US20120128891A1 - Composition for forming resist underlayer film for nanoimprint - Google Patents

Composition for forming resist underlayer film for nanoimprint Download PDF

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Publication number
US20120128891A1
US20120128891A1 US13/386,230 US201013386230A US2012128891A1 US 20120128891 A1 US20120128891 A1 US 20120128891A1 US 201013386230 A US201013386230 A US 201013386230A US 2012128891 A1 US2012128891 A1 US 2012128891A1
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Prior art keywords
group
underlayer film
resist underlayer
resist
compound
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US13/386,230
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Inventor
Satoshi Takei
Tomoya Ohashi
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Nissan Chemical Corp
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Nissan Chemical Corp
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Assigned to NISSAN CHEMICAL INDUSTRIES, LTD. reassignment NISSAN CHEMICAL INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OHASHI, TOMOYA, TAKEI, SATOSHI
Publication of US20120128891A1 publication Critical patent/US20120128891A1/en
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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
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist 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
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • 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
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • 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
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • 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
    • 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
    • G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source

Definitions

  • the present invention relates to a composition for forming an underlayer film between a substrate to be processed and a resist for nanoimprint. More in detail, the present invention relates to an underlayer film forming composition for forming an underlayer film used as an underlayer of a resist for nanoimprint in a pattern forming process by performing heat-baking, light-irradiation, or both of them. The present invention relates also to a forming method of an underlayer film using the underlayer film forming composition and a forming method of a resist pattern for nanoimprint.
  • the fine processing is a processing method for forming fine convexo-concave shapes corresponding to the following pattern on the surface of a substrate by: forming a thin film of a photoresist on a semiconductor substrate such as a silicon wafer; irradiating the resultant thin film with an active ray such as an ultraviolet ray through a mask pattern in which a pattern of a semiconductor device is depicted for development; and subjecting the substrate to etching processing using the resultant photoresist pattern as a protecting film.
  • an active ray such as an ultraviolet ray
  • Patent Document 1 a method for forming a cured film by irradiating an underlayer film of the photoresist with light
  • nanoimprint lithography As a pattern forming method of the next generation, nanoimprint lithography has attracted attention as one technology.
  • the nanoimprint lithography is a method entirely different from conventional lithography using a light source.
  • the nanoimprint lithography is a method for producing a pattern symmetric to a pattern of a template on a substrate by preparing a mold (template) having a pattern symmetric to a pattern produced beforehand and by directly pushing the mold into a resist applied on the substrate.
  • the nanoimprint lithography is characterized in that the resolution of the nanoimprint lithography does not depend on the light source wavelength in comparison with conventional photolithography, so that an expensive apparatus such as an excimer laser exposing apparatus and an electron beam drawing apparatus is not necessary, and consequently, the cost therefor can be reduced (see, for example, Patent Document 2 and Patent Document 3).
  • the nanoimprint lithography is a pattern forming method by: dropping by inkjet a composition of a resist for nanoimprint onto an inorganic substrate such as silicon and gallium, an oxide film, a nitride film, a quartz, a glass, or a polymer film to apply the composition thereon in a film thickness of about some ten nanometers to some micrometers; pressing a template having a fine convexo-concave shape of about some ten nanometers to some ten micrometers pattern size against the composition to pressurize the composition; irradiating the composition with light or heat-baking the composition while the composition is in a pressurized state to cure the composition; and releasing the template from the coating film to obtain a transferred pattern.
  • an inorganic substrate such as silicon and gallium, an oxide film, a nitride film, a quartz, a glass, or a polymer film to apply the composition thereon in a film thickness of about some ten nanometers to some micrometers
  • the substrate and the template are transparent.
  • the nanoimprint lithography is a technology for patterning by a physical contact, so that as the miniaturization is progressed, there is easily caused a problem of a patterning loss such as chipping and peeling of a pattern and foreign matters caused by reattachment of the chipped or peeled pattern (see, for example, Non-patent Document 1). Peeling properties between the template and the resist for nanoimprint and adhesion between the resist for nanoimprint and the base substrate to be processed are important, so that conventionally, there has been attempted to solve a problem of defect or foreign matters by surface modifying treatment of the template or the resist.
  • the resist composition for nanoimprint is classified roughly into a radical crosslinking type, a cation crosslinking type, and a mixed type thereof according to the photoreaction mechanisms (see, for example, Patent Document 4, Patent Document 5, and Patent Document 6).
  • the radical crosslinking type contains a compound derivative having an ethylenic unsaturated bond and uses generally a composition containing a polymerizable compound having a radical polymerizable methacrylate, acrylate, or vinyl group and a photocrosslinking initiator.
  • the cation crosslinking type uses generally a composition containing a polymerizable compound that is a compound derivative having an epoxy or oxetane ring and a photocrosslinking initiator.
  • a radical or a cation that is generated from the photocrosslinking initiator attacks the ethylenic unsaturated bond or the epoxy or oxetane ring respectively, and a chain polymerization and a crosslinking reaction are progressed to form a three-dimensional network structure.
  • a monomer or oligomer having a multifunctional group such as a bifunctional or more group is used as a component, a crosslinked structure can be obtained.
  • the resist for nanoimprint used in this process besides a characteristic of pattern forming, a characteristic of capable of controlling coating properties of a substrate around a step or a via hole, an embedding characteristic capable of filling a via hole without void, a planarizing characteristic capable of forming a planar film on the surface of a substrate, and the like are required.
  • a resist for nanoimprint to a substrate having a large aspect ratio.
  • Patent Document 1 International Publication No. WO 2007/066597 pamphlet
  • Patent Document 2 Japanese Patent Application Publication No. 2006-287012
  • Patent Document 3 Japanese Patent Application Publication No. 2007-305647
  • Patent Document 4 Japanese Patent Application Publication No. 2007-072374
  • Patent Document 5 Japanese Patent Application Publication No. 2008-105414
  • Patent Document 6 Japanese Patent Application Publication No. 2009-51017
  • Patent Document 7 Japanese Patent Application Publication No. 2006-114882
  • Patent Document 8 Japanese Patent Application Publication No. 2005-159358
  • Patent Document 9 Japanese Patent Application Publication No. 2005-532576
  • Non-patent Document 1 I. McMackin, et. al., Proc. of SPIE 6921, 69211L (2008)
  • Non-patent Document 2 Jianjun Hao et. al., Proc. of SPIE 6517, 651729 (2007)
  • Non-patent Document 3 Ken-ichiro Nakamatsu et. al., Japanese Journal of Applied Physics 44, 8186 (2005)
  • the present invention has been invented in the light of the present situation described above. That is, it is an object of the present invention to provide a silicon atom-containing resist underlayer film forming composition for curing a resist underlayer film used as an underlayer of a resist for nanoimprint in nanoimprint lithography of a pattern forming process by light-irradiation or heat-baking to form the resist underlayer film.
  • a composition containing, as components, a polymerizable compound (A) having a small content of low molecular weight components and containing silicon atoms in a content of 5 to 45% by mass, a polymerization initiator (B), and a solvent (C) is suitable as a material for forming a resist underlayer film for nanoimprint, and has completed the present invention.
