WO2018066515A1 - パターン反転のための被覆組成物 - Google Patents
パターン反転のための被覆組成物 Download PDFInfo
- Publication number
- WO2018066515A1 WO2018066515A1 PCT/JP2017/035827 JP2017035827W WO2018066515A1 WO 2018066515 A1 WO2018066515 A1 WO 2018066515A1 JP 2017035827 W JP2017035827 W JP 2017035827W WO 2018066515 A1 WO2018066515 A1 WO 2018066515A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- coating composition
- methyl
- mol
- polysiloxane
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
- B05D1/322—Removable films used as masks
- B05D1/327—Masking layer made of washable film
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2505/00—Polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/105—Intermediate treatments
-
- 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
- G03F7/094—Multilayer resist systems, e.g. planarising layers
Definitions
- the present invention relates to a coating composition for pattern reversal, which is used for forming a fine pattern in connection with creation of an electronic device.
- a composition for forming a resist underlayer film containing a polymer having a unit structure of hydroxyacrylamide has been disclosed (see Patent Document 2).
- An antireflection film-forming composition containing a polymer containing a unit structure of hydroxyalkylene methacrylamide and a unit structure of aromatic alkylene methacrylate is disclosed (see Patent Document 3).
- resist pattern miniaturization proceeds in the future, resolution problems and problems that the resist pattern will collapse after development occur, and it is desired to make the resist thinner. For this reason, it is difficult to obtain a resist pattern film thickness sufficient for substrate processing, and not only the resist pattern but also the resist underlayer film formed between the resist and the semiconductor substrate to be processed functions as a mask during substrate processing. The process to have it has become necessary.
- the present invention provides a pattern reversal coating composition for filling a pattern gap of an organic underlayer film obtained by transferring a resist pattern formed on a substrate to be processed to a lower layer and forming a flat polysiloxane film. Is.
- the present invention provides, as a first aspect, a coating composition coated on a pattern of an organic underlayer film having a resist pattern transferred to a lower layer, and the coating composition has four hydrolyzable groups in the molecule in all silanes.
- the hydrolyzable silane in which the hydrolyzable silane having the four hydrolyzable groups in the molecule is present in a proportion of 50 mol% to 100 mol% is represented by the formula (1):
- R 1 represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group.
- R 2 represents an alkoxy group, an acyloxy group, or a halogen atom
- a represents an integer of 0 to 3.
- the coating according to the first aspect comprising 50 mol% to 100 mol% of a hydrolyzable silane in which a is 0, and 0 mol% to 50 mol% of a hydrolyzable silane in which a is 1 to 2 Composition,
- the hydrolyzable silane represented by the formula (1) is a tetraalkoxysilane in which a is 0 in the formula (1), a methyltrialkoxysilane in which a is 1 in the formula (1), vinyl
- the coating composition according to the second aspect including any one of trialkoxysilane, phenyltrialkoxysilane, and dimethyldialkoxysilane in which a is 2 in formula (1),
- the coating composition according to any one of the first to third aspects, wherein the alcohol is an alkoxy group-containing alcohol,
- the coating composition according to any one of the first to fourth aspects, wherein the alcohol is propylene glycol monomethyl ether, propylene glycol monoethyl ether or 3-methoxybutanol,
- the condensate of the hydrolyzable silane is a hydrolysis condensate using an acid or a base as a catalyst, and the coating composition according to any one of the first to fifth aspects,
- the coating composition according to any one of the first to sixth aspects, wherein the coating composition further includes one or more selected from the group consisting of an acid and a curing catalyst,
- the coating composition is used for coating on a patterned organic underlayer film, and the patterned organic underlayer film is formed by etching a silicon hard mask layer with a resist pattern.
- the coating composition according to any one of the eighth to eighth aspects is applied and subsequently cured to form a polysiloxane film that fills the pattern gap Step (7)
- the method of manufacturing a semiconductor device comprising the step of inverting the pattern the organic underlayer film is etched (8), a step of etching the substrate by a polysiloxane membrane reversed pattern (9).
- the coating composition containing the polysiloxane of the present invention is patterned by transferring this resist pattern to the lower layer without mixing with the patterned organic underlayer film formed on the substrate to be processed and transferring the resist pattern to the lower layer.
- the organic underlayer film can be coated to fill (fill) the pattern gap of the organic underlayer film.
- the present invention is useful as a coating composition to be coated on a pattern of an organic underlayer film in which a resist pattern is transferred to the underlayer.
- the coating composition containing polysiloxane is cured to form polysiloxane, and the organic underlayer film surface can be exposed later by etching back by etching (gas etching). Furthermore, since the organic underlayer film can be removed by etching, the pattern of the organic underlayer film can be reversed to a polysiloxane pattern filled with a coating composition containing polysiloxane.
- the substrate to be processed can be processed by these reversal patterns. If the adhesion between the target substrate to be processed and the film coated thereon is improved by the coating composition containing polysiloxane rather than the organic underlayer film, such pattern inversion is performed. By using it, the substrate to be processed can be processed with a film having high adhesion.
- the organic underlayer film directly above the substrate to be processed is inverted using the pattern of the organic underlayer film having a larger aspect ratio than the photoresist pattern, a high aspect ratio inversion pattern is obtained. It is done. Since the present invention is embedded in an organic underlayer film substrate having a large aspect ratio, coating with a specific polysiloxane composition is effective. Further, in the conventional technique of filling (filling) a polysiloxane composition between photoresist patterns, an organic film is present in the lower layer, which makes it difficult to perform ashing or the like, and may be performed only by gas etching. Many.
- the pattern in order to reverse the pattern of the organic underlayer film directly on the substrate to be processed or on the oxide film with the polysiloxane composition, the pattern is formed by gas etching after being embedded after the polysiloxane composition is embedded. After inversion, the residue can be removed by ashing.
- the present invention is a coating composition coated on a pattern of an organic underlayer film having a resist pattern transferred to the lower layer, and the coating composition is a hydrolyzable silane having four hydrolyzable groups in the molecule.
- a hydrolyzable condensate of hydrolyzable silane present in a proportion of 50 mol% to 100 mol%, and is a coating composition containing a polysiloxane in which the silanol group of the condensate has reacted with an alcohol.
- the polysiloxane in which the silanol group of the condensate has reacted with the alcohol forms a dehydration reaction between the silanol group and the alcohol and forms an alkoxy group by the organic component of the reacted alcohol. And capping of silanol groups. Since the alcohol generated by hydrolysis is removed from the reaction system from the hydrolysis condensate, the reacting alcohol is a separately added alcohol different from the alcohol generated by hydrolysis.
- the hydrolyzable silane represented by the formula (1) is 50 mol% to 100 mol%, or 60 mol% to 100 mol of the hydrolyzable silane in which a is 0 in the formula (1).
- the hydrolyzable silane containing 1 to 2 in formula (1) is contained in a proportion of 0 mol% to 50 mol%, or 0 mol% to 40 mol%.
- R 1 has an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group.
- An organic group which is bonded to a silicon atom by a Si—C bond R 2 represents an alkoxy group, an acyloxy group, or a halogen atom, and a represents an integer of 0 to 3.
- the coating composition containing the polysiloxane of the present invention contains a hydrolysis condensate of the hydrolyzable silane of formula (1) and a solvent. And as an arbitrary component, an acid, alcohol, a curing catalyst, an acid generator, another organic polymer, a light absorbing compound, a surfactant, and the like can be included.
