayer film using the inverted pattern obtained by removing the resist pattern as an etching mask.
- the polysiloxane contained in the composition for forming a pattern reversal film of the present invention is a polysiloxane having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
- R 1 represents an alkyl group having 1 to 8 carbon atoms.
- R 2 represents an acryloyloxy group or a methacryloyloxy group
- n represents an integer of 2 to 4.
- R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, heptyl, hexyl, octyl, cyclohexyl Group etc. are mentioned, Preferably they are a methyl group or an ethyl group.
- the ratio of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2) is preferably 50:50 to 99: 1 in molar ratio, It is preferably 70:30 to 95: 5.
- the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2) may form any structure of a random copolymer, a block copolymer, and an alternating copolymer. Good.
- the polysiloxane contained in the composition for forming a pattern reversal film of the present invention is obtained by, for example, subjecting a silane compound represented by the following formula (3) and a silane compound represented by the following formula (4) to a cohydrolytic condensation reaction. Obtained by.
- R 1 Si (OR 3 ) 3 (3) (Wherein R 1 has the same definition as in formula (1), and R 3 independently represents an alkyl group having 1 to 4 carbon atoms.)
- R 2 (CH 2 ) n Si (OR 4 ) 3 (4) In the formula, R 2 and n are as defined in formula (2), and R 4 each independently represents an alkyl group having 1 to 4 carbon atoms.)
- Examples of the alkyl group having 1 to 4 carbon atoms in the silane compounds represented by the above formulas (3) and (4) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
- a tert-butyl group preferably a methyl group or an ethyl group.
- each R 3 or each R 4 may be the same or may be partially different.
- silane compound represented by the above formula (3) examples include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltriisoiso Methyltrialkoxysilanes such as butoxysilane and methyltri-tert-butoxysilane; ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltriisobutoxy Examples thereof include ethyltrialkoxysilane such as silane and ethyltri-tert-butoxysilane. Among these, methyltrimethoxysilane or methyltriethoxysilane is preferable.
- silane compound represented by the above formula (4) examples include 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropyl.
- Examples include triethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, and 2-methacryloyloxyethyltriethoxysilane.
- 3-methacryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltriethoxysilane are preferable.
- One of these compounds represented by formula (4) may be used alone, or two or more thereof may be used in combination.
- the cohydrolysis condensation reaction of the silane compound represented by the above formula (3) and the silane compound represented by the above formula (4) is typically carried out in the presence of a basic catalyst such as an organic base or an inorganic base.
- a basic catalyst such as an organic base or an inorganic base.
- preferred catalysts include, for example, potassium hydroxide, cesium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and phosphazene base (eg, Phosphazene Base P 4 -t-Bu solution). Can do.
- the amount of the basic catalyst used is usually 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of the silane compound represented by formula (3) and the silane compound represented by formula (4). Part.
- the co-hydrolysis condensation reaction is performed under a temperature condition of 60 ° C. to 80 ° C., for example.
- the concentration of polysiloxane in the composition for forming a pattern reversal film of the present invention can be adjusted as appropriate, and can be, for example, 1% by mass to 30% by mass, particularly 5% by mass to 20% by mass.
- the additive contained in the pattern reversal film forming composition of the present invention is an organic acid having at least two carboxyl groups and / or hydroxy groups.
- the above additives are preferably maleic acid, citric acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, phthalic acid, pyro It is an organic acid selected from the group consisting of merit acid and ascorbic acid.
- the usage-amount of the said additive in the composition for pattern reversal film formation of this invention is 0.01 mass% thru
- Organic solvent contained in the composition for forming a pattern reversal film of the present invention is capable of dissolving the organic acid as the additive, and is preferably selected from alcohols having 2 to 10 carbon atoms. When an organic solvent that does not dissolve the organic acid is applied, the effects of the present invention may not be sufficiently obtained.
- the organic solvent may further contain a resist solvent as long as intermixing with the resist pattern does not occur.
- the alcohol having 2 to 10 carbon atoms may be linear, branched or cyclic, for example, ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, glycerin, 1-butanol, 2 -Butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1,4-butanediol, pentanol, 1-methyl-1-butanol, 2-methyl-1-butanol, 3-methyl-1 -Butanol, cyclopentanol, hexanol, 4-methyl-2-pentanol, cyclohexanol, heptanol, cycloheptanol, octyl alcohol, nonyl alcohol, decyl alcohol, diethylene glycol, dipropylene glycol, triethylene glycol tripropi Glycol, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, 4-methoxy-1-but
- composition for forming a pattern reversal film of the present invention may contain various additives such as a surfactant, if desired.
- Surfactant is an additive for improving the coating property of the composition for forming a pattern reversal film.
- Known surfactants such as nonionic surfactants and fluorine-based surfactants can be used.
- the composition for forming a pattern reversal film of the present invention is 0.01% by mass or more and 0.5% by mass or less.
- it can be added in a proportion of 0.2% by mass or less, preferably 0.1% by mass or less.
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxye Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as lensorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc
- EF301, EF303, EF352 Mitsubishi Materials Electronics Kasei Co., Ltd. (formerly Gemco)), MegaFuck [registered trademark] F171, F173, R-30 (DIC Corporation), Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass ( Made by Co., Ltd.) Fluorosurfactants, may be mentioned organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co.). These surfactants may be added alone or in combination of two or more.