  • the present invention is, according to a first aspect, a composition for forming a resist underlayer film used for nanoimprint in a pattern forming process using nanoimprint by performing heat-baking, light-irradiation, or both of them, the composition containing a silicon atom-containing polymerizable compound (A), a polymerization initiator (B), and a solvent (C);
  • the composition for forming the resist underlayer film according to the first aspect in which the polymerizable compound (A) contains silicon atoms in a content of 5 to 45% by mass;
  • the composition for forming the resist underlayer film according to the first aspect or the second aspect in which the polymerizable compound (A) is a polymerizable compound having at least one cation polymerizable reactive group, a polymerizable compound having at least one radical polymerizable reactive group, or both of them and the polymerization initiator (B) is a photopolymerization initiator;
  • the composition for forming the resist underlayer film according to the first aspect or the second aspect in which the polymerizable compound (A) is a polymerizable compound having at least one cation polymerizable reactive group, a polymerizable compound having at least one radical polymerizable reactive group, or both of them and the polymerization initiator (B) is a thermopolymerization initiator;
  • the composition for forming the resist underlayer film according to the third aspect or the fourth aspect in which the cation polymerizable reactive group is an epoxy group, an oxetane group, or an organic group containing any one of or both of them;
  • the composition for forming the resist underlayer film according to the third aspect or the fourth aspect in which the radical polymerizable reactive group is a vinyl group or an organic group containing a vinyl group;
  • R 1 is an epoxy group, an oxetane group, a vinyl group, or a polymerizable organic group which contains one to three of an epoxy group, an oxetane group, and a vinyl group and is bonded to a silicon atom through a Si—C bond
  • R 3 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, or an organic group which has a mercapto group, an amino group, or a cyano group and is bonded to a silicon atom through a Si—C bond
  • R 2 is a halogen atom, a C 1-8 alkoxy group, or an acyloxy group
  • a is an integer of 1 b is an integer of 0, 1, or 2, where a+b is an integer of 1, 2, or 3
  • R 4 is an epoxy group, an oxetane group, a vinyl group, or a polymerizable organic group which contains one to three of an epoxy group, an oxetane group, and a vinyl group and is bonded to a silicon atom through a Si—C bond
  • R 5 is a halogen atom, a C 1-8 alkoxy group, or an acyloxy group
  • Y is an oxygen atom, a methylene group, or a C 2-20 alkylene group
  • c is an integer of 1 or 2), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof;
  • R 11 and R 13 are individually an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, or an organic group which has a mercapto group, an amino group, or a cyano group and is bonded to a silicon atom through a Si—C bond;
  • R 12 is a halogen atom, a C 1-8 alkoxy group, or an acyloxy group; and
  • a 1 and b 1 are individually an integer of 0, 1, or 2, where a 1 +b 1 is an integer of 0, 1, or 2) and
  • R 14 is a C 1-5 alkyl group;
  • X is a halogen atom, a C 1-8 alkoxy group, or an acyloxy group;
  • Y 1 is a methylene group or a C 2-20 alkylene group; and
  • c 1 is an integer of 0 or 1), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof;
  • the composition for forming the resist underlayer film according to any one of the first aspect to the sixth aspect in which the silicon atom-containing polymerizable compound (A) contains a combination of a polymerizable compound (A1) and a polymerizable compound (A2) in which an abundance ratio between silicon atoms in (A1) and silicon atoms in (A2) in a molar ratio is 100:0 to 50, and is a polymerizable organic group-having condensation product having a weight average molecular weight of 100 to 100,000 produced by hydrolyzing the polymerizable compound (A1) and the polymerizable compound (A2) and by condensing the resultant hydrolyzed products;
  • the composition for forming the resist underlayer film according to any one of the first aspect to the eleventh aspect further containing a crosslinkable compound, a surface modifier, or both of them;
  • a forming method of a laminated structure used in a pattern forming process using nanoimprint including: a process of applying the composition for forming the resist underlayer film as described in the first aspect to the twelfth aspect on a substrate to form a resist underlayer film; a process of performing heat-baking, light-irradiation, or both of them relative to the resist underlayer film to cure the resist underlayer film; and a process of applying a resist composition for nanoimprint on the resist underlayer film and heat-baking the resultant coating to form a resist for nanoimprint;
  • a forming method of a laminated structure used in a pattern forming process using nanoimprint including: a process of applying the composition for forming the resist underlayer film as described in the first aspect to the twelfth aspect on a substrate to form a resist underlayer film; a process of performing heat-baking, light-irradiation, or both of them relative to the resist underlayer film to cure the resist underlayer film; a process of applying a resist composition for nanoimprint on the resist underlayer film and heat-baking the resultant coating to form a resist for nanoimprint; and a process of imprinting by a step and repeat method;
  • the forming method according to the thirteenth aspect or the fourteenth aspect in which the substrate is a substrate which has a hole having an aspect ratio represented by height/diameter of 0.01 or more or a step having an aspect ratio represented by height/width of 0.01 or more;
  • a resist underlayer film obtained by performing heat-baking, light-irradiation, or both of them relative to the resist underlayer film forming composition of the present invention exhibits applying-type hardmask characteristics having a dry etching rate smaller than that of a resist under an oxygen gas condition and has a dry etching rate larger than that of a resist under a fluorine-based gas (such as CF 4 ) condition.
  • the resist underlayer film forming composition of the present invention contains silicon atoms that are an inorganic atom derived from an organic silicon compound in a content of 5 to 45% by mass, so that the plasma etching rate of the resist underlayer film forming composition by an oxygen gas becomes smaller and the resist underlayer film forming composition becomes an etching-resistant hardmask layer.
  • a fluorine-based gas (such as CF 4 ) used during etching according to a resist pattern of the resist underlayer film of the present invention has a satisfactorily high etching rate relative to the resist underlayer film of the present invention in comparison with an etching rate relative to a resist.
  • the resist underlayer film of the present invention is removed by etching to transfer the resist pattern to the underlayer film of the present invention, and by using the formed resist film and the formed resist underlayer film as a protecting film, the substrate can be processed.
  • a resist underlayer film obtained from the resist underlayer film forming composition exhibits high adhesion to a resist for nanoimprint and a base substrate and is excellent in peeling properties between a template and a resist for nanoimprint.
  • a template having a fine convexo-concave shape is pressed against a resist for nanoimprint formed on the resist underlayer film to pressurize the resist and the resist composition is cured by light-irradiation or heat-baking while the composition is in a pressurized state, when the template is released from the coating film, by high adhesion between the underlayer film of the present invention and the resist for nanoimprint, it is less likely to cause a problem of a patterning loss such as chipping, collapse, and peeling of a resist pattern and foreign matters caused by reattachment of resist pieces.
  • the underlayer film of the present invention has excellent planarity and excellent surface smoothness and planarizes an unevenness of a base substrate, so that the underlayer film can homogenize the film thickness of a resist formed as an upper layer of the underlayer film, and as a result thereof, the underlayer film brings high resolution in a lithography process.
  • the resist underlayer film of the present invention causes no intermixing with a resist formed as an upper layer of the resist underlayer film, is insoluble in a photoresist solvent, causes no diffusion of a low molecular weight substance from the underlayer film to the resist film as an upper layer of the resist underlayer film during application or heating-drying, and has an advantageous rectangular nano-patterning characteristic.
  • the resist underlayer film can be formed by light-irradiation without performing heat-baking at a high temperature. Therefore, a contamination of peripheral equipment by volatilization or sublimation of a low molecular weight component can be prevented. Further, heat-baking at a high temperature is not required, so that when a low molecular weight component is used in the resist underlayer film forming composition, there is no fear of sublimation or the like and a relatively large amount of a low molecular weight component can be used in the resist underlayer film forming composition.
  • the resist underlayer film can be formed. Then, there can also be formed a resist underlayer film further more excellent in filling properties of a hole and planarizing properties of a semiconductor substrate.
  • the present invention is a composition for forming a resist underlayer film for nanoimprint in a pattern forming process using nanoimprint by performing heat-baking, light-irradiation, or both of them.
  • the composition for forming a resist underlayer film for nanoimprint containins a silicon atom-containing polymerizable compound (A), a polymerization initiator (B), and a solvent (C).
  • the polymerizable compound (A) is a polymerizable organic group-containing organic silicon compound, a hydrolysis product of the polymerizable organic group-containing organic silicon compound, a condensation product of the hydrolysis product of the polymerizable organic group-containing organic silicon compound, or a mixture thereof.