- the solid content in the coating composition containing the polysiloxane of the present invention is, for example, 0.1 mass% to 50 mass%, or 0.1 mass% to 30 mass%, or 0.1 mass% to 25 mass%.
- the solid content is obtained by removing the solvent component from all the components of the coating composition containing polysiloxane.
- the ratio of the hydrolyzable silane, its hydrolyzate, and its hydrolysis condensate in the solid content is 20% by mass or more, for example, 50% by mass to 100% by mass, 60% by mass to 99% by mass, 70%. % By mass to 99% by mass.
- hydrolyzable silane, its hydrolyzate, and its hydrolysis condensate can also be used as a mixture thereof. It can be used as a condensate obtained by hydrolyzing a hydrolyzable silane and condensing the obtained hydrolyzate. It is also possible to use a partial hydrolyzate in which hydrolysis is not completely completed or a mixture in which a silane compound is mixed with the hydrolyzed condensate when obtaining the hydrolyzed condensate.
- This condensate is a polymer having a polysiloxane structure.
- the alkyl group is a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n- Propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl -N-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n
- a cyclic alkyl group can also be used.
- a cyclic alkyl group having 1 to 10 carbon atoms includes a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2 -Ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl Group, 1,2-di
- the alkenyl group is an alkenyl group having 2 to 10 carbon atoms, and includes an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group.
- aryl group examples include aryl groups having 6 to 20 carbon atoms, such as phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p- Chlorophenyl group, o-fluorophenyl group, p-mercaptophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-aminophenyl group, p-cyanophenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group, o -Biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenan
- organic group having an epoxy group examples include glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, and epoxycyclohexyl.
- Examples of the organic group having an acryloyl group include acryloylmethyl, acryloylethyl, acryloylpropyl, and the like.
- Examples of the organic group having a methacryloyl group include methacryloylmethyl, methacryloylethyl, methacryloylpropyl, and the like.
- Examples of the organic group having a mercapto group include ethyl mercapto, butyl mercapto, hexyl mercapto and octyl mercapto.
- Examples of the organic group having a cyano group include cyanoethyl and cyanopropyl.
- alkoxy group having 1 to 20 carbon atoms examples include alkoxy groups having a linear, branched, and cyclic alkyl moiety having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, and an i-propoxy group.
- the acyloxy group having 2 to 20 carbon atoms is, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butyl Carbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propyl Carbonyloxy group, n-hexylcarbonyloxy group, 1- Tyl-n-p
- halogen atom examples include fluorine, chlorine, bromine and iodine.
- the hydrolyzable silane represented by the above formula (1) is tetraalkoxysilane in which a is 0 in formula (1), methyltrialkoxysilane, vinyltrialkoxysilane or phenyl in which a is 1 in formula (1). It is preferable that the trialkoxysilane and the hydrolyzable silane in which a is 2 in the formula (1) include any of dimethyldialkoxysilanes.
- hydrolyzable condensate of the hydrolyzable silane a polysiloxane in which the silanol group of the condensate has reacted with an alcohol can be used.
- Examples of the alcohol include methanol, ethanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert- Amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2- Hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1- Pentanol, 2-methyl-2-pentanol, 2-methyl- -Pentanol, 3-methyl-1-pentanol, 3-methyl-2-
- Alkoxy group-containing alcohols are particularly preferred, and examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and particularly propylene glycol monomethyl ether and propylene.
- Glycol monoethyl ether can be preferably used.
- the hydrolyzable condensate of hydrolyzable silane can react with an alcohol at an arbitrary ratio.
- the resulting polysiloxane has a (silanol group) :( silanol group reacted with alcohol) of 100: 1 to 1: 100, or 10: 1 to 1:10, typically 0.75: 0.15 to 0. It can be present in a molar ratio of .55: 0.10.
- hydrolysis condensate polysiloxane
- the hydrolyzable condensate (polyorganosiloxane) of the hydrolyzable silane can obtain a condensate having a weight average molecular weight of 1,000 to 1,000,000, or 1,000 to 100,000. These molecular weights are molecular weights obtained in terms of polystyrene by gel permeation chromatography (hereinafter abbreviated as GPC) analysis.
- GPC gel permeation chromatography
- GPC measurement conditions are, for example, GPC apparatus (trade name HLC-8220 GPC, manufactured by Tosoh Corporation), GPC column (trade names Shodex KF803L, KF802, KF801, Showa Denko), column temperature is 40 ° C., eluent (elution solvent) Is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml / min, and the standard sample is polystyrene (manufactured by Showa Denko KK).
- an alkoxysilyl group an acyloxysilyl group, or a halogenated silyl group
- 0.5 to 100 mol, preferably 1 to 10 mol of water is used per mol of the hydrolyzable group.
- hydrolysis catalyst 0.001 mol to 10 mol, preferably 0.001 mol to 1 mol of hydrolysis catalyst can be used per mol of the hydrolyzable group.
- the reaction temperature during the hydrolysis and condensation is usually 20 ° C to 80 ° C.
- Hydrolysis may be performed completely or partially. That is, a hydrolyzate or a monomer may remain in the hydrolysis condensate.
- a catalyst can be used in the hydrolysis and condensation.
- An acid or a base can be used as the hydrolysis catalyst.
- hydrolysis catalyst examples include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
- Examples of the metal chelate compound as the hydrolysis catalyst include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri -N-Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxy bis (acetylacetonato) titanium , Di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (Acetylacetonate) Titanium, Di-t- Toxi-bis (acetylacetonato) titanium, monoethoxy-tris (acetylaceton
- Organic acids as hydrolysis catalysts are, for example, 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, sebacin Acid, gallic acid, merit acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, Examples include monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fuma
- Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
- Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazine.
- Examples include zabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide.
- the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.
- organic solvent used in the hydrolysis examples include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di -Aromatic hydrocarbon solvents such as i-propyl benzene, n-amyl naphthalene, trimethylbenzene; methanol, ethanol, ethanol
- acetone methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di- Ketone solvents such as i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchon are preferred from the viewpoint of storage stability of the solution.
- the coating composition containing the polysiloxane of the present invention may contain a curing catalyst.
- the curing catalyst functions as a curing catalyst when a coating film containing polyorganosiloxane composed of a hydrolysis condensate is heated and cured.
- ammonium salts As the curing catalyst, ammonium salts, phosphines, phosphonium salts, and sulfonium salts can be used.
- the formula (D-1) (Wherein m is an integer of 2 to 11, n is an integer of 2 to 3, R 21 is an alkyl group or an aryl group, and Y ⁇ is an anion), a quaternary ammonium salt having the structure (D-2): (Wherein R 22 , R 23 , R 24 and R 25 represent an alkyl group or an aryl group, N represents a nitrogen atom, Y ⁇ represents an anion, and R 22 , R 23 , R 24 and R 25 represent A quaternary ammonium salt having a structure represented by the formula: Formula (D-3): A quaternary ammonium salt having the structure (wherein R 26 and R 27 represent an alkyl group or an aryl group, Y ⁇ represents an anion), Formula (D-4): A quaternary ammonium salt having the structure (wherein R 28 represents an alkyl group or an aryl group, Y ⁇ represents an anion), Formula (D-5)
- the formula (D-7) (Wherein, R 31, R 32, R 33, and R 34 represents an alkyl group or an aryl group, P is a phosphorus atom, Y - represents an anion, and R 31, R 32, R 33 , and R 34 Are each bonded to a phosphorus atom by a CP bond).