- the above-mentioned pattern reversal film forming composition is applied to a substrate and baked at a temperature of 80 ° C. to 180 ° C. It is a method including the process to do.
- the substrate for example, a semiconductor substrate such as a silicon substrate is used, and a stepped substrate on which a resist pattern is formed is used.
- the reverse pattern forming method of the present invention includes (a) a step of forming a resist pattern on a substrate to be processed, (b) applying the above-described composition for forming a pattern reverse film so as to cover the resist pattern, A step of forming a pattern reversal film by heating at a temperature of from 1 to 180 ° C., (c) a step of etching back the pattern reversal film to expose the surface of the resist pattern, and (d) removing the resist pattern. And a step of forming a reverse pattern.
- a resist material is applied onto the substrate to be processed by an appropriate application method such as a spinner or a coater, and is usually dried at a temperature of about 80 ° C. to 180 ° C. To form a resist film.
- the thickness of the resist at this time is usually 10 nm to 1000 nm.
- the resist film is exposed using a light source such as visible light, ultraviolet light, and X-rays through a mask having a predetermined pattern, and the exposed portion is developed with a developer. Then, if necessary, post-exposure heating (PEB: Post Exposure Bake) is performed to form a predetermined resist pattern.
- PEB Post Exposure Bake
- a substrate used for manufacturing a precision integrated circuit element for example, a semiconductor substrate such as a silicon substrate coated with a silicon oxide film, a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate
- a semiconductor substrate such as a silicon substrate coated with a silicon oxide film, a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate
- Glass substrates including alkali-free glass, low alkali glass, and crystallized glass
- glass substrates on which an ITO film is formed can be used.
- an underlayer film having an organic or inorganic antireflection ability may be formed in advance on the substrate to be processed.
- a positive resist comprising a novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified resist comprising a photoacid generator and a binder having a group which decomposes with an acid to increase the alkali dissolution rate, an alkali-soluble binder, Chemically amplified resist composed of a low molecular weight compound that decomposes with a photoacid generator and acid to increase the alkali dissolution rate of the resist, a binder and an acid having a group that decomposes with a photoacid generator and acid to increase the alkali dissolution rate
- chemically amplified resists composed of low molecular weight compounds that decompose by the above-mentioned and increase the alkali dissolution rate of the resist, such as Sumitomo Chemical Co., Ltd., trade names PAR710, PAR855 and JSR Corporation, trade names AR2772
- the resist developer examples include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline
- An aqueous solution of an alkali such as a quaternary ammonium salt such as pyrrole or a cyclic amine such as piperidine can be used.
- an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.
- a preferred developer is an aqueous solution of a quaternary ammonium salt, more preferably an aqueous solution of tetramethylammonium hydroxide.
- the step of applying the above-described composition for forming a pattern reversal film so as to cover the resist pattern and forming the pattern reversal film is performed by a substrate (step difference) formed on the surface of the resist pattern.
- the above-mentioned composition for forming a pattern reversal film is applied onto a substrate by an appropriate application method such as a spinner or a coater. Thereafter, baking is performed at a temperature of 80 ° C. to 180 ° C. to form a pattern reversal film.
- the organic solvent in the coating film can be quickly volatilized by baking at 80 ° C. to 150 ° C.
- the baking time at this time is usually 10 seconds to 300 seconds, preferably 30 seconds to 180 seconds.
- the thickness of the pattern reversal film is not particularly limited, but is usually 10 nm to 1000 nm, preferably 50 nm to 500 nm.
- a step of etching back the pattern reversal film to expose the surface of the resist pattern, and (d) a step of removing the resist pattern and forming a reversal pattern are performed. More specifically, the pattern reversal film formed as described above is etched back until the resist pattern surface is exposed, and then the resist pattern is removed by, for example, O 2 etching (ashing). A desired inversion pattern is formed.
- the etch back process dry etching using a fluorine-based gas such as CF 4 , wet etching using an aqueous solution or organic solvent of an organic acid or organic base, a CMP method, or the like is used, and the processing conditions can be adjusted as appropriate.
- a known dry etching apparatus can be used for removing the resist pattern, and the processing conditions can be adjusted as appropriate.
- the pattern reversal film of the present invention that is, the pattern reversal film obtained by coating and heating the resist pattern on the substrate to be processed is resisted from the substrate to be processed by an organic solvent usually used for peeling the resist pattern. It can be removed along with the pattern.
- the present invention is also directed to a method for removing the pattern reversal film. After the reverse pattern is formed from the pattern reverse film, only the reverse pattern can be removed. It does not specifically limit as an organic solvent used as a peeling agent used here, According to the composition for pattern reversal film formation to be used, and a resist material, it can select suitably.
- examples of the organic solvent used as a release agent for removing the pattern reversal film include sulfoxides such as dimethyl sulfoxide (DMSO); dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethylene) sulfone, tetramethylene.
- DMSO dimethyl sulfoxide
- dimethyl sulfone diethyl sulfone
- bis (2-hydroxyethylene) sulfone 2,3-hydroxyethylene
- Sulfones such as sulfone and sulfolane; Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide; N-ethyl-2-pyrrolidone Lactams such as N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone and N-hydroxyethyl-2-pyrrolidone; ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone , ⁇ -caprolactone, ⁇ Lactones such as caprolactone; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone; ethylene glycol , Ethylene glyco
- dimethyl sulfoxide, dimethyl imidazolidinone, dimethylacetamide, sulfolane, ⁇ -butyrolactone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, ethyl lactate, and cyclohexanone are preferable.