  • the polymerizable compound (A) is a polymerizable compound having at least one cation polymerizable reactive group, a polymerizable compound having at least one radical polymerizable reactive group, or a combination thereof, and as the polymerization initiator (B), a photopolymerization initiator can be used.
  • the cation polymerization of the polymerizable compound (A) is progressed to form an underlayer film.
  • the cation polymerizable reactive group is preferably an epoxy group, an oxetane group, or an organic group containing any one of or both of them.
  • the polymerizable compound (A) is a polymerizable compound having at least one radical polymerizable ethylenic unsaturated bond such as a vinyl group and an organic group containing a vinyl group, and as the photopolymerization initiator, a photo radical polymerization initiator can be used.
  • a photo radical polymerization initiator By irradiating an underlayer film containing the polymerizable compound (A) with light and by an action of the photo radical polymerization initiator, the radical polymerization of the polymerizable compound (A) is progressed to form the underlayer film.
  • the ethylenic unsaturated bond is preferably a vinyl group.
  • the vinyl group is preferably an organic group containing an acryloxy group or a methacryloxy group.
  • the polymerizable compound (A) is the condensation product
  • thermo cation polymerization initiator or a photo cation polymerization initiator can be used.
  • thermo radical polymerization initiator or a photo radical polymerization initiator can be used.
  • the polymerizable compound (A) there can be used a combination of a polymerizable compound having at least one cation polymerizable reactive group and a polymerizable compound having at least one radical polymerizable reactive group, and as the polymerization initiator (B), a photopolymerization initiator can be used.
  • a photopolymerization initiator By irradiating the resist underlayer film with light, the photo cation polymerization and the photo radical polymerization are progressed to form the resist underlayer film.
  • the thermopolymerization is progressed and then, by performing light-irradiation, the photo cation polymerization and the photo radical polymerization are progressed, so that the resist underlayer film can also be formed.
  • thermopolymerization by a cation polymerizable reactive group such as an epoxy group and an epoxy group-containing organic group
  • a radical polymerizable reactive group a vinyl group or a vinyl group-containing organic group
  • the polymerizable compound (A) may contain a thermally cation polymerizable reactive group and a photo radical polymerizable reactive group in a ratio of 10:90 to 90:10.
  • the contact angle of the surface of the resist underlayer film is high, so that when the resist underlayer film forming composition is applied on a substrate, the liquid easily spreads on the surface of the substrate. Then, after the photopolymerization is performed, the contact angle of the surface of the resist underlayer film becomes lower, so that the resist underlayer film is excellent in the adhesion thereof to a resist film overcoated on the surface of the resist underlayer film.
  • the adhesion is easily influenced particularly by a vinyl group and there can be used a method for enhancing the adhesion of the resist underlayer film to the overcoated resist.
  • the method includes: enhancing the contact angle of the resist underlayer film before performing the photo radical polymerization to spread the resist underlayer film forming composition on the substrate and to satisfactorily enhance the planarity of the resist underlayer film; and then lowering the contact angle of the resist underlayer film after performing the photo radical polymerization.
  • the silicon atom-containing polymerizable compound (A) there can be used a silicon atom-containing polymerizable compound (A1) containing at least one of organic silicon compound selected from a group consisting of an organic silicon compound of Formula (I):
  • R 1 is an epoxy group, an oxetane group, a vinyl group, or a polymerizable organic group which contains one to three of an epoxy group, an oxetane group, and a vinyl group and is bonded to a silicon atom through a Si—C bond
  • R 3 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, or an organic group which has a mercapto group, an amino group, or a cyano group and is bonded to a silicon atom through a Si—C bond
  • R 2 is a halogen atom, a C 1-8 alkoxy group, or an acyloxy group
  • a is an integer of 1 b is an integer of 0, 1, or 2, where a+b is an integer of 1, 2, or 3
  • R 4 is an epoxy group, an oxetane group, a vinyl group, or a polymerizable organic group which contains one to three of an epoxy group, an oxetane group, and a vinyl group and is bonded to a silicon atom through a Si—C bond
  • R 5 is a halogen atom, a C 1-8 alkoxy group, or an acyloxy group
  • Y is an oxygen atom, a methylene group, or a C 2-20 alkylene group
  • c is an integer of 1 or 2
  • Preferred examples of the organic silicon compound of Formula (1) corresponding to the polymerizable compound (A1) include: a vinyl group-containing silane compound such as methacrylamidetrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, (methacryloxymethyl)bis(trimethyloxy)methylsilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyldimethylchlorosilane, 2-methacryloxyethyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropyltrichiorosilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltripropoxysilane, 3-methacryloxypropyltrichlor
  • an epoxy group-containing silane compound such as glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxy
  • Preferred examples of the organic silicon compound of Formula (II) corresponding to the polymerizable compound (A1) include: an epoxy group-containing silane compound such as bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyldisiloxane, di(glycidoxypropyl)tetramethyldisiloxane, and di(glycidoxypropyl)tetraphenyldisiloxane; and a vinyl group-containing silane compound such as di(3-methacryloxypropyl)tetramethyldisiloxane, di(3 -methacryloxypropyl)tetraphenyldisiloxane, di(3-acryloxypropyl)tetramethyldisiloxane, and di(3-acryloxypropyl)tetraphenyldisiloxane.
  • an epoxy group-containing silane compound such as bis[2-(3,4-epoxycyclohexyl)ethy
  • Preferred examples of the organic silicon compound of Formula (II) corresponding to the polymerizable compound (A1) include: an epoxy group-containing silane compound such as bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyldisiloxane, di(glycidoxypropyl)tetramethyldisiloxane, and di(glycidoxypropyl)tetraphenyldisiloxane; and a vinyl group-containing silane compound such as di(3 -methacryloxypropyl)tetramethyldisiloxane, di(3-methacryloxypropyl)tetraphenyldisiloxane, di(3-acryloxypropyl)tetramethyldisiloxane, and di(3-acryloxypropyl)tetraphenyldisiloxane,
  • an epoxy group-containing silane compound such as bis[2-(3,4-epoxycyclohexyl)ethy
  • the polymerizable compound (A1) is a silicon atom-containing polymerizable compound (A1) containing at least one of organic silicon compound selected from a group consisting of the organic silicon compound of Formula (I) and the organic silicon compound of Formula (II), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof.
  • the polymerizable compound (A1) can be combined with a silicon atom-containing polymerizable compound (A2) containing no polymerizable organic group such as an epoxy group and a vinyl group.
  • the silicon atom-containing polymerizable compound (A2) is a silicon atom-containing compound containing at least one of organic silicon compound selected from a group consisting of
  • R 11 and R 13 are individually an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, or an organic group which has a mercapto group, an amino group, or a cyano group and is bonded to a silicon atom through a Si—C bond;
  • R 12 is a halogen atom, a C 1-8 alkoxy group, or an acyloxy group; and a and b are individually an integer of 0, 1, or 2, where a+b is an integer of 0, 1, or 2) and an organic silicon compound of Formula (IV):
  • R 14 is a C 1-5 alkyl group; X is a halogen atom, a C 1-8 alkoxy group, or an acyloxy group; Y is a methylene group or a C 2-20 alkylene group; and c 1 is an integer of 0 or 1), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof.
  • Preferred examples of the organic silicon compound of Formula (III) corresponding to the polymerizable compound (A2) include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, ⁇ -ch
  • Preferred examples of the organic silicon compound of Formula (IV) corresponding to the polymerizable compound (A2) include methylenebismethyldimethoxysilane, ethylenebisethyldimethoxysilane, propylenebisethyldiethoxysilane, and butylenebismethyldiethoxysilane.