- the formula (D-8) (However, R 35 , R 36 , and R 37 are alkyl groups or aryl groups, S is a sulfur atom, Y ⁇ is an anion, and R 35 , R 36 , and R 37 are CS bonds, respectively. And a tertiary sulfonium salt which is bonded to a sulfur atom.
- the compound of the above formula (D-1) is a quaternary ammonium salt derived from an amine, m represents an integer of 2 to 11, and n represents an integer of 2 to 3.
- R 21 of this quaternary ammonium salt represents an alkyl group or aryl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as a linear alkyl group such as an ethyl group, a propyl group or a butyl group, or a benzyl group. Cyclohexyl group, cyclohexylmethyl group, dicyclopentadienyl group and the like.
- Anions (Y ⁇ ) include halide ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 — ). And acid groups such as alcoholate (—O ⁇ ).
- the compound of the above formula (D-2) is a quaternary ammonium salt represented by R 22 R 23 R 24 R 25 N + Y ⁇ .
- R 22 , R 23 , R 24 and R 25 are an alkyl group or aryl group having 1 to 18 carbon atoms, or a silane compound bonded to a silicon atom by a Si—C bond.
- the anion (Y ⁇ ) includes halide ions such as chlorine ion (Cl ⁇ ), bromine ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ).
- This quaternary ammonium salt can be obtained commercially, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzyl chloride. Examples include ammonium and trimethylbenzylammonium chloride.
- the compound of the above formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 have 1 to 18 carbon atoms, and R 26 and R 27 carbon atoms. Is preferably 7 or more.
- R 26 can be exemplified by methyl group, ethyl group, propyl group, phenyl group and benzyl group
- R 27 can be exemplified by benzyl group, octyl group and octadecyl group.
- the anion (Y ⁇ ) includes halide ions such as chlorine ion (Cl ⁇ ), bromine ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ). And acid groups such as alcoholate (—O ⁇ ).
- This compound can be obtained as a commercial product.
- imidazole compounds such as 1-methylimidazole and 1-benzylimidazole are reacted with alkyl halides and aryl halides such as benzyl bromide and methyl bromide. Can be manufactured.
- the compound of the above formula (D-4) is a quaternary ammonium salt derived from pyridine
- R 28 is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, For example, a butyl group, an octyl group, a benzyl group, and a lauryl group can be exemplified.
- the anion (Y ⁇ ) includes halide ions such as chlorine ion (Cl ⁇ ), bromine ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ).
- this compound can be obtained as a commercial product, it is produced, for example, by reacting pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or an aryl halide. I can do it. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.
- the compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline or the like, and R 29 is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms.
- the aryl group include a methyl group, an octyl group, a lauryl group, and a benzyl group.
- R 30 is an alkyl group or aryl group having 1 to 18 carbon atoms. For example, in the case of quaternary ammonium derived from picoline, R 30 is a methyl group.
- the anion (Y ⁇ ) includes halide ions such as chlorine ion (Cl ⁇ ), bromine ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ).
- alcoholate (-O -) can be mentioned an acid group and the like.
- This compound can also be obtained as a commercial product.
- a substituted pyridine such as picoline is reacted with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride or benzyl bromide, or an aryl halide.
- alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride or benzyl bromide, or an aryl halide.
- Examples of this compound include N-benzy
- the compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, m represents an integer of 2 to 11, and n represents an integer of 2 to 3.
- Anions (Y ⁇ ) include halide ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 — ). And acid groups such as alcoholate (—O ⁇ ). It can be produced by reacting an amine with a weak acid such as carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid.
- the anion (Y ⁇ ) is (HCOO ⁇ ), and when acetic acid is used, the anion (Y ⁇ ) is (CH 3 COO). - ) When phenol is used, the anion (Y ⁇ ) is (C 6 H 5 O ⁇ ).
- the compound of the above formula (D-7) is a quaternary phosphonium salt having a structure of R 31 R 32 R 33 R 34 P + Y — .
- R 31, R 32, R 33, and R 34 is is a silane compound bonded to a silicon atom by an alkyl group or aryl group having 1 to 18 carbon atoms, or Si-C bonds, preferably R 31 through R 34 of the four substituents of 34 are a phenyl group or a substituted phenyl group, and examples thereof include a phenyl group and a tolyl group, and the remaining one is an alkyl group having 1 to 18 carbon atoms, A silane compound bonded to a silicon atom by an aryl group or Si—C bond.
- Anions (Y ⁇ ) include halide ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 — ). And acid groups such as alcoholate (—O ⁇ ).
- This compound can be obtained as a commercial product, for example, a halogenated tetraalkylphosphonium such as tetra-n-butylphosphonium halide, tetra-n-propylphosphonium halide, or a trialkylbenzyl halide such as triethylbenzylphosphonium halide.
- Triphenylmonoalkylphosphonium halides such as phosphonium, triphenylmethylphosphonium halide, triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritolylmonoarylphosphonium halide, or tritolyl monohalogenate Examples thereof include alkylphosphonium (the halogen atom is a chlorine atom or a bromine atom).
- halogens such as triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide, triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, and halogens such as tritolylmonophenylphosphonium halide.
- Preferred is a tolylyl monoarylphosphonium halide, or a tolyl monoalkylphosphonium halide such as a tolyl monomethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).
- the phosphines include methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, phenylphosphine and other first phosphine, dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, diphenylphosphine and other second phosphine.
- tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine and dimethylphenylphosphine.
- the compound of the above formula (D-8) is a tertiary sulfonium salt having a structure of R 35 R 36 R 37 S + Y — .
- R 35, R 36, and R 37 is an alkyl group or aryl group having 1 to 18 carbon atoms or is a silane compound bonded to a silicon atom by Si-C bonds, preferably R 35 to 3 R 37,
- Two of the substituents are a phenyl group or a substituted phenyl group, and examples thereof include a phenyl group and a tolyl group, and the other one is an alkyl group having 1 to 18 carbon atoms or an aryl group. It is.
- a halide ion such as, carboxylate (-COO -), iodide ion (I), sulfonato (-SO 3 - ), Alcoholate (—O ⁇ ), maleate anion, nitrate anion and the like.
- This compound can be obtained as a commercial product, for example, a trialkylsulfonium halide such as tri-n-butylsulfonium halide, tri-n-propylsulfonium halide, or a trialkylbenzyl halide such as diethylbenzylsulfonium halide.
- a trialkylsulfonium halide such as tri-n-butylsulfonium halide, tri-n-propylsulfonium halide, or a trialkylbenzyl halide such as diethylbenzylsulfonium halide.
- Halogenated diphenylmonoalkylsulfonium such as sulfonium, halogenated diphenylmethylsulfonium, halogenated diphenylethylsulfonium, halogenated triphenylsulfonium, (halogen atom is chlorine or bromine atom), tri-n-butylsulfonium carboxylate, tri-n- Trialkylsulfonium carboxylates such as propylsulfonium carboxylate and dialkylbenzylsulfones such as diethylbenzylsulfonium carboxylate Um-carboxylate, diphenylmethyl sulfonium carboxylate, diphenyl monoalkyl sulfonium carboxylate, triphenylsulfonium carboxylate such as diphenylethyl sulfonium carboxylate. Further, triphenylsulfonium halide and triphenylsulfonium
- a nitrogen-containing silane compound can be added as a curing catalyst.
