WO2018074358A1 - レジストパターン被覆用水溶液及びそれを用いたパターン形成方法 - Google Patents
レジストパターン被覆用水溶液及びそれを用いたパターン形成方法 Download PDFInfo
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- WO2018074358A1 WO2018074358A1 PCT/JP2017/037190 JP2017037190W WO2018074358A1 WO 2018074358 A1 WO2018074358 A1 WO 2018074358A1 JP 2017037190 W JP2017037190 W JP 2017037190W WO 2018074358 A1 WO2018074358 A1 WO 2018074358A1
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- QEMAHOAOSMCXJQ-UHFFFAOYSA-N CC(C(CO)OC(C1O)OC)C1O Chemical compound CC(C(CO)OC(C1O)OC)C1O QEMAHOAOSMCXJQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
- C09D105/16—Cyclodextrin; Derivatives thereof
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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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
- G03F7/004—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
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- 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
- G03F7/20—Exposure; Apparatus therefor
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- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- 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
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- 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
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- 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
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- 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
Definitions
- the present invention relates to a resist pattern coating aqueous solution capable of preventing collapse of a line-shaped or columnar resist pattern, and miniaturizing a line-shaped or columnar resist pattern or enlarging a hole diameter of a resist pattern in which holes (holes) are formed. . Furthermore, the present invention relates to a pattern forming method and a reverse pattern forming method using the aqueous solution.
- fine processing by lithography using a resist composition is performed.
- the microfabrication forms a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, and irradiates with an actinic ray such as ultraviolet rays through a mask pattern on which a device pattern is drawn, and develops it.
- This is a processing method in which fine irregularities corresponding to the pattern are formed on the substrate surface by etching the substrate using the obtained photoresist pattern as a protective film.
- Patent Documents 1 to 4 a method of applying on a resist pattern and miniaturizing the resist pattern and a coating material used for the method are known (for example, Patent Documents 1 to 4). By adopting this method, it becomes possible to further miniaturize a resist pattern produced by lithography employing exposure using an ArF excimer laser that has already been put into practical use.
- the aqueous solution containing the water-soluble resin described in Patent Document 1 uses water having a higher surface tension as a solvent as compared with an organic solvent, there is a difficulty in application to a resist pattern. Therefore, it is necessary to add a surfactant or use a water-soluble alcohol mixed with water. Since the resist pattern refinement composition described in Patent Document 2 is a solution that does not contain a polymer, the ratio of refinement tends to vary depending on the shape of the resist pattern to be refined.
- the pattern refinement treatment agent described in Patent Document 3 contains an acid generator component, and the baking treatment temperature after applying the pattern refinement treatment agent is 130 ° C. or higher, or A step of exposing after applying the pattern refining treatment agent must be added.
- the method for forming a fine pattern described in Patent Document 4 narrows a resist pattern formed by a negative development process, that is, forms a coating film on the resist pattern, and then heats the resist pattern. It is to reduce the space width which is an interval between them. Therefore, the fine pattern forming method is not intended to reduce the width or diameter of the resist pattern.
- An object of the present invention is to provide a resist pattern coating aqueous solution that can prevent collapse of the resist pattern by reducing the Laplace force between the resist patterns.
- Another object of the present invention is to provide an aqueous solution for coating a resist pattern that contains an organic sulfonic acid or a salt thereof, and can reduce a line-shaped or columnar resist pattern, or can increase the pore size of the resist pattern. To do. Furthermore, it aims at providing the formation method of the resist pattern using this aqueous solution, and the formation method of the inversion pattern using this aqueous solution.
- the present invention can form a finer pattern than the conventional fine pattern forming composition, and can reduce the width of the resist pattern size in line or column, or the pore size of the resist pattern.
- the enlargement width can be easily controlled, and at the same time, it is used in a general developing cup provided in a coater / developer by using water and optionally a specific water-soluble organic solvent such as isopropyl alcohol.
- the present inventors have found an aqueous solution for coating a resist pattern that can be used in the developing cup because of excellent compatibility with other solutions (for example, a developing solution and a rinsing solution containing a surfactant).
- the first aspect of the present invention is a component A: cyclodextrin selected from the group consisting of ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin, or a derivative of the cyclodextrin, and component B: water as a main component
- the content ratio of the component A is 0.1% by mass to 10% by mass with respect to 100% by mass of the entire aqueous solution.
- the cyclodextrin derivative is, for example, a compound having at least one unit represented by the following formula (1a), formula (1b), formula (1c), or formula (1d).