  • the polymerizable compound (A2) is a silicon atom-containing polymerizable compound (A2) containing at least one of organic silicon compound selected from a group consisting of the organic silicon compound of Formula (III) and the organic silicon compound of Formula (IV), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof.
  • the silicon atom-containing polymerizable compound (A) contains the polymerizable compound (A1) or a combination of the polymerizable compound (A1) and the polymerizable compound (A2).
  • the molar ratio of the polymerizable compound (A1):the polymerizable compound (A2) in the polymerizable compound (A) is 100:0 to 50.
  • the combination is preferably a condensation product having a weight average molecular weight of 100 to 100,000 and a polymerizable organic group and being produced by hydrolyzing the polymerizable compound (A1) and the polymerizable compound (A2) and by condensing the resultant hydrolyzed products.
  • water for hydrolyzing and condensing the organic silicon compound, there is used water in an amount of more than 1 mole and 100 moles or less, preferably 1 mole to 50 moles, relative to 1 mole of a hydrolyzable group (such as a chlorine atom and an alkoxy group) of the organic silicon compound.
  • a hydrolyzable group such as a chlorine atom and an alkoxy group
  • the production of the polymerizable compound (A) of the present invention is characterized in that when at least one of silane compound selected from the above compounds is hydrolyzed and condensed, a catalyst is used.
  • a catalyst capable of being used in this case include a chelate compound of a metal such as titanium and aluminum, an acid catalyst, and an alkaline catalyst.
  • the silicon atom-containing polymerizable compound (A) contains the organic silicon compound of Formula (I) or a combination of the organic silicon compound of Formula (I) and the organic silicon compound of Formula (III), and is preferably a polymerizable organic group-having condensation product having a weight average molecular weight of 100 to 1,000,000 produced by hydrolyzing an organic silicon compound containing an organic silicon compound in which the value of a+b or the values of a+b and a 1 +b 1 in the organic silicon compound of Formula (I) or in both of the organic silicon compound of Formula (I) and the organic silicon compound of Formula (III) become(s) 1 in a ratio of 5 to 75% by mass and by condensing the resultant hydrolyzed product.
  • the resist underlayer film forming composition of the present invention is produced ordinarily by dissolving or dispersing the polymerizable compound (A) in an organic solvent.
  • the organic solvent is at least one selected from a group consisting of an alcohol solvent, a ketone solvent, an amide solvent, an ester solvent, and an aprotic solvent.
  • a component such as ⁇ -diketone, colloidal silica, colloidal alumina, an organic polymer, a surfactant, a silane coupling agent, a radical generator, a triazene compound, and an alkaline compound.
  • the organic silicon compound used in the present invention is hydrolyzed and condensed ordinarily in an organic solvent.
  • organic solvent used for the hydrolysis examples include: aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, n-amylnaphthalene, and trimethylbenzene; monoalcohol solvents such as methanol, ethanol, n-propan
  • polyalcohol solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,4,hexanediol-2,5,heptanediol -2,4,2-ethylhexanediol -1,3,diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin;
  • polyalcohol solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,4,hexanediol-2,5,heptanediol -2,4,2-ethylhexanediol -1,3,diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin;
  • ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone;
  • ether solvents such as ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether,
  • ester solvents such as diethyl carbonate, methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl
  • nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, sulfolane, and 1,3-propane sultone.
  • nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone
  • sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, te
  • propylene glycol monomethyl ether propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, in terms of preservation solubility of the solution thereof.
  • a catalyst When the organic silicon compound is hydrolyzed and condensed, a catalyst may be used.
  • the catalyst used in this case include a metal chelate compound, an organic acid, an inorganic acid, an organic base, and an inorganic base.
  • the metal chelate compound include: titanium chelate compounds such as triethoxy•mono(acetylacetonate)titanium, tri-n-propoxy•mono(acetylacetonate)titanium, tri-isopropoxy•mono(acetylacetonate)titanium, tri-n-butoxy•mono(acetylacetonate)titanium, tri-sec-butoxy•mono(acetylacetonate)titanium, tri-tert-butoxy•mono(acetylacetonate)titanium, diethoxy•bis(acetylacetonate)titanium, di-n-propoxy•bis(acetylacetonate)t
  • zirconium chelate compounds such as triethoxy•mono(acetylacetonate)zirconium, tri-n-propoxy•mono(acetylacetonate)zirconium, tri-isopropoxy•mono(acetylacetonate)zirconium, tri-n-butoxy•mono(acetylacetonate)zirconium, tri-sec-butoxy•mono(acetylacetonate)zirconium, tri-tert-butoxy•mono(acetylacetonate)zirconium, diethoxy•bis(acetylacetonate)zirconium, di-n-propoxy•bis(acetylacetonate)zirconium, di-isopropoxy•bis(acetylacetonate)zirconium, di-n-butoxy•bis(acetylacetonate)zirconium, di-sec-butoxy•bis(acetylacetonate)zirconium,
  • organic acid examples include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linolic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid
  • Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclo octane, diazabicyclo nonane, diazabicyclo undecene, and tetramethylammonium hydroxide.
  • Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.
  • metal chelate compounds, organic acids, and inorganic acids are preferred and more preferred are titanium chelate compounds and organic acids. These catalysts may be used individually or in combination of two or more types thereof.
  • polymerizable compounds containing no silicon atom below may be used to be copolymerized (hybridization) or mixed with the above silicon atom-containing polymerizable compounds.
  • ethylenic unsaturated bond-having polymerizable compound containing no silicon atom examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, nonapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2-bis[4-(acryloxydiethoxy)phenyl]propane, 2,2-bis[4-(methacryloxydiethoxy)phenyl]propane, 3-phenoxy-2-propanoyl acrylate, 1,6-bis(3-acryloxy-2-hydroxypropyl)-hexyl ether, pentaerythrito
  • Examples of the ethylenic unsaturated bond-having polymerizable compound containing no silicon atom also include urethane compounds that can be obtained by a reaction between a multivalent isocyanate compound and a hydroxyalkyl unsaturated carboxylic acid ester compound, compounds that can be obtained by a reaction between a multivalent epoxy compound and a hydroxyalkyl unsaturated carboxylic acid ester compound, diallyl ester compounds such as diallyl phthalate, and divinyl compounds such as divinyl phthalate.
  • Examples of the cation polymerizable moiety-having polymerizable compound containing no silicon atom include a compound having a cyclic ether structure such as an epoxy ring and an oxetane ring, a vinyl ether structure, a vinyl thioether structure, or the like.
  • the epoxy ring-having polymerizable compound containing no silicon atom is not particularly limited, as such a polymerizable compound, a compound having one to six, or two to four epoxy ring(s) can be used.
  • examples of the epoxy ring-having polymerizable compound include compounds having two or more glycidyl ether structures or glycidyl ester structures that can be produced from a compound having two or more hydroxy groups or carboxy groups such as diol compounds, triol compounds, dicarboxylic acid compounds, and tricarboxylic acid compounds and a glycidyl compound such as epichlorohydrin.
  • epoxy ring-having polymerizable compound containing no silicon atom examples include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexane dicarboxylic acid diglycidyl ester, 4,4′-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, trimethylolethane triglycidyl ether, triglycidyl-p-aminophenol, tetraglycidyl meta-xylenedi
  • the oxetane ring-having polymerizable compound containing no silicon atom is not particularly limited, as such a polymerizable compound, a compound having one to six, or two to four oxetane ring(s) can be used.
  • Examples of the oxetane ring-having polymerizable compound containing no silicon atom include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3,3-diethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 1,4-bis(((3-ethyl-3-oxetanyl)methoxy)methyl)benzene, di((3-ethyl-3-oxetanyl)methyl) ether, and pentaerythritoltetrakis((3-ethyl-3-oxetanyl)methyl) ether.