- the nitrogen-containing silane compound include imidazole ring-containing silane compounds such as N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole.
- the curing catalyst is 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyorganosiloxane.
- Hydrolyzable silane is hydrolyzed using a catalyst in a solvent to condense, and the resulting hydrolyzed condensate (polymer) simultaneously removes by-product alcohol, used hydrolysis catalyst, and water by distillation under reduced pressure. be able to. Moreover, the acid and base catalyst used for hydrolysis can be removed by neutralization or ion exchange.
- the coating composition containing the polysiloxane of the present invention the coating composition containing the hydrolysis condensate (polysiloxane) can be added with an organic acid, an alcohol, or a combination thereof for stabilization.
- organic acid examples include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, trifluoroacetic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid, and salicylic acid. It is done. Of these, oxalic acid and maleic acid are preferred.
- the organic acid to be added is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the condensate (polyorganosiloxane).
- coating is preferable, for example, methanol, ethanol, propanol, isopropanol, a butanol etc. are mentioned.
- the added alcohol may be 1 to 20 parts by mass with respect to 100 parts by mass of the coating composition containing polysiloxane.
- the coating composition containing polysiloxane may contain one or more selected from the group consisting of an acid and a curing catalyst.
- the coating composition containing the polysiloxane of the present invention can contain an organic polymer compound, a photoacid generator, a surfactant, and the like, if necessary, in addition to the above components.
- the dry etching rate decrease in film thickness per unit time
- attenuation coefficient decrease in film thickness per unit time
- refractive index refractive index
- Examples of the photoacid generator contained in the coating composition containing the polysiloxane of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
- onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormalbutanesulfonate, diphenyliodonium perfluoronormaloctanesulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium camphor.
- Iodonium salt compounds such as sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenyls Sulfonium salt compounds such as phosphonium trifluoromethanesulfonate, and the like.
- sulfonimide compounds include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormalbutanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide. Can be mentioned.
- disulfonyldiazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzenesulfonyl). And diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
- photoacid generator Only one type of photoacid generator can be used, or two or more types can be used in combination.
- the proportion thereof is 0.01 to 15 parts by mass, or 0.1 to 10 parts by mass with respect to 100 parts by mass of the condensate (polyorganosiloxane). Or 0.5 mass part thru
- the surfactant is effective in suppressing the occurrence of pinholes and installations when the coating composition containing the polysiloxane of the present invention is applied to a substrate.
- Examples of the surfactant contained in the coating composition containing the polysiloxane of the present invention include polyoxyethylene alkyl such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether.
- Ethers polyoxyethylene octylphenol ether, polyoxyethylene alkylallyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate Sorbitan fatty acid esters such as rate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene Nonionic surface activity such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Agents, trade names F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, R-08, R-30, R-30N
- surfactants may be used alone or in combination of two or more.
- the ratio is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0 with respect to 100 parts by mass of the condensate (polyorganosiloxane). 0.01 parts by mass to 1 part by mass.
- a rheology adjusting agent, an adhesion aid and the like can be added to the coating composition containing the polysiloxane of the present invention.
- the rheology modifier is effective to improve the fluidity of the coating composition containing the polysiloxane.
- Adhesion aids are effective in improving the adhesion to the semiconductor substrate.
- any solvent can be used without particular limitation as long as it can dissolve the solid content.
- solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , E
- the organic underlayer film used in the present invention is obtained by applying and curing an organic underlayer film forming composition. Curing can be performed by heating at about 150 ° C. to 230 ° C.
- the organic underlayer film forming composition may contain a coating film resin and a solvent. As needed, a crosslinking agent, an acid, an acid generator, a light absorbing compound, and the like can be contained.
- the coating resin is a resin capable of mainly forming a film, and examples thereof include novolak resins, condensed epoxy resins, (meth) acrylic resins, polyether resins, and silicon-containing resins.
- the solid content of the composition is 0.1% to 70% by weight, or 0.1% to 60% by weight.
- Solid content is the content rate of the component remove
- the coating resin is 1% to 99.9% by weight, or 50% to 99.9% by weight, or 50% to 95% by weight, or 50% to 90% by weight. Can be contained.
- the coating resin has a weight average molecular weight of 600 to 1000000, or 600 to 200000.
- the silicon hard mask used in the present invention is obtained by applying and curing a silicon hard mask forming composition.
- the condensate obtained by hydrolyzing hydrolyzable silane is mentioned. This is a polysiloxane, including organopolysiloxanes.
- a condensate obtained by hydrolyzing a hydrolyzable silane is a hydrolyzable silane having four hydrolyzable groups, a hydrolyzable silane having three hydrolyzable groups, and a hydrolyzate having two hydrolyzable groups. It is obtained by hydrolyzing at least one hydrolyzable silane selected from the group consisting of a degradable silane and a hydrolyzable silane having one hydrolyzable group.
- Hydrolysis is performed by adding a catalyst (for example, an acid catalyst or a basic catalyst) in an organic solvent, followed by condensation by heating to obtain a hydrolyzed condensate (polysiloxane, organopolysiloxane).
- a catalyst for example, an acid catalyst or a basic catalyst
- the solid content of the composition is 0.1% to 70% by weight, or 0.1% to 60% by weight. Solid content is the content rate of the component remove
- the coating resin is contained in the solid content in a proportion of 1% to 99.9% by weight, or 50% to 99.9% by weight, or 50 to 95% by weight, or 50% to 90% by weight. can do.
- the coating resin has a weight average molecular weight of 600 to 1000000, or 600 to 200000.
- the silicon hard mask can also be formed by vapor deposition.
- a substrate used for manufacturing a semiconductor device for example, a silicon wafer substrate, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, and a low dielectric constant material (low-k)).
- the composition used in the present invention is coated on a material (coated substrate, etc.) by an appropriate coating method such as a spinner or a coater.
- a film is formed by firing.
- the conditions for firing are appropriately selected from firing temperatures of 80 ° C. to 250 ° C. and firing times of 0.3 minutes to 60 minutes.
- the firing temperature is 150 ° C. to 250 ° C.
- the firing time is 0.5 minutes to 2 minutes.
- the film thickness of the formed film is, for example, 10 nm to 1000 nm, 20 nm to 500 nm, 50 nm to 300 nm, or 100 nm to 200 nm.
- a photoresist layer is formed on the hard mask. Formation of the photoresist layer can be performed by a well-known method, that is, by applying a photoresist composition solution onto the lower layer film and baking.
- the film thickness of the photoresist is, for example, 50 nm to 10,000 nm, 100 nm to 2000 nm, or 200 nm to 1000 nm.
- the substrate can be processed by selecting an appropriate etching gas.
- a fluorine-based gas that provides a sufficiently high etching rate for photoresist as an etching gas
- an oxygen-based gas that provides a sufficiently high etching rate for the hard mask as an etching gas.
- Organic underlayer film can be processed.
- the substrate can be processed by reversing the pattern.
- the photoresist is not particularly limited as long as it is sensitive to light used for exposure. Either a negative photoresist or a positive photoresist can be used.
