Classifications

• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
  • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
  • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/148—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • 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
• • 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
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • 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
  • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • 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
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
  • H01B19/02—Drying; Impregnating
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
  • H01B19/04—Treating the surfaces, e.g. applying coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
• • 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
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

• the present invention relates to a coating composition for producing an interlayer insulating film, an interlayer insulating film, a semiconductor element, and a method for producing an interlayer insulating film.
• Nanoimprint technology is attracting attention as a technology that can form nanoscale fine patterns with high resolution, such as semiconductor integrated circuits, microelectromechanical systems (MEMS), sensor elements, magnetic recording media, optical devices, and optical films for flat panel displays. It is expected to be applied to manufacturing. Recently, it has been attracting attention for reasons other than resolution, and since it is possible to directly pattern complex three-dimensional shapes without photoresist, etching, and vapor deposition processes, there is a possibility that device manufacturing can be greatly simplified and manufacturing costs can be reduced. Therefore, application to materials with various functions is being considered.
• MEMS microelectromechanical systems
• Non-Patent Document 1 a poly (methylsilsesquioxane) -based SOG material is directly imprinted and then vitrified to produce an insulating film having a pattern.
• Patent Document 1 room temperature imprint using organosilica SOG or HSQ (hydrogenated silsesquioxane polymer) is adopted.
• Patent Document 2 a fine pattern having a high elastic modulus is formed by optical nanoimprint using a composition composed of a mixture of silica nanoparticles and a photocurable monomer.
• Non-Patent Document 1 employs pattern formation by thermal imprinting using a high-viscosity SOG material, high-temperature (200 ° C.) and high-pressure (3.4 MPa) imprinting under vacuum is used. It is extremely difficult to improve the throughput because a print pressing step is required and it takes a long time to raise and lower the temperature.
• Patent Document 1 since the technique described in Patent Document 1 requires a pressing step of high pressure (25 kgf / cm 2 ) and long time (10 minutes), the effect of improving the throughput is limited. In addition, it cannot be applied to a process with a long cycle time because it needs to be pressed within 10 minutes due to the problem of stability after application.
• silica nanoparticles have a large particle size component of several hundred nm and secondary particles due to aggregation, they are not uniformly filled in the fine pattern of the mold, and the application is replica molding. Limited to use.
• a coating composition for producing an interlayer insulating film capable of producing a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity at high throughput, and production of an interlayer insulating film.
• the development of a method is required.
• An object of the present invention is to provide a coating composition for producing an interlayer insulating film, which has a high Young's modulus and a low relative permittivity and can produce a patterned interlayer insulating film with high throughput. ..
• Another object of the present invention is to provide a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity.
• Another object of the present invention is to provide a semiconductor device having a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity.
• Another object of the present invention is to provide a method for producing an interlayer insulating film capable of producing a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity at a high throughput. ..
• the present inventors have conducted diligent studies in order to solve the above problems. As a result, by using a coating composition for producing an interlayer insulating film containing a polymerizable compound having a specific group, a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity can be obtained. We have found that it can be manufactured with throughput, and have completed the present invention.
• the present invention is a polymerizable silicon compound having two or more polymerizable groups, and at least one of the two or more polymerizable groups is a polymerizable group Q represented by the following formula (1).
• a coating composition for producing an interlayer insulating film which contains a sex compound (A) and a photopolymerization initiator (B). * -O-RY ... (1)
• R represents an unsubstituted or substituted alkylene group having 1 to 12 carbon atoms which may contain a single bond or a heteroatom.
• Y represents a polymerizable group.
• the present invention is an interlayer insulating film obtained by curing the coating composition for producing an interlayer insulating film.
• the present invention is a semiconductor device having the interlayer insulating film.
• the present invention A step A of applying the coating composition for manufacturing an interlayer insulating film onto a base material, a step B of pressing an imprint mold having an uneven pattern formed on the surface of the coating composition for manufacturing an interlayer insulating film, and the above.
• This is a method for producing an interlayer insulating film having a step E of forming.