- propylene glycol monomethyl ether, propylene glycol monomethyl ether cetate, ethyl lactate, cyclohexanone, or a mixture of two or more thereof is most preferable.
- the weight average molecular weight shown to the following synthesis example of this specification is a measurement result by gel permeation chromatography (henceforth GPC).
- the measuring equipment and measuring conditions used are as follows.
- GPC device HLC-8220GPC (manufactured by Tosoh Corporation)
- GPC column Shodex [registered trademark] KF803L, KF802, KF801 (manufactured by Showa Denko KK) Column temperature: 40 ° C
- Solvent tetrahydrofuran (THF)
- Flow rate 1.0 mL / min Standard sample: Polystyrene (manufactured by Showa Denko KK)
- the solution was refluxed for 1 hour with stirring to remove the solvent (mainly methanol).
- the solvent mainly methanol
- the same amount of toluene as the removed solvent was added.
- the solution became turbid after most of the methanol was removed.
- Further refluxing and subsequent removal of the solvent made the solution clear again when most of the water was removed.
- the temperature was slowly raised to about 105 ° C. over about 1 hour.
- the resulting clear solution was then cooled and about 230 g of toluene was added.
- 3 g of acetic acid was added and stirred for 0.5 hours.
- the resulting solution was washed 3 times with 100 mL of demineralized water.
- the solution was refluxed for 1 hour with stirring to remove the solvent (mainly methanol).
- the solvent mainly methanol
- the same amount of toluene as the removed solvent was added.
- the solution became turbid after most of the methanol was removed.
- Further refluxing and subsequent removal of the solvent made the solution clear again when most of the water was removed.
- the temperature was slowly raised to about 105 ° C. over about 1 hour.
- the resulting clear solution was then cooled and about 330 g of toluene was added. To this, 3 g of acetic acid was added and stirred for 0.5 hours.
- the resulting solution was washed once with 100 mL of demineralized water.
- the mixture was reacted at 85 ° C. for 4 hours in an oil bath.
- the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol produced during the reaction was removed to obtain a reaction product (polysiloxane).
- acetone was substituted with 4-methyl-2-pentanol using an evaporator to obtain a resin 3 solution.
- the solid content concentration of the obtained resin 3 solution was measured by a firing method. It was 25% by mass.
- the weight average molecular weight (Mw) of the obtained resin 3 (solid content) was 2,000.
- the resin 3 obtained in this synthesis example does not correspond to the polysiloxane having the structural unit represented by the formula (1) and the structural unit represented by the formula (2).
- Example 1 Resin 1 / ascorbic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.025 g of ascorbic acid (0.5% by mass with respect to the mass of resin 1) and 100 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m.
- a forming composition was obtained.
- Example 2 Resin 1 / Maleic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.025 g of maleic acid (0.5% by mass with respect to the mass of Resin 1) and 75 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m.
- a forming composition was obtained.
- Example 3 Resin 1 / salicylic acid (addition amount: 0.5% by mass)]
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.025 g of salicylic acid (0.5% by mass with respect to the mass of resin 1) and 75 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore diameter of 0.1 ⁇ m to form a pattern reversal film.
- a composition was obtained.
- Example 4 Resin 1 / 3-hydroxybenzoic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.025 g of 3-hydroxybenzoic acid (0.5% by mass with respect to the mass of resin 1) and 75 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m.
- a composition for forming a pattern reversal film was obtained.
- Example 5 Resin 1 / 4-hydroxybenzoic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.025 g of 4-hydroxybenzoic acid (0.5% by mass with respect to the mass of resin 1) and 75 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore diameter of 0.1 ⁇ m.
- a composition for forming a pattern reversal film was obtained.
- Example 6 Resin 1 / 2,6-dihydroxybenzoic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.025 g of 2,6-dihydroxybenzoic acid (0.5% by mass with respect to the mass of resin 1) and 75 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m. It filtered and the composition for pattern reversal film formation was obtained.
- Example 7 Resin 1 / 3,5-dihydroxybenzoic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol. 0.025 g of 3,5-dihydroxybenzoic acid (0.5% by mass with respect to the mass of the resin 1) and 75 g of 4-methyl-2-pentanol were added to the solution, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m. It filtered and the composition for pattern reversal film formation was obtained.
- Example 8 Resin 1 / 3,4,5-trihydroxybenzoic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol. 0.025 g of 3,4,5-trihydroxybenzoic acid (0.5% by mass with respect to the mass of the resin 1) and 75 g of 4-methyl-2-pentanol were added to the solution, respectively, and the solution had a pore size of 0.1 ⁇ m.
- the composition for pattern inversion film formation was obtained by filtering with a filter.
- Example 9 Resin 1 / phthalic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol. 0.025 g of phthalic acid (0.5% by mass with respect to the mass of resin 1) and 75 g of 4-methyl-2-pentanol were added to the solution, respectively, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m to obtain a pattern reversal membrane. A forming composition was obtained.