- a 1 represents an amino group, azide group, mercapto group, methoxy group, acetoxy group or tosyloxy group
- a 2 represents an amino group, azide group, hydroxy group or triphenylmethyl group
- R 2 and R 3 represent Each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or an acetyl group
- R 0 represents an alkylene group having 1 to 4 carbon atoms or an alkenylene group
- R 1 represents an alkylene group having 2 to 4 carbon atoms
- n represents an integer of 2 to 8.
- the B component solvent may further contain at least one water-soluble organic solvent selected from the group consisting of alcohols, esters, ethers and ketones.
- the aqueous solution for resist pattern coating of the first aspect of the present invention optionally further comprises a C component: an organic sulfonic acid represented by the following formula (2) or a salt thereof, and the content ratio of the organic sulfonic acid or a salt thereof is as described above. It is 0.01 mass% thru
- R 4 is an alkyl group or fluorinated alkyl group having a linear, branched or cyclic structure having 1 to 16 carbon atoms, or the alkyl group, fluorinated alkyl group, hydroxy group or carboxy group.
- the alkyl group having the cyclic structure may have a carbonyl group in the main chain
- M + represents a hydrogen ion, an ammonium ion, a pyridinium ion or an imidazolium ion.
- the C component is, for example, an organic sulfonate represented by the following formula (2a).
- the resist film formed on the substrate via the resist underlayer film is exposed, baked, developed with a developing solution, and rinsed with a rinsing solution according to a lithography process.
- a resist film formed on a substrate through a resist underlayer film is subjected to exposure, baking, development with a developer, and development with a rinse and rinse with a rinse according to a lithography process.
- a step of forming a pattern a step of applying the resist pattern coating aqueous solution of the first aspect of the present invention containing the C component so as to cover the resist pattern without drying the resist pattern after the rinsing treatment,
- the substrate coated with the resist pattern coating aqueous solution is spin-dried and then heated at 50 ° C. to 130 ° C. or without being heated, and the coating film is formed.
- a process for removing the coating film by cooling the substrate and then etching the coating film with an etching gas.
- a pattern forming method comprising.
- a resist film formed on a substrate via a resist underlayer film is subjected to exposure, baking, development treatment with a developing solution, and rinsing treatment with a rinsing solution according to a lithography process.
- a step of forming a pattern, a step of coating the resist pattern coating aqueous solution of the first aspect of the present invention so as to cover the resist pattern without drying the resist pattern after the rinsing treatment, and for coating the resist pattern A step of forming a coating film on the surface of the resist pattern without or heating a substrate coated with an aqueous solution after spin drying at 50 ° C. to 130 ° C., and cooling the substrate on which the coating film is formed.
- the step of developing the coating film with a developer, the developing treatment of the coating film A step of applying a filling coating solution containing polysiloxane and a solvent containing water and / or alcohol so as to fill the space between the turns, components other than polysiloxane contained in the filling coating solution, and the coating Removing or reducing the developer used in the development processing for the film to form a coating film, etching back the coating film to expose the upper surface of the resist pattern, and the resist pattern with the upper surface exposed.
- a reversal pattern forming method including a removing step.
- the method further includes a step of rinsing the resist pattern with a rinsing liquid, and then applying the filling coating liquid without drying the resist pattern. You may perform a process.
- the aqueous solution for coating a resist pattern of the present invention is obtained by applying a resist film without drying after exposing, developing and rinsing a resist film, so that the resist pattern is formed on the line-like and / or column-like resist pattern formed on the substrate. Can be applied uniformly. Furthermore, after developing and rinsing, by applying the resist pattern coating aqueous solution of the present invention without drying the resist pattern, the Laplace force acting between the resist patterns can be prevented, and the resist pattern can be prevented from falling. Furthermore, the resist pattern coating aqueous solution of the present invention is used in a general developing cup provided in a coater / developer by using water and optionally a specific water-soluble organic solvent such as isopropyl alcohol as a solvent. Since it has excellent compatibility with other solutions (for example, a developer and a rinse solution containing a surfactant), it can be used in the developer cup.
- the aqueous solution for coating a resist pattern of the present invention contains an organic sulfonic acid or a salt thereof, so that the width of the line pattern is uniformly reduced in the line and space pattern in which the ratio of the width of the line pattern and the width of the space pattern is different. be able to.
- it is possible to increase the hole diameter of a resist pattern in which holes are formed (hereinafter referred to as a hole pattern in this specification) and improve the apparent sensitivity of the resist.
- the reduction ratio of the width or diameter of the resist pattern can be changed by selecting a polymer contained in the resist pattern coating aqueous solution of the present invention. Further, when EUV exposure is put to practical use in the future, it is possible to further miniaturize a resist pattern produced using EUV exposure.
- FIG. 1 shows an image obtained by observing a resist pattern from the upper surface using a CD-SEM.