• a coating composition for producing an interlayer insulating film capable of producing a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity at a high throughput. ..
• the present invention can provide a semiconductor device having a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity.
• an interlayer insulating film capable of producing a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity at a high throughput. ..
• the coating composition for producing an interlayer insulating film is a polymerizable silicon compound having two or more polymerizable groups, and the above two or more. It contains a polymerizable compound (A) in which at least one of the polymerizable groups is a polymerizable group Q represented by the following formula (1), and a photopolymerization initiator (B). * -O-RY ... (1) (In the above formula (1) * Represents a bond to a silicon atom R represents an unsubstituted or substituted alkylene group having 1 to 12 carbon atoms which may contain a single bond or a heteroatom. Y represents a polymerizable group. )
• the cured film obtained by curing the coating composition is different from the case of the composition composed of a mixture of silica nanoparticles and a photocurable monomer. Excellent uniformity. Further, since the polymerizable group Q has a Si—OR bonding portion, it is vitrified by heating the base material after pattern formation, so that the interlayer insulation has a low dielectric constant and a high Young's modulus. A film can be obtained. Further, since the polymerizable group Q can decompose the bonded portion of Si—OR by treatment with an acid, alkali or the like to cut the crosslinked structure, the photocured product is intentionally dissolved and washed. It is possible to do.
• the Si—OR bonding portion of the polymerizable group Q also has thermal decomposability, it is decomposed by heating the substrate after pattern formation, and pores are formed in the interlayer insulating film. It is possible to obtain an interlayer insulating film having a low dielectric constant. Further, since the coating composition has a low viscosity and is photocurable, it can be coated on a substrate at normal temperature and pressure without using a vacuum process such as chemical vapor deposition (CVD) to be photocurable. ..
• the interlayer insulating film can be formed with a higher throughput than before. Therefore, according to the coating composition, a patterned interlayer insulating film having excellent uniformity, a high Young's modulus and a low relative permittivity can be produced with high throughput. Further, since the coating composition is cured at a low shrinkage rate, the interlayer insulating film obtained by curing the coating composition is excellent in crack resistance and flatness. Further, the coating composition can be suitably used particularly for pattern formation of 100 nm or less.
• the polymerizable compound (A) is liquid at room temperature (for example, 25 ° C.) and has two or more polymerizable groups.
• the polymerizable group represents a functional group capable of a polymerization reaction, and specific examples thereof include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable.
• Specific examples of the radically polymerizable group include vinyl group, (meth) acryloyl group, (meth) acryloyloxy group, allyl group, allyloxy group, isopropenyl group, styryl group, vinyloxy group, vinyloxycarbonyl group and vinylcarbonyl.
• Examples thereof include a group, an N-vinylamino group, a methacrylicamide group, an acrylamide group, a maleimide group and the like, and from the viewpoint of photocurability, a (meth) acryloyl group, an acrylamide group, and particularly preferably an acryloyl group are used.
• the group having the polymerizable group may be a group having the polymerizable group.
• a (meth) acryloyl group means an acryloyl group or a methacryloyl group.
• the polymerizable compound (A) has two or more polymerizable groups, and at least one of the groups having the polymerizable group is the polymerizable group Q represented by the formula (1).
• the polymerizable compound (A) has at least one group Q, but when it has three or more polymerizable groups Q, it has excellent photocurability and a cured product having a high elastic modulus can be obtained.
• the polymerizable compound (A) having three or more polymerizable groups Q not only can be cured in low light and in a short time, but also the pattern collapses or breaks in the process of releasing the mold during optical imprinting. This is preferable because it can prevent the above and further improves the detergency and the insulating property.
• R is preferably a single bond or an alkylene group having 1 to 5 carbon atoms.
• Y is a vinyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, an allyl group, an allyloxy group, an isopropenyl group, a styryl group, a vinyloxy group, or a vinyl group.
• a loxycarbonyl group, a vinylcarbonyl group, an N-vinylamino group, an acrylamide group, a methacrylicamide group or a maleimide group are preferable.