- Example 10 Resin 1 / 1,2,4,5-benzenetetracarboxylic acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.025 g of 1,2,4,5-benzenetetracarboxylic acid (0.5% by mass with respect to the mass of the resin 1) and 75 g of 4-methyl-2-pentanol were added, respectively.
- the mixture was filtered through a 1 ⁇ m filter to obtain a pattern reversal film forming composition.
- Example 11 Resin 1 / citric acid
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- a composition was obtained.
- Example 12 Resin 1 / salicylic acid (added amount: 0.1% by mass)]
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.005 g of salicylic acid (0.1% by mass with respect to the mass of resin 1) and 50 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m to form a pattern reversal film.
- a composition was obtained.
- Example 13 Resin 1 / salicylic acid (added amount: 0.25% by mass)]
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.0125 g of salicylic acid (0.25 mass% with respect to the mass of resin 1) and 50 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore diameter of 0.1 ⁇ m to form a pattern reversal film.
- a composition was obtained.
- Example 14 Resin 1 / salicylic acid (added amount: 0.75% by mass)]
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.0375 g of salicylic acid (0.75% by mass with respect to the mass of resin 1) and 50 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m to form a pattern reversal film.
- a composition was obtained.
- Example 15 Resin 1 / salicylic acid (added amount: 1% by mass)]
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- To the solution were added 0.05 g of salicylic acid (1% by mass with respect to the mass of resin 1) and 50 g of 4-methyl-2-pentanol, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m to form a pattern reversal film forming composition. I got a thing.
- Example 16 Resin 1 / salicylic acid (addition amount: 3% by mass)] A 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol. 0.15 g of salicylic acid (3% by mass with respect to the mass of resin 1) and 50 g of 4-methyl-2-pentanol were added to the solution, and the solution was filtered through a filter having a pore size of 0.1 ⁇ m to form a pattern reversal film forming composition. I got a thing.
- Example 17 Resin 1 / salicylic acid (addition amount: 5% by mass)]
- a 10% by mass solution was obtained using 5 g of the resin 1 (polymer) obtained in Synthesis Example 1 and 45 g of 4-methyl-2-pentanol.
- 0.25 g of salicylic acid (5% by mass with respect to the mass of the resin 1) and 50 g of 4-methyl-2-pentanol were added, and the solution was filtered through a filter having a pore size of 0.1 ⁇ m. I got a thing.
- Example 18 Resin 2 / ascorbic acid
- a 10% by mass solution was obtained using 5 g of the resin 2 (polymer) obtained in Synthesis Example 2 and 45 g of 4-methyl-2-pentanol.
- 0.025 g of ascorbic acid (0.5% by mass with respect to the mass of resin 1) and 100 g of 4-methyl-2-pentanol were added, respectively, and the solution was filtered with a filter having a pore size of 0.1 ⁇ m to obtain a pattern reversal membrane.
- a forming composition was obtained.
- PGMEA propylene glycol monomethyl ether acetate
- PGME propylene glycol monomethyl ether
- the film thickness on the silicon substrate was measured in the same manner as described above (film thickness after the rework process).
- the measurement lower limit of the said film thickness measuring apparatus is 10 nm or less, when the film thickness measurement result became 10 nm or less, it was set as "the detection lower limit or less".
- composition for forming a pattern reversal film of the present invention can be removed by an organic solvent and can be reworked.
- ⁇ Patterning example 1 using the composition for forming a pattern reversal film of the present invention An ArF resist solution (product name PAR855, manufactured by Sumitomo Chemical Co., Ltd.) was applied onto a silicon substrate on which an organic underlayer film having a thickness of 200 nm was formed, using a spinner. A resist film having a thickness of 100 nm was formed by heating at 110 ° C. for 60 seconds on a hot plate. Using an exposure apparatus for ArF excimer laser (Nikon Corporation, S307E), exposure was performed under predetermined conditions. The target line width was set to 65 nm line and space, and after exposure, heating (PEB) was performed at 105 ° C.
- PAR855 manufactured by Sumitomo Chemical Co., Ltd.
- An SEM image obtained by observing the cross-sectional shape in this state is shown in FIG.
- the cross-sectional SEM image of the cross-sectional shape of the obtained reverse pattern is shown in FIG.
- FIG. 5 shows a cross-sectional SEM image of the cross-sectional shape as a result of patterning.
- FIG. 6 A resist pattern showing a cross-sectional SEM image shown in FIG. 6 was formed by the same method, apparatus, and conditions as in Patterning Example 1. Subsequently, a pattern reversal film was formed on the resist pattern using the composition for pattern reversal film formation obtained in Example 18, and then dry etching was performed. As shown in the cross-sectional SEM image shown in FIG. The upper part of the pattern was exposed. Next, dry etching is performed by the same method, apparatus and conditions as in the above patterning example 1, the resist pattern is removed to obtain a reverse pattern, and then dry etching is performed using the reverse pattern as an etching mask. The film could be patterned.
- FIG. 8 shows a cross-sectional SEM image of the cross-sectional shape as a result of patterning.
- the pattern reversal film of the present invention As shown in the above-mentioned ⁇ Pattern example 1 using the composition for forming a pattern reversal film of the present invention> and ⁇ Pattern example 2 using the composition for forming a pattern reverse film of the present invention>, the pattern reversal film of the present invention It was confirmed that the intended reverse pattern can be formed using the forming composition.