- the component A contained in the resist pattern coating aqueous solution of the present invention is a cyclodextrin selected from the group consisting of ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin, or a derivative of the cyclodextrin.
- ⁇ -cyclodextrin forms a cyclic structure by combining 6 glucose units represented by the following formula (1)
- ⁇ -cyclodextrin forms a cyclic structure by combining 7 glucose units.
- -Cyclodextrin has a cyclic structure in which eight glucose units are bonded.
- the derivative of cyclodextrin has at least one unit in which at least one of three OH groups is substituted with a substituent in the glucose unit represented by the following formula (1).
- the cyclodextrin derivative has one unit substituted with the substituent, it further has 5, 6 or 7 glucose units represented by the following formula (1).
- the content ratio of the component A contained in the resist pattern coating aqueous solution of the present invention is, for example, 0.01% by mass to 50% by mass, preferably 0.1% by mass to 10% by mass with respect to 100% by mass of the entire aqueous solution. % By mass.
- the B component contained in the aqueous resist pattern coating solution of the present invention is a solvent containing water as a main component.
- the concentration of water in the solvent containing water as a main component is, for example, 51% by mass to 100% by mass, or 80% by mass to 100% by mass.
- the water concentration of 100% by mass means that the solvent containing water as a main component is water.
- the component other than water is at least one water-soluble organic solvent selected from the group consisting of alcohols, esters, ethers, and ketones.
- Examples of the alcohols include alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, n-hexyl alcohol, n-heptyl alcohol, ethylene glycol, propylene glycol, diethylene glycol and the like.
- Examples include glycol solvents and glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol.
- esters examples include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxy Mention may be made of butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl lactate and propyl lactate.
- ethers examples include di-n-propyl ether, di-n-butyl ether, dioxane, and tetrahydrofuran in addition to the glycol ether solvent.
- ketones examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone. be able to.
- the resist pattern coating aqueous solution of the present invention may further contain an organic sulfonic acid represented by the formula (2) or a salt thereof as a C component.
- the organic sulfonic acid include octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid (also known as laurylbenzenesulfonic acid), (1, 3, 5, 7 -Tetramethyloctyl) benzenesulfonic acid, tridecylbenzenesulfonic acid, (1R)-(-)-10-camphorsulfonic acid, (1S)-(+)-10-camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoro Mention may be made of butanesulfonic acid, perfluorooctanesulfonic acid, perflu
- Examples of the salt of the organic sulfonic acid include pyridinium p-toluenesulfonate, pyridinium p-phenolsulfonate, ammonium p-toluenesulfonate, ammonium p-phenolsulfonate, imidazolium p-toluenesulfonate, p- Mention may be made of imidazolium phenolsulfonate. Of these organic sulfonic acids or salts thereof, pyridinium p-phenol sulfonate is preferably used as the C component contained in the aqueous resist pattern coating solution of the present invention.
- the content thereof is, for example, 0.01% by mass to 50% by mass, preferably 0.01% by mass with respect to 100% by mass of the component A. Thru
- the aqueous solution for coating a resist pattern of the present invention may further contain various additives such as a surfactant as necessary as long as the effects of the present invention are not impaired.
- the surfactant is an additive for improving the applicability of the aqueous solution to the substrate.
- Known surfactants such as nonionic surfactants and fluorine-based surfactants can be used.
- the surfactant include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, and 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, polyoxy Nonionic surfactants including polyoxyethylene sorbitan fatty acid esters such as Tylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
- Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate,
- the content ratio is, for example, 0.1% by mass to 5% by mass with respect to 100% by mass of the component A in the aqueous solution, preferably Including 0.2% by mass to 3% by mass.
- the pattern forming method and the reverse pattern forming method using the resist pattern coating aqueous solution of the present invention are performed by exposing, baking, and developing a resist film formed on a substrate via a resist underlayer film according to a lithography process. It has the process of forming a resist pattern by performing the development process and the rinse process with a rinse liquid.
- a substrate used for manufacturing a precision integrated circuit element for example, a semiconductor substrate such as a silicon wafer which may be covered with a silicon oxide film, a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate
- the organic film and / or inorganic film which have antireflection ability are formed as a resist underlayer film.
- a positive resist solution for example, PAR710, PAR855, manufactured by Sumitomo Chemical Co., Ltd., and AR2772, JN, manufactured by JSR Co., Ltd.
- a negative resist solution may be used.
- a light source of an exposure apparatus used for exposure of the resist film for example, radiation selected from the group consisting of i-line, KrF excimer laser, ArF excimer laser, and EUV can be employed.
- the heating temperature when baking (PEB: Post Exposure Bake) on the resist film after exposure is, for example, 80 ° C. to 140 ° C.