• Examples of the polymerizable group Q include those having the following structure.
• the polymerizable compound (A) may be linear or branched.
• the following is an example of the polymerizable compound (A) having a structure having 2 to 6 silicon atoms in the molecule and 1 to 4 oxygen atoms directly bonded to the silicon atoms.
• the number of each is not limited to the number exemplified.
• the number of silicon atoms contained in the molecule of the polymerizable silicon compound (A) is, for example, 2 to 5000, and the number of oxygen atoms directly bonded to the silicon atom can be selected in the range of 1 to 4.
• the polymerizable compound (A) preferably has a structure having 5 or more silicon atoms. This is because the presence of five or more silicon atomic weights improves the crack resistance when the interlayer insulating film is manufactured, and the heat resistance, insulating property, and Young's modulus of the formed insulating film.
• the amount of silicon atoms in the polymerizable compound (A) is preferably 10% by weight or more. When the amount of silicon atoms is 10% by weight or more, the outgas component generated by desorption from the sample surface is suppressed to a small extent, and heat resistance and crack resistance are improved, which is preferable.
• the amount of silicon atoms in the polymerizable compound (A) is preferably 15% by weight or more, more preferably 20% by weight or more.
• the upper limit of the amount of silicon atoms in the polymerizable compound (A) is not particularly limited, but is, for example, 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, still more preferably. It is 60% by weight or less.
• the polymerizable compound (A) is preferably obtained by condensing a monomer represented by the following general formula (A1) and / or a monomer represented by the following general formula (A2) into a silicone oligomer to obtain a silicone oligomer. It is produced by reacting a compound represented by the following general formula (A3).
• R 1 , R 2 , R 3 and R 4 are independently alkyl groups having 1 to 6 carbon atoms, respectively.
• R is the same as R in the above formula (1)
• Y is the same as Y in the above formula (1).
• a silicone oligomer having one or more groups represented by Si-O-RY Since the silicone oligomer has a group represented by Si-O-RY, the composition can have a low viscosity and good UV curability. Further, when the composition containing the silicone oligomer is baked at a high temperature to form an interlayer insulating film, the group represented by Si-ORY is decomposed to form a siloxane bond to form a strong film. It can also be.
• silicone oligomer of the monomer represented by the formula (A1) and / or the monomer represented by the formula (A2) for example, silicone resin KC-89S, silicone resin KR-500, and silicone resin.
• silicone resin KC-89S silicone resin KR-500
• the lower limit of the content of the polymerizable compound (A) in the coating composition is preferably 50% by weight or more, 60% by weight or more, 70% by weight or more or 80% by weight or more of the non-volatile content of the coating composition. ..
• the upper limit of the content of the polymerizable compound (A) in the coating composition is not particularly limited, and is, for example, 99.9% by weight or less, 99% by weight or less, or 95% by weight or less of the non-volatile content of the coating composition. be.
• the weight average molecular weight of the polymerizable compound (A) is preferably in the range of 500 or more, more preferably 1000 or more, preferably 100,000 or less, and more preferably 10,000 or less.
• the weight average molecular weight is 500 or more, the crack resistance in producing the interlayer insulating film and the heat resistance, insulating property, and Young's modulus of the formed insulating film are improved, which is preferable.
• the weight average molecular weight is 100,000 or less, the viscosity is kept low at room temperature, and the filling property into the mold at the time of optical imprinting is excellent, which is preferable.
• the weight average molecular weight is measured by the method described in Examples.
• the synthesis of the polymerizable compound (A) is not particularly limited, and a known and commonly used method can be used. For example, a method of synthesizing a compound having a polymerizable unsaturated group and a hydroxyl group by a dehydroxylation reaction with chlorosilane, a method of synthesizing by transesterification with an alkoxysilane, and the like can be mentioned.