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Abstract
Description
近年、半導体素子の高集積化に伴い、上述のフォトレジストパターンの微細化がますます求められており、高精度な寸法制御を図ったパターン形成方法として、反転マスクパターンの形成方法やその際に用いるパターン反転用の樹脂組成物が提案されている(特許文献1、特許文献2)。
上述の反転マスクパターンにおいてもリワーク性(リワーク可能又は容易な性質をいう)が求められているが、これまで提案されている反転パターン材料にはシリコン原子が含まれているため、アッシング処理を行おうとしても酸化ケイ素に変質硬化するため除去が不可能となり、また、該パターンはベーク処理によって架橋反応が進行していることから、従来のレジスト剥離剤を用いた薬液処理による除去も困難となっていた。
本発明は、レジストパターンの剥離に通常使用される有機溶剤にてリワーク可能なシリコン含有パターン反転膜形成用組成物を提供することを目的とする。
前記添加剤がカルボキシル基及び/又はヒドロキシ基を少なくとも2つ有する有機酸であることを特徴とする組成物に関する。
このため、本発明のパターン反転膜形成用組成物より得られたパターン反転膜は、膜形成時の不良、及び該パターン反転膜から形成された反転パターンに不具合が生じた場合には基板から容易に除去可能であり、基板の再生・再利用が可能であり、半導体製造工程の低コスト化に寄与することが可能である。しかも勿論、本発明のパターン反転膜形成用組成物は、パターン反転膜としての要求性能を満たす膜を形成することができるものである。
[パターン反転膜形成用組成物]
<ポリシロキサン>
本発明のパターン反転膜形成用組成物に含まれるポリシロキサンは、下記式(1)で表される構造単位と、下記式(2)で表される構造単位を有するポリシロキサンである。
nは2乃至4の整数を表す。)
また上記式(1)で表される構造単位と、上記式(2)で表される構造単位は、ランダム共重合体、ブロック共重合体、交互共重合体の何れの構造を形成してもよい。
R1Si(OR3)3 ・・・(3)
(式中、R1は式(1)における定義と同義であり、R3はそれぞれ独立して炭素原子数1乃至4のアルキル基を表す。)
R2(CH2)nSi(OR4)3 ・・・(4)
(式中、R2及びnは式(2)における定義と同義であり、R4はそれぞれ独立して炭素原子数1乃至4のアルキル基を表す。)
なお、式(3)又は式(4)中、各R3又は各R4は、全て同じであっても一部が異なっていても良い。
これらの中でも、メチルトリメトキシシラン又はメチルトリエトキシシランが好ましい。
これら式(3)で表されるシラン化合物は1種を単独で使用してもよいし、2種以上を組み合わせて用いてもよい。
これらの中でも、3-メタクリロイルオキシプロピルトリメトキシシラン、3-メタクリロイルオキシプロピルトリエトキシシランが好ましい。
これら式(4)で表される化合物は1種を単独で使用してもよいし、2種以上を組み合わせて用いてもよい。
使用する塩基性触媒の使用量は、通常、式(3)で表されるシラン化合物と式(4)で表されるシラン化合物の全量100質量部に対して、0.001質量部ないし1質量部である。
上記共加水分解縮合反応は、例えば、60℃ないし80℃の温度条件にて実施される。
本発明のパターン反転膜形成用組成物に含まれる添加剤は、カルボキシル基及び/又はヒドロキシ基を少なくとも2つ有する有機酸である。
上記添加剤として好ましくは、マレイン酸、クエン酸、サリチル酸、3-ヒドロキシ安息香酸、4-ヒドロキシ安息香酸、2,6-ジヒドロキシ安息香酸、3,5-ジヒドロキシ安息香酸、ガリック酸、フタル酸、ピロメリット酸及びアスコルビン酸からなる群から選択される有機酸である。
本発明のパターン反転膜形成用組成物に含まれる前記有機溶媒は、上記添加剤である有機酸を溶解可能なものであり、好ましくは炭素原子数2ないし10のアルコールから選択される。該有機酸を溶解しない有機溶媒が適用される場合、本発明の効果が十分に得られないことがある。前記有機溶媒には、レジストパターンとのインターミキシングが生じない範囲で、レジスト溶剤がさらに含まれていてもよい。
さらに本発明のパターン反転膜形成用組成物は、所望により、界面活性剤等の各種添加剤を含んでいてもよい。
これらの界面活性剤は単独で添加してもよいし、また2種以上の組合せで添加することもできる。
本発明の前記パターン反転膜形成組成物を用いたパターン反転膜の形成方法は、上述のパターン反転膜形成用組成物を基板に塗布し、80℃ないし180℃の温度でベークして、膜形成する工程を含む方法である。
上記基板としては、例えばシリコン基板等の半導体基板が用いられ、さらにレジストパターンが表面に形成された段差基板が用いられる。
また本発明の反転パターン形成方法は、(a)被加工基板上にレジストパターンを形成する工程、(b)前記レジストパターンを被覆するように前述のパターン反転膜形成用組成物を塗布し、80℃ないし180℃の温度で加熱してパターン反転膜を形成する工程、(c)前記パターン反転膜をエッチバックして前記レジストパターンの表面を露出させる工程、及び(d)前記レジストパターンを除去し、反転パターンを形成する工程とを含む。
なお、所望により、被加工基板上に、有機又は無機系の反射防止能を有する下層膜を予め形成していても良い。
なお、アルカリ水溶液からなる現像液で現像した後は、一般に水で洗浄し、乾燥してからその後の工程に用いる。
好ましくは80℃ないし150℃でベークすることにより、塗膜中の有機溶媒を迅速に揮発させることができる。このときのベーク時間は通常10秒ないし300秒間、好ましくは30秒ないし180秒間である。
上記パターン反転膜の膜厚は特に限定されないが、通常10nmないし1000nmであり、好ましくは50nmないし500nmである。
エッチバック処理としてはCF4などのフッ素系ガスを用いるドライエッチングや有機酸若しくは有機塩基の水溶液又は有機溶剤を用いるウェットエッチング、或いはCMP法等が用いられ、処理条件は適宜調整可能である。
またレジストパターンの除去には公知のドライエッチング装置が使用でき、処理条件は適宜調整可能である。
本発明のパターン反転膜、すなわち、被加工基板上のレジストパターンを被覆し、加熱することで得られたパターン反転膜は、レジストパターンの剥離に通常使用される有機溶剤によって、被加工基板からレジストパターンと共に除去することができる。そして本発明は上記パターン反転膜の除去方法も対象とする。上記パターン反転膜から反転パターンを形成後、その反転パターンのみ除去することもできる。