- a positive photoresist comprising a novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist comprising a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, an acid
- a chemically amplified photoresist comprising a low-molecular compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate
- a chemically amplified photoresist composed of a low molecular weight compound that decomposes with an acid to increase the al
- Examples include trade name APEX-E manufactured by Shipley, trade name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and trade name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), Proc. SPIE, Vol. 3999, 365-374 (2000), and fluorine-containing polymer-based photoresists.
- post-exposure heating is performed as necessary.
- the post-exposure heating is performed under conditions appropriately selected from a heating temperature of 70 ° C. to 150 ° C. and a heating time of 0.3 minutes to 10 minutes.
- a resist for electron beam lithography or a resist for EUV lithography can be used instead of a photoresist as a resist.
- the electron beam resist either a negative type or a positive type can be used.
- Chemically amplified resist comprising a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist
- a chemically amplified resist comprising: a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate; and a chemically amplified resist comprising a low-molecular compound that decomposes with an acid to change the alkali dissolution rate of the resist,
- non-chemically amplified resists composed of a binder having a group that changes the alkali dissolution rate by being
- EUV resist a methacrylate resin resist, a methacrylate-polyhydroxystyrene hybrid resin resist, and a polyhydroxystyrene resin resist can be used.
- EUV resist either a negative type or a positive type can be used.
- Chemically amplified resist comprising a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist
- a chemically amplified resist comprising: a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate; and a chemically amplified resist comprising a low-molecular compound that decomposes with an acid to change the alkali dissolution rate of the resist,
- a non-chemically amplified resist composed of a binder having a group that is decomposed by EUV light to change the alkali dissolution rate
- a non-chemically amplified resist composed of a binder having a portion that is cut by EUV light to change the alkali dissolution rate.
- a developer for example, an alkali developer.
- a developer for example, an alkali developer.
- Developers include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine, propylamine, An alkaline aqueous solution such as an aqueous amine solution such as ethylenediamine can be mentioned as an example. Further, a surfactant or the like can be added to these developers.
- the development conditions are appropriately selected from a temperature of 5 ° C. to 50 ° C. and a time of 10 seconds to 600 seconds.
- an organic solvent can be used as a developer. After the exposure, development is performed with a developer (solvent). As a result, for example, when a positive photoresist is used, the unexposed portion of the photoresist is removed, and a photoresist pattern is formed.
- Developers include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxy acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl Ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol No ethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate
- the organic underlayer film pattern obtained by transferring the resist pattern to the lower layer is coated with the composition of the present invention, the organic underlayer film is etched, and the pattern is inverted to the composition of the present invention.
- the portion of the hard mask from which the photoresist has been removed is removed by dry etching to expose the organic underlayer film.
- dry etching tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, hexafluoro Gases such as sulfur fluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used.
- a halogen-based gas is preferably used for dry etching of the hard mask.
- a photoresist made of an organic substance is basically difficult to remove.
- the hard mask containing many silicon atoms is quickly removed by the halogen-based gas. Therefore, it is possible to suppress a decrease in the film thickness of the photoresist accompanying the dry etching of the hard mask. As a result, the photoresist can be used as a thin film.
- the dry etching of the hard mask is preferably performed using a fluorine-based gas.
- fluorine-based gas examples include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), Examples thereof include trifluoromethane and difluoromethane (CH 2 F 2 ).
- the organic underlayer film is removed using the patterned photoresist and hard mask as a protective film.
- the organic underlayer film (underlayer) is preferably formed by dry etching with an oxygen-based gas. This is because a hard mask containing a large amount of silicon atoms is difficult to remove by dry etching using an oxygen-based gas.
- the fluorine-based gas is used as the gas used for etch back. Then, the pattern can be reversed by etching or ashing the organic underlayer film.
- a semiconductor device can be manufactured by the process of processing a board
- reaction product polysiloxane (corresponding to the formula (1-1))
- acetone was replaced with propylene glycol monoethyl ether using an evaporator.
- Mw molecular weight
- the above-obtained polysiloxane 57.51 g, propylene glycol monoethyl ether 42.37 g, and maleic acid 0.119 g were placed in a flask.
- the flask was fitted with a condenser and reacted in an oil bath at 60 ° C. for 15 hours to synthesize a modified polysiloxane having capped silanol groups of the polysiloxane.
- solid content in the obtained reaction product was 11.59 mass% as a result of measuring by the baking method.
- the molecular weight (Mw) of the obtained product (solid content) was 1780. Then, it mixed in the ratio of the following table
- reaction product polysiloxane (corresponding to the formula (1-1))
- acetone was replaced with propylene glycol monoethyl ether using an evaporator.
- solid content in the obtained reaction product was 21.80 mass% as a result of measuring by the baking method.
- molecular weight (Mw) of the obtained product (solid content) was 2050.
- reaction product polysiloxane (corresponding to the formula (1-1))
- acetone was replaced with propylene glycol monoethyl ether using an evaporator.
- solid content in the obtained reaction product was 19.64 mass% as a result of measuring by the baking method.
- molecular weight (Mw) of the obtained product (solid content) was 2350.
- reaction product polysiloxane (corresponding to the formula (1-1))
- acetone was replaced with propylene glycol monoethyl ether using an evaporator.
- Mw molecular weight
- the above-obtained polysiloxane 58.76 g, propylene glycol monoethyl ether 41.12 g, and maleic acid 0.119 g were placed in a flask.
- the flask was equipped with a condenser and reacted in an oil bath at 60 ° C. for 15 hours to synthesize a modified polysiloxane capped with a silanol group of the polysiloxane obtained in Synthesis 1 above.
- solid content in the obtained reaction product was 11.90 mass% as a result of measuring by the baking method.
- the molecular weight (Mw) of the obtained product (solid content) was 2470. Then, it mixed in the ratio of the following table
- reaction product polysiloxane (corresponding to the formula (1-1))
- acetone was replaced with propylene glycol monoethyl ether using an evaporator.
- solid content in the obtained reaction product was 19.62 mass% as a result of measuring by the baking method.
- molecular weight (Mw) of the obtained product (solid content) was 2840.
- reaction product polysiloxane (corresponding to Formula (1-2))
- acetone was replaced with propylene glycol monoethyl ether using an evaporator.
- solid content in the obtained reaction product was 18.99 mass% as a result of measuring by the baking method.
- molecular weight (Mw) of the obtained product (solid content) was 3050.
- reaction product (polysiloxane) (corresponding to the formula (1-1)) .
- acetone was substituted with propylene glycol monomethyl ether using an evaporator.
- Mw molecular weight of the obtained product (solid content) was 2430. 60.01 g of the polysiloxane obtained above, 40.10 g of propylene glycol monomethyl ether, and 0.120 g of maleic acid were placed in a flask.
- the flask was fitted with a condenser and reacted in an oil bath at 60 ° C. for 15 hours to synthesize a modified polysiloxane having capped silanol groups of the polysiloxane.
- solid content in the obtained reaction product was 12.12 mass% as a result of measuring by the baking method.
- the molecular weight (Mw) of the obtained product (solid content) was 2300. Then, it mixed in the ratio of the following table
- reaction product polysiloxane (corresponding to the formula (1-1)) .
- acetone was substituted with 3-methoxybutanol using an evaporator.
- Mw molecular weight of the obtained product (solid content) was 2230. 60.13 g of the polysiloxane obtained above, 40.03 g of 3-methoxybutanol, and 0.120 g of maleic acid were placed in a flask.