• photopolymerization initiator (B) examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 1- [4- (2- (2-). Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- ⁇ 4- [4- [4- [4-] (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propane, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (
• the photopolymerization initiator (B) is available as a commercial product, and is OMNIRAD (registered trademark) 651, 184, 2959, 907, 369, 379, 819, 127, ESACURE (registered trademark). ) KIP150, TZT, KTO46, 1001M, KB1, KS300, KL200, TPO, ITX, EDB (above, manufactured by IGM Resins), Irgacure (registered trademark) OXE01, 02, DAROCUR (registered) Trademarks) 1173, MBF, TPO (above, manufactured by BASF Japan Ltd.) and the like can be mentioned.
• OMNIRAD registered trademark
• the content of the photopolymerization initiator (B) in the coating composition is preferably 100 parts by weight in total of the polymerizable compound (A) and the polymerizable compound (described later) other than the polymerizable compound (A). Is in the range of 0.5 parts by weight or more, more preferably 1 part by weight or more, preferably 20 parts by weight or less, and more preferably 10 parts by weight or less.
• the content of the photopolymerization initiator (B) in the coating composition is 0.5 parts by weight or more with respect to 100 parts by weight of the polymerizable compound (A) and the polymerizable compound other than the polymerizable compound (A). If so, the curability is enhanced and the pattern forming property is excellent.
• the coating composition may contain other formulations as long as the effects of the present invention are not impaired.
• Other formulations include a solvent, a mold release agent, a pore forming agent, a polymerizable monomer other than the polymerizable compound (A), an organic pigment, an inorganic pigment, an extender pigment, an organic filler, an inorganic filler, and a photosensitizer. Examples include sensitizers, ultraviolet absorbers, antioxidants, adhesion aids and the like.
• the solvent can improve the film thickness and surface smoothness by blending the solvent.
• the solvent include aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; aromatics such as toluene, xylene, ethylbenzene and anisole.
• Hydrocarbons alcohols such as methanol, ethanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol; ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol Esters such as monomethyl ether acetate and propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alkyl ethers; ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; ⁇ -butyrolactone And other lactones; N-methylpyrrolidone, dimethylformamide, dimethylacetamide can be used alone or in combination of two or more.
• the content of the solvent can be such that the content of components other than the solvent in the coating composition is preferably in the range of 0.1% by weight or more and less than 100% by weight. ..
• the release agent When the coating composition is difficult to release from the mold during optical imprinting, the release agent reduces the force required for peeling the mold by blending the release agent to form a pattern. It can prevent collapse, deformation and damage.
• the release agent preferably has a function of segregating at the interface with the mold in the coating composition and promoting the release from the mold. Specific examples thereof include compounds having both a functional group having a high affinity for the surface of the mold and a hydrophobic functional group in one molecule.
• Functional groups having a high affinity for the surface of the mold include hydroxyl groups, ether groups, amide groups, imide groups, ureido groups, urethane groups, cyano groups, sulfonamide groups, lactone groups, lactam groups, cyclocarbonate groups, and phosphate esters.
• examples thereof include, for example, when the mold is made of quartz, a hydroxyl group or a polyalkylene glycol group in which the hydroxyl group is etherified is preferable, and when the mold is made of a metal such as nickel, a phosphoric acid ester group or the like is preferable. ..
• the hydrophobic functional group include a functional group selected from a hydrocarbon group, a fluorine-containing group and the like.
• release agent examples include polyoxyalkylene alkyl ether-based surfactants, polyoxyalkylene fatty acid ester-based surfactants, sorbitan fatty acid ester-based surfactants, polyoxyalkylene alkylamine-based surfactants, and fluorine-based surfactants. Examples thereof include activators and acrylic polymerization surfactants.
• the release agent is available as a commercially available product.
• the content of the release agent in the coating composition is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less. The range. When the content of the release agent in the coating composition is 0.1% by weight or more, the releasability is enhanced, which is preferable.
• the pore-forming agent is not particularly limited as long as it can form an interlayer insulating film having a desired pore amount, pore diameter, etc. and can be mixed with the coating composition, but is not particularly limited.