  • the vinyl ether structure-having polymerizable compound containing no silicon atom is not particularly limited, as such a polymerizable compound, a compound having one to six, or two to four vinyl ether structure(s) can be used.
  • vinyl ether structure-having polymerizable compound containing no silicon atom examples include vinyl-2-chloroethyl ether, vinyl-n-butyl ether, 1,4-cyclohexanedimethanol divinyl ether, vinyl glycidyl ether, bis(4-(vinyloxymethyl)cyclohexylmethyl) glutarate, tri(ethyleneglycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether, tris(4-vinyloxy)butyl trimellirate, bis(4-(vinyloxy)butyl) terephthalate, bis(4-(vinyloxy)butyl isophthalate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethyl
  • the polymerization initiator (B) in the underlayer film forming composition of the present invention is not particularly limited so long as the polymerization initiator (B) is a polymerizable compound having an action capable of initiating the polymerization of the polymerizable compound by heat-baking or light-irradiation.
  • the polymerization initiator (B) a compound generating an acid (a Br ⁇ nsted acid or a Lewis acid), a base, a radical, or a cation by light-irradiation or heat-baking can be used.
  • Examples of the polymerization initiator (B) include: a compound capable of generating an active radical by light-irradiation to effect radical polymerization of the polymerizable compound, that is, a photo radical polymerization initiator; and a compound capable of generating a cation species such as a protonic acid and a carbon cation by light-irradiation to effect cation polymerization of the polymerizable compound, that is, a photo cation polymerization initiator.
  • the light-irradiation can be performed using, for example, a light having a wavelength of 150 nm to 1,000 nm, or 200 to 700 nm, or 300 to 600 nm.
  • the photopolymerization initiator there is preferably used a photo radical polymerization initiator generating an active radical or a photo cation polymerization initiator generating a cation species by an exposure dose of 1 to 2,000 mJ/cm 2 , or 10 to 1,500 mJ/cm 2 , or 50 to 1,000 mJ/cm 2 .
  • Examples of the photo radical polymerization initiator include an imidazole compound, a diazo compound, a bisimidazole compound, an N-arylglycine compound, an organic azide compound, a titanocene compound, an aluminate compound, an organic peroxide, an N-alkoxypyridinium salt compound, and a thioxanthone compound.
  • azide compound examples include p-azidebenzaldehyde, p-azideacetophenone, p-azidebenzoic acid, p-azidebenzalacetophenone, 4,4′-diazidechalcone, 4,4′-diazidediphenyl sulfide, and 2,6-bis(4′-azidebenzal)-4-methylcyclohexanone.
  • diazo compound examples include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene borofluoride, 1-diazo-4-N,N-dimethylaminobenzene chloride, and 1-diazo-4-N,N-diethylaminobenzene borofluoride.
  • bisimidazole compound examples include 2,2′-bis(o-chlorophenyl)-4,5,4′,5′4etrakis(3,4,5-trimethoxyphenyl) 1,2′-bisimidazole and 2,2′-bis(o-chlorophenyl) 4,5,4′,5′-tetraphenyl-1,2′-bisimidazole.
  • titanocene compound examples include dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-bisphenyl, dicyclopentadienyl-titanium-bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis(2,4,6-trifluorophenyl), dicyclopentadienyl-titanium-bis(2,6-difluorophenyl), dicyclopentadienyl-titanium-bis(2,4-difluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,3,4,5,6-pentafluorophenyl), bis(methylcyclopentadienyl)-titanium-
  • photo radical polymerization initiator examples include 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3′,4,4′-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.
  • photo cation polymerization initiator examples include sulfonic acid ester, a sulfonimide compound, a disulfonyldiazomethane compound, a dialkyl-4-hydroxysulfonium salt, an arylsulfonic acid-p-nitrobenzyl ester, a silanol-aluminum complex, and ( ⁇ 6-benzene)( ⁇ 5-cyclopentadienyl) iron(II).
  • sulfonimide compound examples include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.
  • disulfonyldiazomethane compound examples include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
  • photo cation polymerization initiator examples include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one.
  • An aromatic iodonium salt compound, an aromatic sulfonium salt compound, an aromatic diazonium salt compound, an aromatic phosphonium salt compound, a triazine compound, and an iron arene complex compound can be used both as a photo radical polymerization initiator and as a photo cation polymerization initiator.
  • aromatic iodonium salt compound examples include diphenyliodoniumhexafluorophosphate, diphenyliodoniumtrifluoromethanesulfonate, diphenyliodoniumnonafluoro-n-butanesulfonate, diphenyliodoniumperfluoro-n-octanesulfonate, diphenyliodoniumcamphorsulfonate, bis(4-tert-butylphenyl)iodoniumcamphorsulfonate, and bis(4-cert-butylphenypiodoniumtrifluoromethanesulfonate.
  • aromatic sulfonium salt compound examples include triphenylsulfoniumhexafluoroantimonate, triphenylsulfoniumnonafluoro n-butanesulfonate, triphenylsulfoniumcamphorsulfonate, and triphenylsulfoniumtrifluoromethanesulfonate.
  • the photopolymerization initiators may be used individually or in combination of two or more types thereof.
  • an acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid, or an acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, bis(4-tert-butylphenyl)iodoniumtrifluoromethane sulfonate, triphenylsulfoniumtrifluoromethane sulfonate, phenyl-bis(trichloromethyl)-s-triazine, be
  • an acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid,
  • the content of the polymerization initiator (B) is, for example, 1 to 20 part(s) by mass, or 3 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound (A).
  • the content of the polymerization initiator (B) is less than this amount, the polymerization reaction is not satisfactorily progressed and the hardness and the wear resistance of the resultant underlayer film may become unsatisfactory.
  • a photo radical polymerization initiator is preferably used as the polymerization initiator.
  • a photo cation polymerization initiator is preferably used as the polymerization initiator.
  • triphenylsulfoniumtrifluoromethane sulfonate and pyridinium p-toluenesulfonic acid are preferably used as the polymerization initiator.
  • the resist underlayer film forming composition of the present invention there may be blended, besides the polymerizable compound (A) and the polymerization initiator (B), if necessary, a surfactant, a sensitizer, an amine compound, a polymer compound, an antioxidant, a thermopolymerization inhibitor, a surface modifier, a defoaming agent, and the like.
  • the formation of a pinhole, a striation, and the like can be suppressed and applicability of the underlayer film forming composition can be enhanced.
  • the surfactant include: a polyoxyethylene alkyl ether compound such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; a polyoxyethylene alkylallyl ether compound such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; a polyoxyethylene-polyoxypropylene block copolymer compound; a sorbitan fatty acid ester compound such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, and sorbitan tristearate; and a polyoxyethylene sorbitan fatty acid ester compound such as polyoxyethylene sorbitan monolaurate, polyoxy
  • the surfactant also include: a fluorinated surfactant such as EFTOP EF301, EF303, and EF352 (trade name; manufactured by Tohkem. Products Corp.), MEGAFAC F171, F173, R-08, and R-30 (trade name; manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited), AsahiGuard AG710 and Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade name; manufactured by Asahi Glass Co., Ltd.); and Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the additive amount thereof is, for example, 0.1 to 5 parts by mass, or 0.5 to 2 parts by mass, relative to 100 parts by mass of the polymerizable compound (A).
  • the sensitizer can be used for enhancing the sensitivity of the photopolymerization initiator relative to light.