- the flask was fitted with a condenser and reacted in an oil bath at 60 ° C. for 15 hours to synthesize a modified polysiloxane having capped silanol groups of the polysiloxane.
- solid content in the obtained reaction product was 12.08 mass% as a result of measuring by the baking method.
- the molecular weight (Mw) of the obtained product (solid content) was 2250. Then, it mixed in the ratio of the following table
- reaction product polysiloxane (corresponding to Formula (1-4))
- acetone was replaced with propylene glycol monoethyl ether using an evaporator.
- solid content in the obtained reaction product was 19.89 mass% as a result of measuring by the baking method.
- molecular weight (Mw) of the obtained product (solid content) was 2220.
- reaction product polysiloxane (corresponding to Formula (1-5))
- acetone was replaced with propylene glycol monoethyl ether using an evaporator.
- solid content in the obtained reaction product was 20.44 mass% as a result of measuring by the baking method.
- molecular weight (Mw) of the obtained product (solid content) was 2350.
- the above-obtained polysiloxane 58.71 g, propylene glycol monoethyl ether 41.17 g, and maleic acid 0.120 g were placed in a flask.
- the flask was fitted with a condenser and reacted in an oil bath at 60 ° C. for 15 hours to synthesize a modified polysiloxane having capped silanol groups of the polysiloxane.
- solid content in the obtained reaction product was 11.65 mass% as a result of measuring by the baking method.
- the molecular weight (Mw) of the obtained product (solid content) was 2430. Then, it mixed in the ratio of the following table
- reaction product polysiloxane (corresponding to the formula (1-1))
- acetone was substituted with propylene glycol monomethyl ether acetate using an evaporator.
- solid content in the obtained reaction product was 25.44 mass% as a result of measuring by the baking method.
- molecular weight (Mw) of the obtained product (solid content) was 1850. Then, it mixed in the ratio of the following table
- reaction product polysiloxane (corresponding to the formula (1-1)) .
- acetone was substituted with propylene glycol monomethyl ether acetate using an evaporator.
- solid content in the obtained reaction product was 21.30 mass% as a result of measuring by the baking method.
- molecular weight (Mw) of the obtained product (solid content) was 2100. Then, it mixed in the ratio of the following table
- the polysiloxane contained in the coating composition of the present invention is obtained by reacting a silanol group of the condensate with an alcohol in a hydrolysis condensate of hydrolyzable silane.
- silanol groups and alcohol cause a dehydration reaction to form alkoxy groups due to organic components of the reacted alcohol, and are obtained by capping the silanol groups.
- the ratio of silanol groups in the polymer and the capping ratio of propylene glycol monomethyl ether, propylene glycol monoethyl ether and 3-methoxybutanol were calculated by 1 H NMR. The measurement was performed using JNM-ECA500 (manufactured by JEOL).
- the integration ratio of the chemical shift value (0.0-0.3 ppm) of methyl proton of triethoxymethylsilane was taken as a standard.
- the chemical shift values of methine protons of propylene glycol monomethyl ether and propylene glycol monoethyl ether and methylene protons of 3-methoxybutanol are detected around 3.8 ppm, but they form bonds with silicon atoms by dehydration condensation reaction with silanol groups. In other words, when a capping reaction occurs with respect to the silanol group, the chemical shift values of methine protons and methylene protons move to around 4.2 ppm.
- maleic acid is MA
- trifluoroacetic acid is TFA
- benzyltriethylammonium chloride is BTEAC
- N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is IMIDTEOS
- triphenylsulfonium nitrate is TPSNO3
- malee Monotriphenylsulfonium acid is TPSMA
- triphenylsulfonium trifluoroacetate is TPSTFA
- triphenylsulfonium chloride is TPSCl
- triphenylsulfonium camphorsulfonate is TPSCS
- triphenylsulfonium trifluoromethanesulfonate is TPSTf
- nonafluorobutane Triphenylsulfonium sulfonate
- coating performance evaluation About each coating composition containing the polysiloxane in Example 1 thru
- the stepped substrate is a hole pattern made of SiO 2 having a height of 300 nm and a minimum width of 20 nm. Subsequently, about the film
- a semiconductor substrate 1 represents a wafer
- a semiconductor substrate 2 represents an oxide film, a metal layer, or the like coated thereon.
- an organic underlayer film is formed on a semiconductor substrate
- a silicon hard mask forming composition is applied thereon and baked to form a silicon hard mask layer
- a resist composition is formed on the silicon hard mask layer.
- Steps (1) to (3) for applying and forming a resist layer A step of exposing the resist film; a step of developing the resist after exposure to obtain a resist pattern (4);
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Structural Engineering (AREA)
- Architecture (AREA)
- Silicon Polymers (AREA)
- Materials For Photolithography (AREA)
- Paints Or Removers (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
対象とする被加工基板とその上に被覆される膜との密着性が、有機下層膜よりポリシロキサンを含む被覆組成物による膜の方が改善される場合には、この様なパターンの反転を用いることによって、密着性の高い膜により被加工基板を加工することができる。
従来の技術としてフォトレジストパターン間に、ポリシロキサン系組成物を埋め込(充填)み、その後に酸素系ガスによるエッチングによりポリシロキサンのパターンに反転する方法が行われていた。この手法ではレジストの膜厚は薄いので高アスペクト比の反転パターンは得られない。
また、従来の技術としてフォトレジストパターン間に、ポリシロキサン系組成物を埋め込む(充填)方法では、下層に有機系の膜が存在するためアッシング等の処理が難しく、ガスエッチングのみにより行われる場合が多い。
式(1)中、R1はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、もしくはシアノ基を有する有機基で且つSi-C結合によりケイ素原子と結合しているものであり、R2はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、aは0乃至3の整数を示す。
加水分解し縮合させる際に触媒を用いることができる。
式(D-3):
式(D-4):
式(D-5):
式(D-6):