- examples of the developer used in the development process include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
- Inorganic alkalis primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triethanolamine
- alkalis such as alcohol amines, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, cyclic amines such as pyrrole and piperidine, and the like.
- 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.
- Examples of the shape of the resist pattern to be formed include a line shape, a column shape, and a hole pattern.
- a linear resist pattern either an isolated line pattern or a line and space pattern may be formed.
- the shape of the linear resist pattern is not limited to a straight line, and may be a bent shape.
- rinsing liquid used for the rinsing treatment examples include an aqueous solution containing a surfactant, pure water, and ultrapure water.
- the pattern forming method and the reverse pattern forming method using the resist pattern coating aqueous solution of the present invention further include a step of applying the resist pattern coating aqueous solution of the present invention so as to cover the resist pattern after the rinsing treatment. Have. In this step, it is important not to dry the resist pattern. This is because when the resist pattern is dried, the resist pattern may fall down.
- etching gas examples include O 2 and N 2.
- Gas mixture, O 2 gas, CF 4 gas, Cl 2 gas, HBr gas, SiF 4 gas, HCl gas, He gas, and Ar gas, and the above-mentioned alkaline aqueous solution is applied as the developer. be able to.
- the above-mentioned specific example can be applied as a rinse liquid used for the rinse process after the said development process.
- a filling coating solution containing polysiloxane and a solvent containing water and / or alcohols is applied so as to fill between the patterns of the resist pattern.
- the process of carrying out As the polysiloxane that is a component of the coating solution for filling, a known material used for the coating solution applied to the resist pattern can be employed.
- the specific example of alcohol which the above-mentioned C component can contain as components other than water is applicable as alcohol.
- the reverse pattern forming method using the resist pattern coating aqueous solution of the present invention further includes a step of forming a coating film by removing or reducing components other than polysiloxane and the rinsing liquid contained in the filling coating liquid.
- the step is, for example, spin drying the substrate on which the filling coating liquid is applied, or heating after spin drying.
- the spin dry is to dry while rotating the substrate.
- components other than polysiloxane contained in the coating liquid for filling are polysiloxane, a solvent containing water and / or alcohols, and an additive added as necessary.
- the reverse pattern forming method using the resist pattern coating aqueous solution of the present invention further includes a step of etching back the coating film to expose the upper surface of the resist pattern, and a step of removing the resist pattern from which the upper surface is exposed.
- the etch back is performed, for example, by dry etching using a fluorine-based gas such as CF 4 , wet etching using an aqueous solution of an organic acid or an organic base, wet etching using an organic solvent, or a CMP method, and the processing conditions are appropriately adjusted. Is possible.
- the resist pattern whose upper surface is exposed is removed by, for example, dry etching using a mixed gas of O 2 and N 2 or O 2 gas.
- Example 1 1.20 g of ⁇ -cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 38.80 g of pure water. Thereafter, the solution was filtered using a microfilter having a pore size of 0.20 ⁇ m (manufactured by GE Healthcare Japan Co., Ltd. (former Whatman)) to prepare an aqueous solution for coating a resist pattern.
- a microfilter having a pore size of 0.20 ⁇ m (manufactured by GE Healthcare Japan Co., Ltd. (former Whatman)) to prepare an aqueous solution for coating a resist pattern.
- Example 2 ⁇ Example 2> 2.20 g of ⁇ -cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 37.80 g of pure water. Thereafter, the solution was filtered using a microfilter having a pore size of 0.20 ⁇ m (manufactured by GE Healthcare Japan Co., Ltd. (former Whatman)) to prepare an aqueous solution for coating a resist pattern.
- a microfilter having a pore size of 0.20 ⁇ m (manufactured by GE Healthcare Japan Co., Ltd. (former Whatman)) to prepare an aqueous solution for coating a resist pattern.
- Example 3 1.58 g of ⁇ -cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.35 g of pyridinium p-phenolsulfonate were added to 38.38 g of pure water and dissolved. Thereafter, the solution was filtered using a microfilter having a pore size of 0.20 ⁇ m (manufactured by GE Healthcare Japan Co., Ltd. (former Whatman)) to prepare an aqueous solution for coating a resist pattern.
- a microfilter having a pore size of 0.20 ⁇ m
- ⁇ Comparative Example 1> 1.20 g of 18-crown 6-ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 38.80 g of pure water and dissolved. Thereafter, the solution was filtered using a microfilter having a pore size of 0.20 ⁇ m (manufactured by GE Healthcare Japan Co., Ltd. (former Whatman)) to prepare an aqueous solution for coating a resist pattern.
- the photoresist film was exposed through a photomask. It was.
- the photomask is selected according to the resist pattern to be formed.