  • the sensitizer include: a pyrromethene complex compound such as 2,6-diethyl-1,3,5,7,8-pentamethylpyrromethene-BF 2 complex and 1,3,5,7,8-pentamethylpyrromethene-BF 2 complex; a xanthene-based dye such as eosin, ethyleosin, erythrosine, fluorescein, and rose bengal; a ketothiazoline compound such as 1-(1-methylnaphtho[1,2-d]thiazole-2(1H)-ylidene-4-(2,3,6,7)tetrahydro-1H,5H-benzo[ij] quinolizine-9-yl)-3-butene-2-one, and 1-(3-methylbenzothiazole-2(3H)-ylidene-4-(p-dimethylaminopheny
  • Examples of the sensitizer also include 2,4-diphenyl-6-(p-dimethylaminostyryl)-1,3,5-triazine, 2,4-diphenyl-6-(([2,3,6,7]tetrahydro-1 H,5H-benzo[ij]quinolizine-9-yl)-1-ethene-2-yl)-1,3,5-triazonenanthryl-(([2,3,6,7]tetrahydro-1H,5H-benzo[ij] quinolizine-9-yl)-1-ethene-2-yl) ketone, 2,5-bis(p-dimethylaminocinnamylidene)cyclopentanone, and 5,10,15,20 tetraphenylporphyrin.
  • the additive amount thereof is, for example, 0.1 to 20 parts by mass, relative to 100 parts by mass of the polymerizable compound (A).
  • the amine compound can be used for preventing the lowering of the sensitivity of the photopolymerization initiator due to oxygen inhibition.
  • various amine compounds such as aliphatic amine compounds and aromatic amine compounds can be used.
  • the additive amount thereof is, for example, 0.1 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound (A).
  • a polymer compound can be blended in the composition.
  • the type thereof is not particularly limited and there can be used various polymer compounds having a weight average molecular weight of around 1,000 to 1,000,000.
  • the polymer include an acrylate polymer, a methacrylate polymer, a novolac polymer, a styrene polymer, a polyamide, a polyamic acid, a polyester, and a polyimide, that have a benzene ring, a naphthalene ring, or an anthracene ring.
  • the additive amount thereof is, for example, 0.1 to 50 parts by mass, relative to 100 parts by mass of the polymerizable compound (A).
  • the resist underlayer film forming composition of the present invention is preferably used in a solution state in which each component (hereinafter, called “solid content”) such as the polymerizable compound (A) and the polymerization initiator (B) is dissolved in the solvent (C).
  • the solid content is a component remaining after subtracting the solvent from all components of the resist underlayer film forming composition.
  • the solvent can be used so long as the solvent can dissolve the solid content to prepare a homogeneous solution.
  • an organic solvent used for hydrolysis of the organic silicon compound as it is preferably used as the solvent (C) of the resist underlayer film forming composition.
  • Examples of the solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethylcellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxy
  • solvents (C) may be used individually or in combination of two or more types thereof.
  • a solvent having a boiling point of 80 to 250° C., or 100 to 200° C., or 120 to 180° C. is preferably used.
  • the solvent is evaporated in a large amount during the application of the resist underlayer film forming composition to cause an increase of the viscosity of the composition, so that lowering of the applicability of the composition may be caused.
  • the boiling point of the solvent is high, it is considered that drying of the resist underlayer film forming composition after the application thereof takes much time.
  • the solvent can be used in an amount by which the concentration of the solid content of the resist underlayer film forming composition becomes, for example, 0.5 to 50% by mass, or 3 to 40% by mass, or 10 to 30% by mass.
  • the present invention includes a process of applying the resist underlayer film forming composition on a substrate to be processed to form a coating film and a process of performing light-irradiation, heat-baking, or both of them relative to the coating film to form an underlayer film, to produce a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display apparatus.
  • the present invention includes a process of applying the resist underlayer film forming composition of the present invention on a substrate to be processed to form a resist underlayer film, a process of performing heat-baking or light-irradiation relative to the resist underlayer film to cure the resist underlayer film, and a process of applying a resist composition for nanoimprint on the resist underlayer film and heat-baking the composition to form a resist for nanoimprint, so that can form a laminated structure used for a pattern forming process using nanoimprint.
  • the present invention includes a process of applying a resist underlayer film forming composition on a substrate to form a resist underlayer film, a process of performing heat-baking, light-irradiation, or both of them relative to the resist underlayer film to cure the resist underlayer film, a process of applying a resist composition for nanoimprint on the resist underlayer film and heat-baking the resist composition to form a resist for nanoimprint, and a process of performing imprint by a step and repeat method, so that can form a laminated structure used for a pattern forming process using nanoimprint.
  • the present invention further includes a process of imprinting the substrate for a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display that is coated with the resist underlayer film and the resist, a process of parting a template (mold) from the resist after imprinting to obtain a resist pattern without development, a process of etching the underlayer film according to the resist pattern, and a process of processing the substrate according to the patterned photoresist and the patterned underlayer film to produce a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display apparatus.
  • a photo-imprinting method or a thereto-imprinting method can be used for the imprinting.
  • the substrate to be processed is a substrate which has a hole having an aspect ratio represented by height/diameter of 1 or more and is used for a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display apparatus.
  • the resist underlayer film forming composition of the present invention is applied by an appropriate coating method such as spinner, coater, spray, and inkjet to form a coating film. Then, before performing light-irradiation or heat-baking relative to the coating film, if necessary, a drying process can be established. When a resist underlayer film forming composition containing a solvent is used, the drying process is preferably established.
  • the drying process is not particularly limited so long as the drying process is not by a method of heating at a high temperature. This is because, it is considered that when the resist underlayer film forming composition is heated at a high temperature (for example, a temperature of 300° C. or more), the sublimation or the like of the solid content contained in the resist underlayer film is caused, so that an apparatus is contaminated.
  • the drying process can be performed, for example, by heating the substrate on a hot plate at 50 to 100° C. for 0.1 to 10 minutes.
  • the drying process can also be performed, for example, by air-drying the substrate at room temperature (around 20° C.).
  • the method for the light-irradiation is not particularly limited to be used so long as the method is a method capable of acting on the polymerization initiator (B) to effect polymerization of the polymerizable compound (A).
  • the light-irradiation can be performed, for example, by using an ultra high pressure mercury lamp, a flash UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a DEEP-UV (deep ultraviolet) lamp, a xenon short arc lamp, a short arc metal halide lamp, a lamp for YAG laser exciting, a xenon flash lamp, and the like.
  • the light-irradiation can'be performed, for example, by using an ultra high pressure mercury lamp and by irradiating with lights having all wavelengths of around 250 nm to around 650 nm containing bright line spectra having peaks at wavelengths of 289 nm, 297 nm, 303 nm, 313 nm (j ray), 334 nm, and 365 nm (i ray) in an ultraviolet region and wavelengths of 405 nm (h ray), 436 nm (g ray), 546 nm, and 579 nm in a visible light region.
  • a cation species or an active radical is generated from the photopolymerization initiator in the resist underlayer film, and then, by these species and radical, the polymerization reaction of the polymerizable compound in the resist underlayer film is effected. Then, as a result of the polymerization reaction, the resist underlayer film is formed.
  • the thus formed resist underlayer film comes to have a low solubility in a solvent used for a resist composition for nanoimprint applied as an upper layer of the resist underlayer film, such as ethylene glycol monomethyl ether, ethylcellosolve acetate, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, methyl ethyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, methyl pyruvate, ethyl lactate, and butyl lactate. Therefore, the resist underlayer film formed from the resist underlayer film forming composition of the present invention becomes a resist underlayer film causing no intermixing with the overcoated resist for nanoimprint.
  • the conditions for heat-baking (heating) are accordingly selected from the baking temperatures of 80° C. to 300° C. and the baking times of 0.3 to 90 minutes.
  • the conditions are the baking temperature of 130° C. to 300° C. and the baking time of 0.5 to 5 minutes.