• Surfactants having a glycol structure are preferable from the viewpoint of pore-forming property, and among them, pluronic surfactants (triblock copolymers of polyethylene oxide and polypropylene oxide) and tetronic surfactants (ethylenediamine and propylene) are preferable.
• a tetrafunctional block copolymer induced by the continuous addition of oxide and ethylene oxide) is more preferable from the viewpoint of solubility in the coating composition.
• the molecular weight of the surfactant having a polyalkylene glycol structure used in the pore-forming agent is preferably in the range of 200 or more, more preferably 500 or more, preferably 20,000 or less, and more preferably 10,000 or less.
• the pore-forming agent is available as a commercially available product, for example, Epan 410, 420, 450, 485, 680, 710, 720, 740, 750, 785, U.
• the coating composition contains the pore-forming agent, pores can be further formed in the interlayer insulating film, so that the relative permittivity of the interlayer insulating film is lowered, and an interlayer insulating film having further excellent insulating properties can be obtained. It is preferable because it can be formed.
• the content of the pore-forming agent in the coating composition can be appropriately selected according to the amount of pores formed in the interlayer insulating film to be obtained, and preferably the non-volatile content of the coating composition is 0. In the range of 1% by weight or more, more preferably 0.5% by weight or more of the non-volatile content of the coating composition, preferably 20% by weight or less, more preferably 10% by weight or less of the non-volatile content of the coating composition. be.
• the content of the pore-forming agent in the coating composition is 0.1% by weight or more, an interlayer insulating film having a lower relative permittivity and a higher insulating property can be produced, which is preferable. If it is% by weight or less, it is preferable because it has excellent crack resistance.
• Examples of the polymerizable monomer other than the polymerizable compound (A) include a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer.
• the monofunctional polymerizable monomer is a compound having one polymerizable group.
• the polymerizable group represents a functional group capable of a polymerization reaction, and specific examples thereof include a radical polymerizable group and a cationically polymerizable group.
• the polymerizable group of the monofunctional polymerizable monomer is preferably a group that reacts with the polymerizable group of the polymerizable compound (A), for example, the polymerizable group of the polymerizable compound (A).
• A the polymerizable group of the polymerizable compound (A).
• the polymerizable group of the monofunctional polymerizable monomer is also a (meth) acryloyl group.
• the monofunctional polymerizable monomer examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth).
• the silicon-containing monomer is a silicon-containing monomer. This is because since it contains silicon, the dry etching resistance of the curable composition containing the monofunctional polymerizable monomer is improved.
• the silicon-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriacetoxysilane, and 2-trimethoxysilylethyl vinyl ether.
• (meth) acrylate means acrylate or methacrylate.
• the content of the monofunctional polymerizable monomer in the coating composition is preferably 30% by weight or less of the non-volatile content of the coating composition, more preferably 10% by weight or less of the non-volatile content of the coating composition. The range.
• polyfunctional polymerizable monomer examples include 1,2-ethanediol di (meth) acrylate, 1,2-propanediol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate.
• 1,6-hexanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylpropandi (meth) acrylate, tri Methylolpropan tri (meth) acrylate, tris (2- (meth) acryloyloxy) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di (trimethylolpropane) tetra (meth) acrylate, di (Pentaerythritol) Penta (meth) acrylate, di (pentaerythritol) hexa (meth) acrylate, tricyclodecaned
• the content of the polyfunctional polymerizable monomer in the coating composition is preferably 30% by weight or less of the non-volatile content of the coating composition, more preferably 10% by weight or less of the non-volatile content of the coating composition. The range.
• the coating composition preferably has a silicon atom content of 10% by weight or more in the non-volatile content.
• the amount of silicon atoms in the non-volatile content is 10% by weight or more, the outgas component generated by desorption from the sample surface is suppressed to a small extent, and heat resistance and crack resistance are improved, which is preferable.
• the amount of silicon atoms in the non-volatile content is preferably 15% by weight or more, more preferably 20% by weight or more.