焼成することにより膜が形成される。焼成する条件としては、焼成温度80℃乃至250℃、焼成時間0.3分間乃至60分間の中から適宜、選択される。好ましくは、焼成温度150℃乃至250℃、焼成時間0.5分間乃至2分間である。ここで、形成される膜の膜厚としては、例えば、10nm乃至1000nmであり、または20nm乃至500nmであり、または50nm乃至300nmであり、または100nm乃至200nmである。
テトラエトキシシラン95.64g(全シラン中に60モル%含有する)、メチルトリエトキシシラン54.57g(全シラン中に40モル%含有する)及びアセトン100.14gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)49.64gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、20.66質量%であった。また、得られた生成物(固形分)の分子量(Mw)は1760であった。
上記得られたポリシロキサン57.51g、プロピレングリコールモノエチルエーテル42.37g、及びマレイン酸0.119gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.59質量%であった。また、得られた生成物(固形分)の分子量(Mw)は1780であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン109.68g(全シラン中に70モル%含有する)、メチルトリエトキシシラン40.23g(全シラン中に30モル%含有する)及びアセトン99.94gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.15gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、21.80質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2050であった。
上記得られたポリシロキサン54.50g、プロピレングリコールモノエチルエーテル45.38g、及びマレイン酸0.119gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.10質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2090であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン116.52g(全シラン中に75モル%含有する)、メチルトリエトキシシラン33.24g(全シラン中に25モル%含有する)及びアセトン99.84gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.36gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、19.64質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2350であった。
上記得られたポリシロキサン60.49g、プロピレングリコールモノエチルエーテル39.39g、及びマレイン酸0.119gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させ上記合成1で得られたポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.89質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2380であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン123.25g(全シラン中に80モル%含有する)、メチルトリエトキシシラン26.37g(全シラン中に20モル%含有する)及びアセトン99.74gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.64gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、20.22質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2460であった。
上記得られたポリシロキサン58.76g、プロピレングリコールモノエチルエーテル41.12g、及びマレイン酸0.119gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させ上記合成1で得られたポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.90質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2470であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン136.36g(全シラン中に90モル%含有する)、メチルトリエトキシシラン12.97g(全シラン中に10モル%含有する)及びアセトン99.55gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)51.11gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、19.62質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2840であった。
上記得られたポリシロキサン60.56g、プロピレングリコールモノエチルエーテル39.32g、及びマレイン酸0.119gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させ上記合成1で得られたポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.45質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2860であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン149.06g(全シラン中に100モル%含有する)及びアセトン99.37gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)51.59gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-2)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、18.99質量%であった。また、得られた生成物(固形分)の分子量(Mw)は3050であった。
上記得られたポリシロキサン62.57g、プロピレングリコールモノエチルエーテル37.32g、及びマレイン酸0.119gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させ上記合成1で得られたポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.23質量%であった。また、得られた生成物(固形分)の分子量(Mw)は3070であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン116.52g(全シラン中に75モル%含有する)、メチルトリエトキシシラン33.24g(全シラン中に25モル%含有する)及びアセトン99.84gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.36gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノメチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、21.12質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2430であった。
上記得られたポリシロキサン60.01g、プロピレングリコールモノメチルエーテル40.10g、及びマレイン酸0.120gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、12.12質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2300であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン116.52g(全シラン中に75モル%含有する)、メチルトリエトキシシラン33.24g(全シラン中に25モル%含有する)及びアセトン99.84gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.36gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。さらに、エバポレーターを用いてアセトンを3-メトキシブタノールに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、20.13質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2230であった。
上記得られたポリシロキサン60.13g、3-メトキシブタノール40.03g、及びマレイン酸0.120gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、12.08質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2250であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン117.25g(全シラン中に75モル%含有する)、メチルトリエトキシシラン26.76g(全シラン中に20モル%含有する)、ジメチルトリエトキシシラン5.56g(全シラン中に5モル%含有する)及びアセトン99.72gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.71gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-3)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、21.09質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2150であった。
上記得られたポリシロキサン56.90g、プロピレングリコールモノエチルエーテル42.98g、及びマレイン酸0.120gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.55質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2180であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン117.25g(全シラン中に75モル%含有する)、メチルトリエトキシシラン26.75g(全シラン中に20モル%含有する)、ビニルトリメトキシシラン5.56g(全シラン中に5モル%含有する)及びアセトン99.71gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.71gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-4)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、19.89質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2220であった。
上記得られたポリシロキサン60.33g、プロピレングリコールモノエチルエーテル39.55g、及びマレイン酸0.120gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.57質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2260であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン116.04g(全シラン中に75モル%含有する)、メチルトリエトキシシラン26.48g(全シラン中に20モル%含有する)、フェニルトリメトキシシラン7.36g(全シラン中に5モル%含有する)及びアセトン99.93gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.19gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-5)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノエチルエーテルに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、20.44質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2350であった。