  • the resist underlayer film forming composition of the present invention can be applied to a substrate having an aspect ratio represented by height/diameter of 0.01 or more, for example, having a hole of a diameter of 60 to 100,000 nm, or having an aspect ratio represented by height/width of 0.01 or more, for example, having a step of a width of 60 to 100,000 nm.
  • the resist underlayer film forming composition of the present invention can be used for filling such a hole with the underlayer film without causing a gap (void).
  • the underlayer film forming composition of the present invention can be applied to a substrate to be processed having holes of an aspect ratio of 0.01 or more coarsely or finely (substrate having a portion in which holes exist coarsely and a portion in which holes exist finely).
  • the resist underlayer film forming composition of the present invention can be used for forming a planar resist underlayer film on the surface of such a substrate in which holes exist coarsely or finely.
  • the resist underlayer film forming composition of the present invention can also be applied to a substrate to be processed which has a hole or step having an aspect ratio of less than 0.01 and is used for the production of a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display apparatus.
  • the resist underlayer film forming composition of the present invention can also be applied to a substrate having no step or the like.
  • the film thickness of the resist underlayer film formed from the resist underlayer film forming composition of the present invention is on the surface of the substrate, for example, 1 to 10,000 nm, or 5 to 10,000 nm, or 5 to 1,000 nm.
  • a resist is formed on the substrate to be processed used for the production of a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display apparatus.
  • a laminated structure of the resist underlayer film and the resist is formed on the substrate to be processed used for the production of a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display apparatus.
  • the formation of the resist can be performed by an appropriate known method such as spinner, coater, spray, and inkjet, that is, by applying a solution of a resist composition on the resist underlayer film and by performing light-irradiation or heat-baking relative to the resultant coating.
  • the resist formed on the resist underlayer film of the present invention is not particularly limited, and as the resist, any one of an acrylate-type organic acrylic resist and an inorganic resist that are used for general purposes can be used.
  • a photocurable inorganic resist containing, as the main component, a siloxane polymer see Non-patent Document 2
  • an organic resist using polyvinyl alcohol see Non-patent Document 3
  • a resist material composition containing a fluorine additive used in photo nanoimprint lithography There is disclosed an example using a photocurable resin and forming a pattern by photo nanoimprint lithography (Patent Document 8).
  • a resist curable composition for nanoimprint lithography containing a polymerizable compound, a photopolymerization initiator, and an interface active polymerization initiator and having a limited viscosity (Patent Document 9).
  • the pattern forming process by imprint is divided into a bulk transferring method and a step and repeat method.
  • the bulk transferring method is a method including: forming a resist film on the whole surface of the substrate to be processed; and then using a template having the same size as that of the substrate, pressing the template against the substrate to transfer a pattern.
  • the step and repeat method is a method including: using a template processed into a smaller chip size, performing repeatedly the transferring per a size of the template as with the exposure treatment by photolithography; and performing finally the pattern formation on the whole surface of the substrate by imprint.
  • the substrate or the template has warp or unevenness, so that when the substrate to be processed is large or when the formation of a fine pattern is necessary, it becomes difficult to press the template homogeneously and parallel against the substrate to be processed. From described above, the step and repeat method is more preferred.
  • a pattern forming process by photo-imprint is excellent in releasing properties between the template (mold) and the resist, in alignment precision, and in productivity, causes a small amount of defect and a small amount of the change in the pattern size by thermal expansion or thermal contraction of the resist, and takes a short processing time in comparison with a pattern forming process by thermo-imprint.
  • the pattern forming process by photo-imprint is suitable for an application requiring a finer processing.
  • the pattern formation is performed by imprint through an arbitrary template.
  • the pattern formation by imprint is performed by: applying the underlayer film composition of the present invention used as an underlayer of the resist for nanoimprint on a substrate to be processed; applying a resist composition for imprint on the underlayer film as an upper layer thereof; and pressing a light transmittable template against the resist composition and performing heat-baking, light-irradiation, or both of them.
  • the pattern forming process by photo-imprint at least one of the template and the substrate uses a material transmitting an irradiated light.
  • the template has a same-sized pattern to be imprinted.
  • the template can form a pattern according to the desired processing precision, for example, by photolithography, an electron beam drawing method, or the like, in the present invention, the template pattern forming method is not particularly limited.
  • the template applicable to the present invention is not particularly limited, the template may be a template having a predetermined strength and durability.
  • Specific examples of the template include a glass, a quartz, an acrylic resin, a light-transparent resin such as a polycarbonate resin, a transparent metal evaporated film, a flexible film such as polydimethylsiloxane, a photo-cured film, and a metal film. Particularly, in terms of transparency and quality, a patterned quartz is preferred.
  • the non-light transmitting-type template (mold) material is not particularly limited so long as it is a material having a predetermined strength and shape retentivity.
  • a material having a predetermined strength and shape retentivity include a ceramic material, an evaporated film, a magnetic film, a reflecting film, a metal substrate such as Ni, Cu, Cr, and Fe, and a substrate such as SiC, silicone, nitride silicone, polysilicone, oxide silicone, and amorphous silicone, to which the examples are not particularly limited.
  • the shape may be any one of a plate-shape mold and a roll-shape mold. The roll-shape mold is applied particularly when continuous productivity of transferring is necessary.
  • the releasing property between the mold and a cured product of the resist for photo nanoimprint lithography is important, so that there is performed an attempt to solve an adhesion problem by using a mold or surface treatment of a mold, specifically, by using a hydrogenated silsesqui oxane or a fluorinated ethylene propylene copolymer mold.
  • a template that has been subjected to releasing treatment by a silane coupling agent such as a silicone-based or fluorine-based silane coupling agent for enhancing the releasing property between a cured product of a resist for photo nanoimprint lithography and the template.
  • a silane coupling agent such as a silicone-based or fluorine-based silane coupling agent for enhancing the releasing property between a cured product of a resist for photo nanoimprint lithography and the template.
  • a commercially available mold release agent such as tridecafluoro 1,1,2,2-tetrahydrooctyldimethylsilane and Novec EGC-1720 can also be preferably used, to which the examples are not particularly limited.
  • the removal of the resist underlayer film of the present invention and the processing of a semiconductor substrate are performed.
  • the removal of the resist underlayer film can be performed by dry etching using a gas such as tetrafluoromethane, perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, and chlorine trifluoride.
  • the first method using the resist underlayer film formed from the resist underlayer film forming composition of the present invention as a hardmask includes a process of applying the resist underlayer film forming composition of the present invention on a semiconductor substrate and performing heat-baking, light-irradiation, or both of them to form a resist underlayer film, a process of applying a resist composition on the resist underlayer film to form a resist film, a process of imprinting the resist film, a process of parting the template from the resist after imprinting to obtain a resist pattern, a process of etching the resist underlayer film according to the resist pattern, and a process of processing the semiconductor substrate according to the patterned resist and underlayer film, to produce a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display apparatus.
  • the resist underlayer film has a large etching rate same as that of the resist or more under a CF 4 gas condition used during etching of the resist, so that the resist underlayer film of the present invention can be removed by etchingaccording to the resist pattern, and using the resist and the resist underlayer film as protecting films, the semiconductor substrate can be processed.
  • the second method using the resist underlayer film formed from the resist underlayer film forming composition of the present invention as a hardmask includes a process of forming an organic film (a gap filling material or a spin-on carbon material) on a substrate to be processed by an applying-type organic film forming composition, a process of applying the resist underlayer film forming composition of the present invention on the organic film and performing heat-baking, light-irradiation, or both of them to form a resist underlayer film, a process of applying a resist composition on the resist underlayer film to form a resist film, a process of imprinting the resist film, a process of parting the template from the resist after imprinting to obtain a resist pattern, a process of etching the resist underlayer film according to the resist pattern, and a process of processing the semiconductor substrate according to the patterned resist and underlayer film, to produce a semiconductor, a light-emitting diode, a solid-state image pickup device, a recording apparatus, or a display apparatus.