• the total content of the polymerizable compound (A) and the polymerizable monomers other than the polymerizable compound (A) in the non-volatile content of the coating composition is preferably 50% by weight or more. This is because the number of three-dimensional cross-linking points is increased, so that the pattern formation property at the time of imprinting is excellent.
• the interlayer insulating film of the present embodiment is obtained by curing the coating composition.
• the interlayer insulating film of the present embodiment has a high Young's modulus and a low relative permittivity.
• the interlayer insulating film may be a patterned one. Further, the pattern formation may be performed by nanoimprint.
• the interlayer insulating film includes a step A of applying the coating composition onto a substrate, and a step B of pressing an imprint mold having an uneven pattern formed on the surface of the coating composition for producing an interlayer insulating film.
• the step C of photocuring the coating composition for manufacturing an interlayer insulating film, the step D of releasing the mold for imprint, and the step D of baking the coating composition for manufacturing an interlayer insulating film at 200 ° C. or higher are used to bake the interlayer insulating film. It can be produced by the method for producing an interlayer insulating film having the step E of forming the above. According to the method for producing an interlayer insulating film, a patterned interlayer insulating film having a high Young's modulus and a low relative permittivity can be manufactured with high throughput.
• the method of applying the coating composition onto the substrate in the step A is not particularly limited, and is a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, a doctor blade method, and a curtain.
• Various methods such as a coating method, a slit coating method, a screen printing method, and an inkjet method may be used.
• the spin coating method is preferable from the viewpoints of film thickness adjustment, surface smoothness, in-plane film thickness uniformity, and throughput.
• the base material can be selected according to various uses, for example, quartz, sapphire, glass, plastic, ceramic material, vapor-deposited film (CVD, PVD, sputter), magnetic film, reflective film, Ni, Cu, Cr, Fe. , Metal substrate such as stainless steel, paper, SOG (Spin On Glass), SOC (Spin On Carbon), polyester film, polycarbonate film, polymer substrate such as polyimide film, TFT array substrate, PDP electrode plate, ITO Examples thereof include a conductive base material such as metal, an insulating base material, a semiconductor manufacturing substrate such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon.
• the shape of the base material is not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet shape, or a three-dimensional shape having curvature on the entire surface or a part thereof. Further, there are no restrictions on the hardness, thickness, etc. of the base material.
• the imprint mold on which the uneven pattern is formed in advance is pressed against the surface of the coating composition on the base material.
• the imprint mold As the material of the imprint mold, as a material that transmits light, a silicone material such as quartz, ultraviolet transmissive glass, sapphire, diamond, polydimethylsiloxane, fluororesin, cycloolefin resin, and other resin materials that transmit light, etc. Can be mentioned. Further, as long as the base material used is a material that transmits light, the imprint mold may be a material that does not transmit light. Examples of the material that does not transmit light include metal, SiC, mica, and the like. Among these, a quartz mold is particularly preferable because it transmits ultraviolet rays well, has high hardness, and has high surface flatness, plate thickness uniformity, and parallelism.
• the imprint mold can be selected from any shape such as a flat shape, a belt shape, a roll shape, and a roll belt shape.
• a mold that has been subjected to a mold release treatment in order to improve the mold releasability between the coating composition and the mold surface may be used.
• the mold release treatment include treatment with a silicone-based or fluorine-based silane coupling agent.
• the method for producing the interlayer insulating film is such that the coating composition on the substrate is used before the step B in order to remove the solvent from the coating composition.
• the temperature of the prebaking can be appropriately determined, and is, for example, 50 ° C. or higher, preferably 70 ° C. or higher, 150 ° C. or lower, preferably 120 ° C. or lower.
• the method of curing the coating composition is a method of irradiating light from the mold side when the mold is a material that transmits light, and a method of irradiating light from the base material side when the base material is a material that transmits light.
• the light used for light irradiation may be light that the photopolymerization initiator (B) reacts with, and in particular, 450 nm because the photopolymerization initiator (B) easily reacts and can be cured at a lower temperature.
• Light having the following wavelengths active energy rays such as ultraviolet rays, X-rays, and ⁇ -rays
• the coating composition may be heated to a temperature at which sufficient fluidity can be obtained at the time of light irradiation.