- post exposure bake (PEB) is performed at 105 ° C. for 60 seconds, and after cooling, 0.26N tetramethylammonium hydroxide aqueous solution as a developer in an industrial standard 60 second single paddle process.
- PEB post exposure bake
- 0.26N tetramethylammonium hydroxide aqueous solution as a developer in an industrial standard 60 second single paddle process.
- pure water was applied and rinsed, and then dried by spin drying.
- the target resist pattern was formed through the above steps. About the formed line and space pattern, the measurement of the width of a line pattern and the presence or absence of pattern collapse were performed.
- a resist pattern that was dried without applying a resist pattern coating aqueous solution was used as a reference.
- the resist pattern exposure amount (mJ / cm 2 ) was determined after the coating film was formed. It was confirmed that even if the resist pattern was thinned by increasing it by 1 mJ / cm 2 , the collapse of the resist pattern was suppressed.
- FIG. 1 when the resist pattern was observed using the CD-SEM, it was determined that the resist pattern was “collapsed” when it was confirmed that the resist pattern was in a collapsed state and when the resist pattern was bent or wavy.
- resist pattern refinement test The resist underlayer film forming composition described in Example 1 of International Publication No. 2015/046149 was applied on a silicon wafer by a spinner so as to have a film thickness of 5 nm.
- the silicon wafer was placed on a hot plate and heated at 205 ° C. for 1 minute to form a resist underlayer film.
- an EUV resist was applied to a thickness of 40 nm and baked. Thereafter, a silicon wafer having a resist film on which a line-and-space pattern was drawn was manufactured using an ASML (manufactured) EUV exposure machine NXE3300.
- the produced silicon wafer was cut into chips and developed using a 0.26N aqueous tetramethylammonium hydroxide solution as a developing solution. Thereafter, pure water was applied to remove the developer, rinsed, and then dried on a hot plate at 100 ° C. for 30 seconds to obtain a reference line-and-space pattern of 1: 1. Further, a silicon wafer cut into a chip shape produced according to the above production procedure was developed using the developer. Then, after rinsing with pure water to remove the developer, the resist pattern coating aqueous solution prepared in Example 3 was applied on the resist pattern before being dried after being developed and rinsed, and then at 70 ° C. for 60 seconds. Baking was performed to form a coating film.