ここで使用する剥離剤として使用する有機溶剤としては特に限定されず、使用するパターン反転膜形成用組成物、そしてレジスト材料によって適宜選択することができる。
中でも、ジメチルスルホキシド、ジメチルイミダゾリジノン、ジメチルアセトアミド、スルホラン、γ-ブチロラクトン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、乳酸エチル、シクロヘキサノンが好ましい。特にプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルセテート、乳酸エチル、シクロヘキサノン又はこれらのうち2種以上を混合したものが最も好ましい。
[GPC条件]
GPC装置:HLC-8220GPC(東ソー(株)製)
GPCカラム:Shodex〔登録商標〕KF803L,KF802,KF801(昭和電工(株)製)
カラム温度:40℃
溶媒:テトラヒドロフラン(THF)
流量:1.0mL/分
標準試料:ポリスチレン(昭和電工(株)製)
[合成例1:ポリ(メチル-コ-3-メタクリロイルオキシプロピル)シルセスキオキサン:[(メチル)SiO3/2]0.80[(メタクリロイルオキシプロピル)SiO3/2]0.20の合成]
フラスコに、トルエン80g、3-メタクリロイルオキシプロピルトリメトキシシラン0.10mol、メチルトリメトキシシラン0.40mol、水2.40mol、水酸化セシウム水溶液(50質量%)1g、メタノール200g及び2,6-ジ-tert-ブチル-4-メチルフェノール40mgを仕込み、透明溶液を調製した。前記溶液を撹拌しながら1時間に亘って還流し、溶媒(主にメタノール)を除去した。さらに還流を続け、一定の溶液濃度を維持するために、除去された溶媒と同量のトルエンを添加した。ほとんどのメタノールが除去された後、この溶液は混濁した。さらに還流を続け、溶媒を引き続き除去したところ、大部分の水が除去された時点で溶液は再度透明になった。
続いて温度を約1時間かけてゆっくりと約105℃に上昇させた。その後、得られた透明溶液を冷却し、約230gのトルエンを加えた。ここに3gの酢酸を加え、0.5時間に亘って撹拌した。得られた溶液を、100mLの脱塩水で3回洗浄した。その後、該溶液を孔径1μmの濾紙で濾過した。得られたろ液を50℃の回転式エバポレータに投入し、トルエンを除去した。得られた生成物(固体樹脂)を真空下、常温にて、2時間に亘って乾燥させ、樹脂1を得た。樹脂1の重量平均分子量(Mw)は26,000であった。
フラスコに、トルエン80g、3-メタクリロイルオキシプロピルトリメトキシシラン0.10mol、メチルトリメトキシシラン0.40mol、水2.40mol、水酸化セシウム水溶液(50質量%)0.5g、メタノール300g及び2,6-ジ-tert-ブチル-4-メチルフェノール50mgを仕込み、透明溶液を調製した。前記溶液を撹拌しながら1時間に亘って還流し、溶媒(主にメタノール)を除去した。さらに還流を続け、一定の溶液濃度を維持するために、除去された溶媒と同量のトルエンを添加した。ほとんどのメタノールが除去された後、この溶液は混濁した。さらに還流を続け、溶媒を引き続き除去したところ、大部分の水が除去された時点で溶液は再度透明になった。
続いて温度を約1時間かけてゆっくりと約105℃に上昇させた。その後、得られた透明溶液を冷却し、約330gのトルエンを加えた。ここに3gの酢酸を加え、0.5時間に亘って撹拌した。得られた溶液を、100mLの脱塩水で1回洗浄した。その後、該溶液を孔径1μmの濾紙で濾過した。得られたろ液を50℃の回転式エバポレータに投入し、トルエンを除去した。得られた生成物(固体樹脂)を真空下、常温にて、2時間に亘って乾燥させ、樹脂2を得た。樹脂2の重量平均分子量(Mw)は13,000であった。
フラスコに、テトラエトキシシラン27.08g(65mol%)、メチルトリエトキシシラン10.70g(30mol%)、フェニルトリメトキシシラン1.98g(5mol%)及びアセトン59.65gを仕込んだ。このフラスコに冷却管を取り付け、調製しておいた塩酸水溶液(0.01mol/L)13.15gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し、数分間撹拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応液の入ったフラスコを放冷してからエバポレータにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た。さらに、エバポレータを用いてアセトンを4-メチル-2-ペンタノールに置換し、樹脂3の溶液を得た、尚、得られた樹脂3の溶液の固形分濃度は、焼成法により測定した結果、25質量%であった。また、得られた樹脂3(固形分)の重量平均分子量(Mw)は2,000であった。なお、本合成例で得られた樹脂3は、前記式(1)で表される構造単位及び前記式(2)で表される構造単位を有するポリシロキサンに該当しない。
[実施例1:樹脂1 / アスコルビン酸]
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にアスコルビン酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール100gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にマレイン酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にサリチル酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に3-ヒドロキシ安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に4-ヒドロキシ安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に2,6-ジヒドロキシ安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に3,5-ジヒドロキシ安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に3,4,5-トリヒドロキシ安