• the temperature at the time of heating is preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
• the mold is released to obtain a coating composition in which the uneven pattern transferred from the uneven pattern of the mold is formed.
• the step D is performed after the temperature of the coating composition has dropped to around room temperature (25 ° C.).
• the polymerizable compound (A) contained in the coating composition has the group Q. Since the group Q is a hydrolyzable group, the mold can be washed well by performing a hydrolyzing treatment after curing. Examples of the hydrolyzable cleaning liquid used for cleaning the mold include acids, alkalis, hot water and the like.
• the acid cleaning solution examples include sulfuric acid, hydrochloric acid, nitrate, carbonic acid, acetic acid, phosphoric acid, royal water, dilute hydrofluoric acid, persulfated water, and excess water of hydrochloric acid.
• examples thereof include not only inorganic alkalis such as various silicates, phosphates and carbonates, but also organic alkalis such as tetramethylammonium hydrochloride, aqueous ammonia, aqueous hydrogen ammonia, and excess ammonia. Since the alkaline cleaning solution may dissolve SiO 2 , an acid cleaning solution is preferable when the mold is glass or quartz, and sulfuric acid hydrogen peroxide is particularly preferable.
• the rectangularity of the mold may be impaired by the dissolution action of SiO 2 in the alkaline cleaning liquid. Therefore, the mold can be cleaned without damaging the fine pattern by using the acid cleaning liquid.
• the cleaning method is not particularly limited, and examples thereof include spraying, showering, dipping, warming dipping, ultrasonic dipping, spinning method, bubbling, rocking method, brushing, steam, polishing, and the like.
• the spin method is particularly preferable for preventing reattachment.
• the temperature of the bake can be appropriately determined, for example, 200 ° C. or higher, preferably 250 ° C. or higher, 1000 ° C. or lower, preferably 900 ° C. or lower.
• the bake temperature can be set to 200 ° C. or higher, an interlayer insulating film having a high Young's modulus can be obtained.
• the weight average molecular weight of the polymerizable compound was measured by the following method. Measuring device: "HLC-8320 GPC” manufactured by Tosoh Corporation Column: 2 columns of “Shodex LF604" manufactured by Shoko Science Co., Ltd. Column temperature: 40 ° C.
• Detector RI (Differential Refractometer) Developing solvent: Toluene (Synthesis Examples 1 and 4), tetrahydrofuran (Synthesis Examples 2 and 3) Flow velocity: 0.5 mL / min Sample: A solution diluted to 0.5% by mass in terms of resin solid content using a developing solvent and filtered through a microfilter Injection volume: 20 ⁇ L Standard sample: The following monodisperse polystyrene Tosoh Co., Ltd. "A-500" Tosoh Corporation "A-5000" Tosoh Corporation "F-4" Tosoh Corporation "F-40" Tosoh Corporation "F-288"
• OMNIRAD369 (OMNIRAD369 (B) as the photopolymerization initiator (B) was added to a total of 100 parts by weight of the polymerizable compound (A) and the monofunctional polymerizable monomer. 2 parts by weight of IGM) and 1 part by weight of Nonion S-202 (polyoxyethylene-stearyl ether, manufactured by Nichiyu Co., Ltd.) as a release agent are mixed and dissolved, and then propylene glycol monomethyl ether acetate is used as a solvent. Dilute the active ingredient to 40-60% with The coating compositions for producing each interlayer insulating film according to Examples 1 to 6 and Comparative Examples 1 to 5 were prepared.
• A-1 The polymerizable compound (A-1)
• A-2 The polymerizable compound (A-2)
• A-3 The polymerizable compound (A-3)
• A-4 The polymerizable compound (A-4)
• A'-1 Polymethylsilsesqui synthesized by polycondensing methyltrimethoxysilane, 1,2-bis (triethoxysilyl) ethane, and dimethyldimethoxysilane prepared by the method shown in the experimental section of Non-Patent Document 1.