- the coating film is developed with a developer, and the resist pattern after the coating film is developed with the developer is rinsed with a rinse solution, dried at 100 ° C. for 30 seconds, and then the trimmed line pattern is developed.
- the width was measured.
- Table 2 below. In Table 2, when it was confirmed that the obtained resist pattern was a rectangular pattern with no collapse or collapse, the pattern shape was judged as “good”. From the results shown in Table 2, the pattern obtained by forming the coating film using the resist pattern coating aqueous solution of Example 3 and then developing, rinsing and drying the line pattern width compared to the reference pattern It was confirmed that was reduced by 2 nm. Further, roughness (LWR) was measured for the line and space pattern on which the coating film was formed. The LWR is an abbreviation for “Line Width Roughness”.
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Abstract
Description
本発明のレジストパターン被覆用水溶液に含まれるA成分は、α-シクロデキストリン、β-シクロデキストリン及びγ-シクロデキストリンからなる群から選択されるシクロデキストリン、又は前記シクロデキストリンの誘導体である。ここで、α-シクロデキストリンは下記式(1)で表されるグルコース単位が6個結合し環状構造を形成し、β-シクロデキストリンは該グルコース単位が7個結合し環状構造を形成し、γ-シクロデキストリンは該グルコース単位が8個結合し環状構造を形成している。また、前記シクロデキストリンの誘導体は、下記式(1)で表されるグルコース単位において、3つのOH基のうち少なくとも1つが置換基で置換された単位を少なくとも1つ有する。前記シクロデキストリンの誘導体が前記置換基で置換された単位を1つ有する場合、下記式(1)で表されるグルコース単位をさらに5個、6個又は7個有する。
本発明のレジストパターン被覆用水溶液に含まれるB成分は、水を主成分とする溶剤である。水を主成分とする溶剤中の水の濃度は、例えば51質量%乃至100質量%、又は80質量%乃至100質量%である。水の濃度が100質量%とは、前記水を主成分とする溶剤が水から成ることを意味する。該溶剤が水以外の成分を含む場合、該水以外の成分は、アルコール類、エステル類、エーテル類及びケトン類からなる群から選択される少なくとも1種の水溶性有機溶剤である。
本発明のレジストパターン被覆用水溶液は、C成分として前記式(2)で表される有機スルホン酸又はその塩をさらに含有してもよい。前記有機スルホン酸として、例えば、オクチルベンゼンスルホン酸、ノニルベンゼンスルホン酸、デシルベンゼンスルホン酸、ウンデシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸(別名:ラウリルベンゼンスルホン酸)、(1,3,5,7-テトラメチルオクチル)ベンゼンスルホン酸、トリデシルベンゼンスルホン酸、(1R)-(-)-10-カンファースルホン酸、(1S)-(+)-10-カンファースルホン酸、トリフルオロメタンスルホン酸、パーフルオロブタンスルホン酸、パーフルオロオクタンスルホン酸、ノナフルオロ-1-ブタンスルホン酸、p-トルエンスルホン酸及び1-ナフタレンスルホン酸を挙げることができる。また、前記有機スルホン酸の塩として、例えば、p-トルエンスルホン酸ピリジニウム、p-フェノールスルホン酸ピリジニウム、p-トルエンスルホン酸アンモニウム、p-フェノールスルホン酸アンモニウム、p-トルエンスルホン酸イミダゾリウム、p-フェノールスルホン酸イミダゾリウムを挙げることができる。これらの有機スルホン酸又はその塩のうち、本発明のレジストパターン被覆用水溶液に含まれるC成分として、p-フェノールスルホン酸ピリジニウムが好ましく用いられる。
本発明のレジストパターン被覆用水溶液は、必要に応じて界面活性剤等の各種添加剤を、本発明の効果を損なわない限りにおいてさらに含んでもよい。界面活性剤は、基板に対する該水溶液の塗布性を向上させるための添加物である。ノニオン系界面活性剤、フッ素系界面活性剤のような公知の界面活性剤を用いることができる。
本発明のレジストパターン被覆用水溶液を用いた、パターン形成方法及び反転パターン形成方法は、基板上にレジスト下層膜を介して形成されたレジスト膜に対し、リソグラフィープロセスにしたがって露光、ベーク、現像液で現像処理、及びリンス液でリンス処理を行うことによってレジストパターンを形成する工程を有する。ここで、前記基板として、精密集積回路素子の製造に使用される基板(例えば、酸化珪素膜、窒化珪素膜又は酸化窒化珪素膜で被覆されていてもよいシリコンウエハー等の半導体基板、窒化珪素基板、石英基板、無アルカリガラス基板、低アルカリガラス基板、結晶化ガラス基板、及びITO膜が形成されたガラス基板)を挙げることができる。そして、前記基板には、レジスト下層膜として、反射防止能を有する有機膜及び/又は無機膜が形成されている。そのレジスト下層膜が形成された基板上にレジスト膜を形成するために使用するレジスト溶液として、ポジ型レジスト溶液(例えば、住友化学(株)製PAR710、同PAR855、及びJSR(株)製AR2772JN)を用いることができる。前記ポジ型レジスト溶液に替えて、ネガ型レジスト溶液を使用することもできる。