  • the resist underlayer film has a large etching rate same as that of the resist or more under a CF 4 gas condition used during etching of the resist, so that the underlayer film of the present invention can be removed by etchingaccording to the resist pattern and the resist pattern can be transferred to the resist underlayer film of the present invention.
  • the resist underlayer film has a far smaller etching rate than that of the organic film (having the same etching characteristic as that of the resist) under an O 2 (oxygen) gas condition used during etching of the organic film that is formed under the present invention.
  • the resist pattern transferred to the resist underlayer film of the present invention can further be transferred to the organic film, and using the organic film as a protecting film, the substrate to be processed can be processed.
  • the resist underlayer film forming composition of the present invention can be formed for the purpose of planarization of the substrate.
  • the molar ratio of 3-glycidoxypropyltrimethoxysilane and monomethyltrimethoxysilane was 50%:50%.
  • the obtained polysiloxane resin had a weight average molecular weight of 1,300 and a number average molecular weight of 1,000.
  • the obtained polysiloxane resin had a weight average molecular weight of 900 and a number average molecular weight of 800.
  • the obtained polysiloxane resin had a weight average molecular weight of 1,200 and a number average molecular weight of 1,000.
  • Example 1 to Example 3 Each of the solutions of the resist underlayer film forming compositions obtained in Example 1 to Example 3 was applied on a semiconductor substrate (silicon wafer substrate) by a spinner to form a coating film.
  • the coating film was irradiated with all wavelengths from a lamp enhanced at 380 nm (manufactured by Ore Manufacturing Co., Ltd.; metal halide lamp) (exposure dose: 200 ml/cm 2 ). Then, for removing the solvent and drying the coating film, the coating film was heated on a hot plate at 130° C. for 1 minute to form a resist underlayer film (film thickness: 179 nm).
  • the resist underlayer film was immersed in ethyl lactate and propylene glycol monomethyl ether both of which are solvents used for a resist for imprint, and butyl acrylate contained in the resist for imprint used in the present invention. It was confirmed that the resist underlayer films obtained from the resist underlayer film forming compositions obtained in Example 1 to Example 3 were insoluble in these solvents.
  • the resist underlayer film was formed on a silicon wafer substrate from each of the solutions of the resist underlayer film forming compositions obtained in Example 1 to Example 3 in a film thickness described in Table 1. Then, using a spectro-ellipsometer, the refractive index (n value) and the attenuation coefficient (k value) at a wavelength of 633 nm of the underlayer film were measured and these measured values are shown in Table 1.
  • Examples 1 to 3 mean the result of the evaluation of the resist underlayer films obtained from the resist underlayer film forming compositions of Examples 1 to 3.
  • the resist underlayer film was formed on a silicon wafer substrate from each of the solutions of the resist underlayer film forming compositions obtained in Example 1 to Example 3 in a film thickness described in Table 2. Then, using an RIE system ES401 (manufactured by Nippon Scientific Co., Ltd.) and under a condition of using O 2 and CF 4 as a dry etching gas, the dry etching rate (loss amount of film thickness per unit time) of the underlayer film was measured. The obtained result is shown as selectivity of the dry etching rate.
  • the ratio of the dry etching rate of the underlayer film when the dry etching rate of a photoresist for KrF laser lithography (manufactured by Shin-Etsu Chemical Co., Ltd.; trade name: SEPR 430) under the same conditions is assumed to be 1.00, is the selection ratio of the dry etching rate.
  • Examples 1 to 3 mean the result of the evaluation of the resist underlayer films obtained from the resist underlayer film forming compositions of Examples 1 to 3.
  • a step and repeat method by a photonanoimprint apparatus manufactured by Molecular Imprints, Inc.; trade name: IMPRIO
  • IMPRIO photonanoimprint apparatus
  • the substrate to be processed on which liquid drops of the resist material were applied was placed parallel to a quartz template in which 80 nm lines were carved with the same interval so that the distance between the substrate and the template was homogeneous. At a rate of from 0.4 mm/sec to 0.003 mm/sec, the distance was reduced to lower the position of the template toward the substrate to be processed.
  • a load was applied to the template with a pressing pressure of 1.0 to 1.5 N to adhere completely a convexo-concave portion of the template to the substrate.
  • the substrate with the template was subjected to light-irradiation (for 20 seconds) to photo-cure the resist for imprint. The position of the template was elevated to complete the forming process of the resist pattern by photonanoimprint.
  • Examples 1 to 3 mean the results of evaluating the photoimprint using the resist underlayer films obtained from the resist underlayer film forming compositions of Examples 1 to 3. Comparative Example 1 is a result of evaluating the photoimprint without using the resist underlayer film forming composition.
  • the evaluation result 1 indicates rectangularity of the resist pattern.
  • (advantageous) indicates a result in which an angle formed by a resist side wall and the surface of the resist underlayer film was 80 to 100°, and (failure) indicates a result in which the above angle was less than 80° or 101° or more.
  • the evaluation result 2 indicates curing properties of the resist that was confirmed by the above-described dissolution test in a resist solvent.
  • (advantageous) indicates a result in which when the substrate was immersed in ethyl lactate and propylene glycol monoethyl ether, the difference in the film thickness of the resist between before and after the immersion was 1 nm or less.
  • (failure) indicates a result in which the difference in the film thickness of the resist between before and after the immersion was 1 nm or more and the resist pattern shape disappeared in the solvent after the immersion.
  • the evaluation result 3 indicates fluidity (film-remaining property) of the resist on the resist underlayer film.
  • (advantageous) indicates a result in which the resist spread homogeneously into the size of the template, and further, film-remaining of the resist was homogeneous.
  • (pass) indicates a result in which although film-remaining of the resist had unevenness, the resist spread homogeneously into the size of the template.
  • (failure) indicates a result in which the resist did not spread homogeneously into the size of the template.
  • the evaluation 4 indicates peeling properties of the resist from the template. (advantageous) indicates a result in which the resist did not adhere to the template and the pattern forming succeeded, and (failure) indicates a result in which a part of the resist adhered to the template and the pattern on the substrate was peeled.
  • the resist underlayer films obtained from the compositions for forming the resist underlayer film for nanoimprint of Examples 1 to 3 did not adhere to the template and a pattern of 80 nm line (ratio of line:space was 1:1) could be homogeneously produced in an area of 2.5 ⁇ 2.5 cm 2 .
  • the resist underlayer films obtained from the compositions for forming the resist underlayer film for nanoimprint of Examples 2 and 3 were used, the resist liquid drop could more easily spread before the light-irradiation by the imprint process and the resist underlayer films were excellent in resist fluidity (film-remaining property).
  • the interaction of the resist underlayer film with the resist was improved, so that it is considered that the mold-releasing property of the resist from the template became the best.
  • the composition for forming the resist underlayer film for nanoimprint of Example 2 is a composition for forming the resist underlayer film for nanoimprint by which the contact angle with water that was 67° before the light-irradiation after the film-formation of the resist underlayer film was reduced to 63° after the light-irradiation (with a lamp enhanced at 380 nm (manufactured by Ore Manufacturing Co., Ltd.; metal halide lamp), exposure dose: 2 J/cm 2 ).
  • the composition for forming the resist underlayer film for nanoimprint of Example 3 is a composition for forming the resist underlayer film for nanoimprint by which the contact angle measured by a contact angle meter (DM; manufactured by Kyowa Interface Science Co., Ltd.) with water that was 71° before the light-irradiation after the film-formation of the resist underlayer film was reduced to 58° after the light-irradiation (with a lamp enhanced at 380 nm (manufactured by Ore Manufacturing Co., Ltd.; metal halide lamp), exposure dose: 2 J/cm 2 ).
  • DM contact angle meter

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