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にフタル酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に1,2,4,5-ベンゼンテトラカルボン酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液クエン酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にサリチル酸0.005g(樹脂1の質量に対して0.1質量%)、4-メチル-2-ペンタノール50gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にサリチル酸0.0125g(樹脂1の質量に対して0.25質量%)、4-メチル-2-ペンタノール50gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にサリチル酸0.0375g(樹脂1の質量に対して0.75質量%)、4-メチル-2-ペンタノール50gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にサリチル酸0.05g(樹脂1の質量に対して1質量%)、4-メチル-2-ペンタノール50gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にサリチル酸0.15g(樹脂1の質量に対して3質量%)、4-メチル-2-ペンタノール50gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にサリチル酸0.25g(樹脂1の質量に対して5質量%)、4-メチル-2-ペンタノール50gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例2で得られた樹脂2(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にアスコルビン酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール100gを夫々加え、溶液を孔径0.1μmのフィルタでろ過しパターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)3.5gと4-メチル-2-ペンタノール96.5gを用いて3.5質量%の溶液を得た。溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。
合成例3で得られた樹脂3(ポリマー)溶液10gに、サリチル酸0.0125g(樹脂3(固形分)の質量に対して0.5質量%)、4-メチル-2-ペンタノール60gを夫々加えた。溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。
合成例3で得られた樹脂3(ポリマー)溶液10gに、3-ヒドロキシ安息香酸0.0125g(樹脂3(固形分)の質量に対して0.5質量%)、4-メチル-2-ペンタノール60gを夫々加えた。溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。なお、本比較例で用いた安息香酸は、カルボキシル基及び/又はヒドロキシ基を少なくとも2つ有する有機酸に該当しない。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に4-メチル安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。なお、本比較例で用いた4-メチル安息香酸は、カルボキシル基及び/又はヒドロキシ基を少なくとも2つ有する有機酸に該当しない。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に4-ブロモ安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。なお、本比較例で用いた4-ブロモ安息香酸は、カルボキシル基及び/又はヒドロキシ基を少なくとも2つ有する有機酸に該当しない。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液に4-アミノ安息香酸0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。なお、本比較例で用いた4-アミノ安息香酸は、カルボキシル基及び/又はヒドロキシ基を少なくとも2つ有する有機酸に該当しない。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にトコフェロール0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。なお、本比較例で用いたDL-α-トコフェロールは、カルボキシル基及び/又はヒドロキシ基を少なくとも2つ有する有機酸に該当しない。
合成例1で得られた樹脂1(ポリマー)5gと4-メチル-2-ペンタノール45gを用いて10質量%の溶液を得た。その溶液にトコフェロール酢酸エステル0.025g(樹脂1の質量に対して0.5質量%)、4-メチル-2-ペンタノール75gを夫々加え、溶液を孔径0.1μmのフィルタでろ過し、パターン反転膜形成用組成物を得た。なお、本比較例で用いた酢酸DL-α-トコフェロールは、カルボキシル基及び/又はヒドロキシ基を少なくとも2つ有する有機酸に該当しない。
実施例1乃至18及び比較例1乃至9の各パターン反転膜形成用組成物について次の試験を行った。
シリコン基板上に、上記実施例又は比較例のパターン反転膜形成用組成物を塗布し、110℃/60秒間加熱ベークすることによりパターン反転膜を得て、膜厚測定装置(東朋テクノロジー(株)製、NanoSpec 6100)を用いて膜厚を測定した(塗布後の膜厚)。
次に、有機溶剤(プロピレングリコールモノメチルエーテルアセテート(PGMEA):プロピレングリコールモノメチルエーテル(PGME)=7:3(質量比))を用いて浸漬処理を行い、パターン反転膜の剥離試験を行った。その後、シリコン基板上の膜厚を上記と同様に測定した(リワーク処理後の膜厚)。
なお、上記膜厚測定装置の測定下限値は10nm以下であることから、膜厚測定結果が10nm以下となった場合には「検出下限以下」とした。
以上、得られた結果を表1に示す。