本発明のレジストパターン被覆用水溶液を用いた反転パターン形成方法は、レジストパターンのパターン間を充填するように、ポリシロキサンと水及び/又はアルコール類を含有する溶剤とを含む充填用塗布液を塗布する工程を有する。この充填用塗布液の成分であるポリシロキサンとして、レジストパターンに塗布される塗布液に用いられる公知の材料を採用することができる。また、アルコール類として、前述のC成分が水以外の成分として含有することができるアルコール類の具体例を適用することができる。
α-シクロデキストリン(東京化成工業(株)製)1.20gを純水38.80gに加え溶解させた。その後孔径0.20μmのミクロフィルター(GEヘルスケア・ジャパン(株)(旧ワットマン社)製)を用いてろ過して、レジストパターン被覆用水溶液を調製した。
α-シクロデキストリン(東京化成工業(株)製)2.20gを純水37.80gに加え溶解させた。その後孔径0.20μmのミクロフィルター(GEヘルスケア・ジャパン(株)(旧ワットマン社)製)を用いてろ過して、レジストパターン被覆用水溶液を調製した。
α-シクロデキストリン(東京化成工業(株)製)1.58g、及びp-フェノールスルホン酸ピリジニウム0.35gを、純水38.38gに加え溶解させた。その後孔径0.20μmのミクロフィルター(GEヘルスケア・ジャパン(株)(旧ワットマン社)製)を用いてろ過して、レジストパターン被覆用水溶液を調製した。
18-クラウン6-エーテル(東京化成工業(株)製)1.20gを、純水38.80gに加え溶解させた。その後孔径0.20μmのミクロフィルター(GEヘルスケア・ジャパン(株)(旧ワットマン社)製)を用いてろ過して、レジストパターン被覆用水溶液を調製した。
実施例1乃至実施例3及び比較例1で調製したレジストパターン被覆用水溶液に純水をさらに加えて、スピンコーター(1500rpm、60秒間)にて50nm、100nmの膜厚になるようにシリコンウエハー上に塗布し、そのシリコンウエハーを100℃で60秒間ベークした。その後、前記シリコンウエハー上の塗膜を確認することで、各レジストパターン被覆用水溶液の該シリコンウエハー上への塗布性を評価した。その結果を下記表1に示す。表1において、シリコンウエハー上に前記レジストパターン被覆用水溶液を均一に塗布できた場合“良好”と判断し、前記レジストパターン被覆用水溶液が該シリコンウエハー上でムラのある不均一な状態である場合“塗布不良”と判断した。
国際公開第2015/046149号の比較例1に記載のレジスト下層膜形成組成物を、スピナーによりシリコンウエハー上に塗布した。そのシリコンウエハーをホットプレート上に配置し、205℃で1分間加熱し、膜厚80nmのレジスト下層膜を形成した。このレジスト下層膜の上に、市販のフォトレジスト溶液(住友化学(株)製、商品名:PAR855)をスピナーにより塗布し、ホットプレート上で105℃にて60秒間加熱してフォトレジスト膜(膜厚0.10μm)を形成した。
国際公開第2015/046149号の実施例1に記載のレジスト下層膜形成組成物を、スピナーによりシリコンウエハー上に5nmの膜厚になるように塗布した。そのシリコンウエハーをホットプレート上に配置し、205℃で1分間加熱しレジスト下層膜を形成した。このレジスト下層膜上に、EUVレジストを40nmの膜厚になるように塗布し、ベークした。その後、ASML社(製)EUV露光機NXE3300を用いて、ラインアンドスペースパターンが描画されたレジスト膜を有するシリコンウエハーを作製した。さらに作製したシリコンウエハーをチップ状にカットし、現像液として0.26規定のテトラメチルアンモニウムヒドロキシド水溶液を用いて現像した。その後、現像液を除去するため純水を塗布し、リンスした後、ホットプレートにて100℃で30秒間乾燥させ、リファレンスとなるラインアンドスペース1:1のパターンを得た。さらに上記作製手順にしたがって作製した、チップ状にカットしたシリコンウエハーを、上記現像液を用いて現像した。その後、現像液を除去するため純水でリンスした後、実施例3で調製したレジストパターン被覆用水溶液を、現像及びリンス処理を経た乾燥させる前のレジストパターン上に塗布し、70℃で60秒間ベークし被覆膜を形成した。さらに前記被覆膜を現像液で現像し、前記被覆膜を現像液で現像後のレジストパターンを、リンス液でリンス処理し、100℃で30秒間乾燥させた後、トリミングされたラインパターンの幅を測長した。その結果を、下記表2に示す。表2において、得られたレジストパターンが倒れや倒壊の無い矩形のパターンであることを確認できた場合、パターン形状が“良好”と判断した。表2の結果から、実施例3のレジストパターン被覆用水溶液を用いて被覆膜を形成後、現像、リンス処理及び乾燥させて得られたパターンは、リファレンスのパターンと比較して、ラインパターン幅が2nm縮小したことが確認できた。また、該被覆膜が形成されたラインアンドスペースパターンについて、ラフネス(LWR)の測定を行った。前記LWRとは、“Line Width Roughness”の略称である。
Claims (10)
- A成分:α-シクロデキストリン、β-シクロデキストリン及びγ-シクロデキストリンからなる群から選択されるシクロデキストリン、又は前記シクロデキストリンの誘導体、及び
B成分:水を主成分とする溶剤