• Substituted composition A'-4 Silicone oligomer having an acryloyl group and a methoxy group (manufactured by Shin-Etsu Chemical Co., Ltd., KR-513)
• A'-5 Silicone having acryloyl groups at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-2445)
• Poroxamine compound tetrafunctional ethylene oxide / propylene oxide block copolymer, BASF, Tetronic150R1
• a coating composition for producing an interlayer insulating film is applied onto the above-mentioned substrate with an adhesive film using a spin coater so as to have a thickness of about 2 to 3 ⁇ m, prebaked at 80 ° C. for 60 seconds, and then centered in a nitrogen atmosphere. After irradiating with parallel light of 1 kW DeepUV lamp having a wavelength of 365 nm for 100 mJ / cm 2 (about 4 seconds) and photocuring, it is baked on a hot plate at 350 ° C. for 60 seconds to cure the coating composition for producing an interlayer insulating film. A non-patterned film of the interlayer insulating film was obtained. The film thickness was measured with an optical interference type film thickness meter (OPTM-A1 manufactured by Otsuka Electronics Co., Ltd.).
• OTM-A1 optical interference type film thickness meter
• the coating composition for producing an interlayer insulating film used for producing the above-mentioned non-patterned film is further diluted with propylene glycol monomethyl ether acetate as a solvent so that the active ingredient becomes about 10%, and the above-mentioned adhesion film is obtained.
• the coating composition for producing an interlayer insulating film is cured in the same manner. A non-patterned film having an insulating film thickness of about 100 to 200 nm was obtained.
• the film thickness was measured with an optical interference type film thickness meter (OPTM-A1 manufactured by Otsuka Electronics Co., Ltd.). Using the above-mentioned non-patterned film, the non-dielectric constant at 1 MHz was evaluated by the CV method using a mercury probe (CVmap92A manufactured by Oyama Co., Ltd.). The evaluation criteria are shown below.
• C Relative permittivity ⁇ 6.0
• the coating composition for producing an interlayer insulating film used for producing the above-mentioned non-patterned film having a thickness of about 2 to 3 ⁇ m is further diluted with propylene glycol monomethyl ether acetate as a solvent so that the active ingredient is about 20%. Then, filtration was carried out using a nylon filter having a pore size of 0.01 ⁇ m to prepare a coating composition for producing an interlayer insulating film used for producing a pattern film.
• a coating composition for producing an interlayer insulating film was applied onto the above-mentioned substrate with an adhesive film using a spin coater so as to have a thickness of about 500 nm, and then prebaked at 80 ° C. for 60 seconds to remove the solvent.
• This base material was set on the lower stage of an optical nanoimprint apparatus (NM-0401, manufactured by Meisho Kiko Co., Ltd.) by vacuum suction.
• a mold (NIM PH-350 manufactured by NTT Advanced Technology, Inc.) made of quartz having a line / space pattern of about 350 nm to 10 ⁇ m and a groove depth of about 350 nm is fixed to the base glass, and the periphery of the mold is sputtered.
• Table 1 shows the formulation and evaluation results of each Example and Comparative Example.
• the unit of the numerical value in Table 1 indicates the weight ratio.
• the coating composition for producing an interlayer insulating film of the present invention can be used for producing an interlayer insulating film using various imprinting techniques, and is particularly used for producing an interlayer insulating film for forming nano-sized fine patterns. It can be preferably used as a coating composition. Specifically, semiconductor integrated circuits, microelectromechanical systems (MEMS), sensor elements, optical disks, magnetic recording media such as high-density memory disks, optical components such as diffraction grids and relief holograms, nanodevices, optical devices, flat panels.
• MEMS microelectromechanical systems
• Optical films and polarizing elements for manufacturing displays thin films for liquid crystal displays, organic transistors, color filters, overcoat layers, microlens arrays, immunoanalytical chips, DNA separation chips, microreactors, nanobiodevices, optical waveguides, optical filters, It can be used for producing a photonic liquid crystal, a modeled object by 3D printing, or the like.

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