膜厚200nmの有機下層膜を形成したシリコン基板上に、ArF用レジスト溶液(製品名PAR855、住友化学(株)製)を、スピナーを用いて塗布した。ホットプレート上で、110℃で60秒間加熱することにより膜厚100nmのレジスト膜を形成した。ArFエキシマレーザー用露光装置((株)ニコン製、S307E)を用い、所定の条件で露光した。目的の線幅を65nmラインアンドスペースとし、露光後、105℃で60秒間加熱(PEB)を行い、さらにアルカリ現像及びリンス処理を行い、レジストパターンを得た。得られたレジストパターンについて、断面の形状をSEMにて撮影した。得られた断面SEM像を図1に示す。
得られたレジストパターン上に、実施例1で得たパターン反転膜形成用組成物を塗布し、1,500rpmで60秒スピンして該組成物中の有機溶媒をスピンドライし、110℃で60秒間ベーク処理を行い、パターン反転膜を形成した。得られたパターン反転膜について、断面の形状をSEMにて撮影した。結果を図2に示す。
上記パターニング例1と同様の方法、装置及び条件で、図6に示す断面SEM像を示すレジストパターンを形成した。続いて、レジストパターン上に、実施例18で得たパターン反転膜形成用組成物を用いてパターン反転膜を形成した後、ドライエッチングを行い、図7に示す断面SEM像に示すように前記レジストパターン上部を露呈させた。次に上記パターニング例1と同様の方法、装置及び条件で、ドライエッチングを行い、前記レジストパターンを除去して反転パターンを得、その後、該反転パターンをエッチングマスクとしてドライエッチングしたところ、前記有機下層膜にパターニング可能であった。パターニングした結果の断面形状の断面SEM像を図8に示す。
Claims (7)
- 前記添加剤が
マレイン酸、クエン酸、サリチル酸、3-ヒドロキシ安息香酸、4-ヒドロキシ安息香酸、2,6-ジヒドロキシ安息香酸、3,5-ジヒドロキシ安息香酸、ガリック酸、フタル酸、ピロメリット酸及びアスコルビン酸からなる群から選択される有機酸である、
請求項1に記載のパターン反転膜形成用組成物。 - 前記有機溶媒が、炭素原子数2乃至10のアルコール類から選択される、
請求項1又は請求項2に記載のパターン反転膜形成用組成物。 - 前記ポリシロキサンが、
前記式(1)で表される構造単位と前記式(2)で表される構造単位をモル比で50:50乃至99:1で含むことを特徴とする、
請求項1乃至請求項3のうちいずれか一項に記載のパターン反転膜形成用組成物。 - 被加工基板上にレジストパターンを形成する工程、
前記レジストパターンのパターンを被覆するように、請求項1乃至請求項4のうちいずれか一項に記載のパターン反転膜形成用組成物を塗布し、80℃ないし180℃の温度で加熱してパターン反転膜を形成する工程、
前記パターン反転膜をエッチバックして前記レジストパターンの表面を露出させる工程、及び
前記レジストパターンを除去し、反転パターンを形成する工程
とを含む反転パターン形成方法。 - 請求項1乃至請求項4のうちいずれか一項に記載のパターン反転膜形成用組成物により、被加工基板上のレジストパターンを被覆し、加熱することで得られたパターン反転膜を、有機溶剤によって前記レジストパターンと共に剥離するパターン反転膜の除去方法。
- 前記有機溶剤は、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル及びシクロヘキサノンからなる群から選択される1種又は2種以上からなる、請求項6に記載のパターン反転膜の除去方法。
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JP2014157299A (ja) * | 2013-02-18 | 2014-08-28 | Shin Etsu Chem Co Ltd | パターン形成方法及びパターン反転膜材料 |
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WO2016031563A1 (ja) * | 2014-08-25 | 2016-03-03 | 日産化学工業株式会社 | Socパターン上でのパターン反転のための被覆用組成物 |
JPWO2016031563A1 (ja) * | 2014-08-25 | 2017-06-08 | 日産化学工業株式会社 | Socパターン上でのパターン反転のための被覆用組成物 |
US10139729B2 (en) | 2014-08-25 | 2018-11-27 | Nissan Chemical Industries, Ltd. | Coating composition for pattern reversal on soc pattern |
CN105301903A (zh) * | 2015-11-16 | 2016-02-03 | 北京中科紫鑫科技有限责任公司 | 一种形成光刻胶组合物 |
JP2018046205A (ja) * | 2016-09-15 | 2018-03-22 | 株式会社Screenホールディングス | 基板処理装置および基板処理方法 |
US11243469B2 (en) | 2016-09-15 | 2022-02-08 | SCREEN Holdings Co., Ltd. | Substrate processing apparatus and substrate processing method |
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JP5773176B2 (ja) | 2015-09-02 |
CN103443711B (zh) | 2016-10-12 |
SG193961A1 (en) | 2013-11-29 |
SG10201602107SA (en) | 2016-05-30 |
US20140017896A1 (en) | 2014-01-16 |
KR20140022022A (ko) | 2014-02-21 |
TW201307441A (zh) | 2013-02-16 |
JPWO2012132686A1 (ja) | 2014-07-24 |
TWI553042B (zh) | 2016-10-11 |
CN103443711A (zh) | 2013-12-11 |
US9165781B2 (en) | 2015-10-20 |
KR101713689B1 (ko) | 2017-03-08 |
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