を含み、水溶液全体100質量%に対して前記A成分の含有割合は0.1質量%乃至10質量%である、レジストパターン被覆用水溶液。 - 前記B成分の溶剤は、アルコール類、エステル類、エーテル類及びケトン類からなる群から選択される少なくとも1種の水溶性有機溶剤をさらに含む、請求項1又は請求項2に記載のレジストパターン被覆用水溶液。
- C成分:下記式(2)で表される有機スルホン酸又はその塩をさらに含み、該有機スルホン酸又はその塩の含有割合は前記A成分100質量%に対して0.01質量%乃至50質量%である、請求項1乃至請求項3のいずれか一項に記載のレジストパターン被覆用水溶液。
- 基板上にレジスト下層膜を介して形成されたレジスト膜に対し、リソグラフィープロセスにしたがって露光、ベーク、現像液で現像処理、及びリンス液でリンス処理を行うことによってライン状又は柱状のレジストパターンを形成する工程、
前記リンス処理後、前記レジストパターンを乾燥させることなく、該レジストパターンを被覆するように請求項1乃至請求項5のいずれか一項に記載のレジストパターン被覆用水溶液を塗布する工程、及び
前記レジストパターン被覆用水溶液が塗布された基板をスピンドライ後50℃乃至130℃で加熱し又は加熱せずに前記レジストパターンの表面に被覆膜を形成する工程、
を含むパターン形成方法。 - 基板上にレジスト下層膜を介して形成されたレジスト膜に対し、リソグラフィープロセスにしたがって露光、ベーク、現像液で現像処理、及びリンス液でリンス処理を行うことによってレジストパターンを形成する工程、
前記リンス処理後、前記レジストパターンを乾燥させることなく、該レジストパターンを被覆するように請求項4又は請求項5に記載のレジストパターン被覆用水溶液を塗布する工程、
前記レジストパターン被覆用水溶液が塗布された基板をスピンドライ後50℃乃至130℃で加熱し又は加熱せずに前記レジストパターンの表面に被覆膜を形成する工程、及び
前記被覆膜が形成された前記基板を冷却し、その後該被覆膜をエッチングガスでエッチングすることによって該被覆膜を除去する工程、
を含むパターン形成方法。 - 基板上にレジスト下層膜を介して形成されたレジスト膜に対し、リソグラフィープロセスにしたがって露光、ベーク、現像液で現像処理、及びリンス液でリンス処理を行うことによってレジストパターンを形成する工程、
前記リンス処理後、前記レジストパターンを乾燥させることなく、該レジストパターンを被覆するように請求項4又は請求項5に記載のレジストパターン被覆用水溶液を塗布する工程、
前記レジストパターン被覆用水溶液が塗布された基板をスピンドライ後50℃乃至130℃で加熱し又は加熱せずに前記レジストパターンの表面に被覆膜を形成する工程、
前記被覆膜が形成された前記基板を冷却し、その後該被覆膜に対し現像液で現像処理する工程、及び
前記被覆膜に対する現像処理後、前記レジストパターンをリンス液でリンス処理する工程、
を含むパターン形成方法。 - 基板上にレジスト下層膜を介して形成されたレジスト膜に対し、リソグラフィープロセスにしたがって露光、ベーク、現像液で現像処理、及びリンス液でリンス処理を行うことによってレジストパターンを形成する工程、
前記リンス処理後、前記レジストパターンを乾燥させることなく、該レジストパターンを被覆するように請求項1乃至請求項5のいずれか一項に記載のレジストパターン被覆用水溶液を塗布する工程、
前記レジストパターン被覆用水溶液が塗布された基板をスピンドライ後50℃乃至130℃で加熱し又は加熱せずに前記レジストパターンの表面に被覆膜を形成する工程、
前記被覆膜が形成された前記基板を冷却し、その後該被覆膜に対し現像液で現像処理する工程、
前記被覆膜に対する現像処理後、前記レジストパターンのパターン間を充填するように、ポリシロキサンと水及び/又はアルコール類を含有する溶剤とを含む充填用塗布液を塗布する工程、
前記充填用塗布液に含まれるポリシロキサン以外の成分及び前記被覆膜に対する現像処理に使用した現像液を除去し又は減少させて塗膜を形成する工程、
前記塗膜をエッチバックして前記レジストパターンの上面を露出させる工程、及び
上面が露出した前記レジストパターンを除去する工程、
を含む反転パターン形成方法。 - 基板上にレジスト下層膜を介して形成されたレジスト膜に対し、リソグラフィープロセスにしたがって露光、ベーク、及び現像液で現像処理を行うことによって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を被覆するように請求項1乃至請求項5のいずれか一項に記載のレジストパターン被覆用水溶液を塗布する工程、
前記レジストパターン被覆用水溶液が塗布された基板をスピンドライ後50℃乃至130℃で加熱し又は加熱せずに前記レジストパターンの表面に被覆膜を形成する工程、
前記被覆膜が形成された前記基板を冷却し、その後該被覆膜に対し現像液で現像処理する工程、
前記被覆膜に対する現像処理後、前記レジストパターンをリンス液でリンス処理する工程、
前記リンス処理後、前記レジストパターンを乾燥させることなく、該レジストパターンのパターン間を充填するように、ポリシロキサンと水及び/又はアルコール類を含有する溶剤とを含む充填用塗布液を塗布する工程、
前記充填用塗布液に含まれるポリシロキサン以外の成分及び前記リンス液を除去し又は減少させて塗膜を形成する工程、
前記塗膜をエッチバックして前記レジストパターンの上面を露出させる工程、及び
上面が露出した前記レジストパターンを除去する工程、
を含む反転パターン形成方法。
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US16/343,342 US20190243251A1 (en) | 2016-10-19 | 2017-10-13 | Aqueous solution for resist pattern coating and pattern forming method using the same |
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