上記得られたポリシロキサン58.71g、プロピレングリコールモノエチルエーテル41.17g、及びマレイン酸0.120gをフラスコに入れた。このフラスコに、冷却管を取り付けオイルバスにて60℃で15時間反応させポリシロキサンのシラノール基をキャッピングした変性ポリシロキサンを合成した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、11.65質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2430であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン95.64g(全シラン中に60モル%含有する)、メチルトリエトキシシラン54.57g(全シラン中に40モル%含有する)及びアセトン100.14gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)49.64gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。
さらに、エバポレーターを用いてアセトンをプロピレングリコールモノメチルエーテルアセテートに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、25.44質量%であった。また、得られた生成物(固形分)の分子量(Mw)は1850であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
テトラエトキシシラン109.68g(全シラン中に70モル%含有する)、メチルトリエトキシシラン40.23g(全シラン中に30モル%含有する)及びアセトン99.94gをフラスコに入れた。このフラスコに、冷却管を取り付け調製しておいた塩酸水溶液(0.01モル/リットル)50.15gを入れた滴下ロートをセットし、室温下で塩酸水溶液をゆっくり滴下し数分攪拌した。その後オイルバスにて85℃で4時間反応させた。反応終了後、反応溶液の入ったフラスコを放冷してからエバポレーターにセットし、反応中生成したエタノールを除去して反応生成物(ポリシロキサン)を得た(式(1-1)に相当)。さらに、エバポレーターを用いてアセトンをプロピレングリコールモノメチルエーテルアセテートに置換した。尚、得られた反応生成物中の固形分は、焼成法により測定した結果、21.30質量%であった。また、得られた生成物(固形分)の分子量(Mw)は2100であった。その後、下表の割合で混合し、孔径0.1μmのフィルターでろ過してパターン反転のためのポリシロキサンを含む被覆組成物を得た。
本発明の被覆組成物に含まれるポリシロキサンは、加水分解性シランの加水分解縮合物において、該縮合物が有するシラノール基がアルコールと反応して得られるものである。上記ポリシロキサンは、シラノール基とアルコールが脱水反応を起こし、反応したアルコールの有機成分によるアルコキシ基を形成するものであり、シラノール基のキャッピングによって得られるものである。
ポリマー中のシラノール基比率、およびプロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルおよび3-メトキシブタノールのキャッピング比率は1H NMRにて算出した。測定はJNM-ECA500(JEOL製)を用いて行った。まずトリエトキシメチルシランのメチルプロトンの化学シフト値(0.0-0.3ppm)の積分比を取り基準とした。プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルのメチンプロトンおよび3-メトキシブタノールのメチレンプロトンの化学シフト値は3.8ppm付近に検出されるが、シラノール基との脱水縮合反応によりケイ素原子と結合を形成した場合、すなわちシラノール基に対してキャッピング反応が起こった場合、メチンプロトンおよびメチレンプロトンの化学シフト値が4.2ppm付近に移動する。4.2ppm付近に移動したメチンプロトンおよびメチレンプロトンの積分比を測定し、先に測定したトリエトキシメチルシランのメチルプロトンの積分比を比較することで、ポリマー中のケイ素原子1個に対するプロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルおよび3-メトキシブタノールのキャッピング比率を算出した。得られたポリシロキサン中のSi原子1モルに対する残存するSiOH基、キャッピングされたSiOH基のモル数の割合を下記表に示す。下表中でプロピレングリコールモノエチルエーテルはPGEE、プロピレングリコールモノメチルエーテルはPGME及び3―メトキシブタノールはMBと略した。
上記合成例1乃至合成例11、比較合成例1及び2で得られたポリシロキサン、酸、硬化触媒、添加剤、溶媒を下表に示す割合で混合し、0.1μmのフッ素樹脂製のフィルターで濾過することによって、ポリシロキサンを含む被覆組成物の溶液をそれぞれ調製した。下表中のポリマーの添加割合はポリマー溶液の添加量ではなく、ポリマー自体の添加量を示した。
下表中でマレイン酸はMA、トリフルオロ酢酸はTFA、ベンジルトリエチルアンモニウムクロリドはBTEAC、N-(3-トリエトキシシリプロピル)-4,5-ジヒドロイミダゾールはIMIDTEOS、トリフェニルスルホニウム硝酸塩はTPSNO3、マレイン酸モノトリフェニルスルフォニウムはTPSMA、トリフェニルスルホニウムトリフルオロ酢酸塩はTPSTFA、トリフェニルスルホニウムクロリドはTPSCl、トリフェニルスルホニウムカンファースルホン酸塩はTPSCS、トリフェニルスルホニウムトリフルオロメタンスルホン酸塩はTPSTf、ノナフルオロブタンスルホン酸トリフェニルスルホニウムはTPSNf、トリフェニルスルホニウムアダマンタンカルボキシ-1,1,2-トリフルオロブタンスルホン酸塩はTPSAdTF、ジヒドロキシフェニルフェニルスルホニウムpトルエンスルホン酸塩はDHTPPSpTS、ビスフェニルスルホンはBPS、プロピレングリコールモノメチルエーテルアセテートはPGMEA、プロピレングリコールモノエチルエーテルはPGEE、プロピレングリコールモノメチルエーテルはPGME、3―メトキシブタノールはMB、乳酸エチルはEL及びPnPはプロピレングリコール-n-プロピルエーテルと略した。各添加量は質量部で示した。
実施例1乃至実施例30、比較例1及び比較例2におけるポリシロキサンを含む各被覆組成物について、下記のように被覆性能評価を行った。その評価結果を下表に示す。
被覆性能を評価するために、図2の段差基板上に、スピンコーターを用いて、回転数1500rpm、60秒間の条件にて、実施例1乃至実施例30、比較例1及び比較例2のポリシロキサンを含む各被覆組成物を塗布し、その後200℃のホットプレート上で1分間乾燥することにより、ポリシロキサンを含む被覆組成物による膜を形成した。ポリシロキサンを含む被覆組成物の膜厚は180nm。前記段差基板は、SiO2から成る高さ300nm、最少幅が20nmのホールパターン。次いで、得られたポリシロキサンを含む被覆組成物による膜について、断面SEMにより断面の形状を観察し被覆性能を評価。ボイドの発生無く良好な被覆性を示したポリシロキサンを含む被覆組成物の被覆性を良好とし、ボイドが発生したポリシロキサンを含む被覆組成物の被覆性を不良と評価した。
図1において、半導体基板上に有機下層膜を形成し、その上にシリコンハードマスク形成組成物を塗布し焼成しシリコンハードマスク層を形成し、前記シリコンハードマスク層の上にレジスト用組成物を塗布しレジスト層を形成する工程(1)乃至工程(3)。前記レジスト膜を露光する工程、露光後にレジストを現像しレジストパターンを得る工程(4)。レジストパターンによりシリコンハードマスクをエッチングし、パターン化されたシリコンハードマスク層により有機下層膜をエッチングしパターン化された有機下層膜を形成する工程(5)及び工程(6)。パターン化された有機下層膜にポリシロキサンを含む被覆組成物を塗布しエッチバックで有機下層膜面を露出する工程(7)。有機下層膜をエッチングしてパターンを反転する工程(8)。反転したパターンのポリシロキサン膜により基板をエッチング加工する工程(9)。
Claims (9)
- レジストパターンを下層に転写した有機下層膜のパターン上に被覆される被覆組成物であり、該被覆組成物は全シラン中に4つの加水分解性基を分子内に有する加水分解性シランが50モル%乃至100モル%の割合で存在する加水分解性シランの加水分解縮合物において、該縮合物が有するシラノール基がアルコールと反応したポリシロキサンを含む被覆組成物。
- 前記4つの加水分解性基を分子内に有する加水分解性シランが50モル%乃至100モル%の割合で存在する加水分解性シランが式(1):
- 前記式(1)で表される加水分解性シランが式(1)中、aが0であるテトラアルコキシシラン、式(1)中aが1であるメチルトリアルコキシシラン、ビニルトリアルコキシシラン、又はフェニルトリアルコキシシラン、式(1)中aが2であるジメチルジアルコキシシランのうちいずれかを含む請求項2に記載の被覆組成物。
- アルコールがアルコキシ基含有アルコールである請求項1乃至請求項3のいずれか1項に記載の被覆組成物。
- アルコールがプロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル又は3-メトキシブタノールである請求項1乃至請求項4のいずれか1項に記載の被覆組成物。
- 前記加水分解性シランの縮合物が、酸、又は塩基を触媒とした加水分解縮合物である請求項1乃至請求項5のいずれか1項に記載の被覆組成物。
- 前記被覆組成物が更に酸、及び硬化触媒からなる群から選ばれた一つ以上を含む請求項1乃至請求項6のいずれか1項に記載の被覆組成物。
- 前記被覆組成物は、パターン化された有機下層膜上に被覆するのに用いられ、該パターン化された有機下層膜は、レジストパターンによりシリコンハードマスク層をエッチングし、パターン化されたシリコンハードマスク層により有機下層膜をエッチングし形成される請求項1乃至請求項7のいずれか1項に記載の被覆組成物。
- 半導体基板上に有機下層膜を形成する工程(1)、その上にシリコンハードマスク形成組成物を塗布し焼成しシリコンハードマスク層を形成する工程(2)、前記シリコンハードマスク層の上にレジスト用組成物を塗布しレジスト層を形成する工程(3)、前記レジスト膜を露光し、露光後にレジストを現像しレジストパターンを得る工程(4)、レジストパターンによりシリコンハードマスク層をエッチングする工程(5)、パターン化されたシリコンハードマスク層により有機下層膜をエッチングしパターン化された有機下層膜を形成する工程(6)、パターン化された有機下層膜上に請求項1乃至請求項8のいずれか1項に記載の被覆組成物を塗布し続いて硬化させ、パターン間隙を埋めるポリシロキサン膜を形成する工程(7)、有機下層膜をエッチングしてパターンを反転する工程(8)、反転したパターンのポリシロキサン膜により基板をエッチング加工する工程(9)を含む半導体装置の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/339,489 US20190292403A1 (en) | 2016-10-04 | 2017-10-02 | Coating composition for pattern inversion |
KR1020197008063A KR102478337B1 (ko) | 2016-10-04 | 2017-10-02 | 패턴반전을 위한 피복 조성물 |
CN201780061137.XA CN109790414B (zh) | 2016-10-04 | 2017-10-02 | 用于图案反转的被覆组合物 |
JP2018543893A JP7011229B2 (ja) | 2016-10-04 | 2017-10-02 | パターン反転のための被覆組成物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-196747 | 2016-10-04 | ||
JP2016196747 | 2016-10-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018066515A1 true WO2018066515A1 (ja) | 2018-04-12 |
Family
ID=61831877
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/035827 WO2018066515A1 (ja) | 2016-10-04 | 2017-10-02 | パターン反転のための被覆組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20190292403A1 (ja) |
JP (1) | JP7011229B2 (ja) |
KR (1) | KR102478337B1 (ja) |
CN (1) | CN109790414B (ja) |
TW (1) | TWI818900B (ja) |
WO (1) | WO2018066515A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190108828A (ko) * | 2018-03-15 | 2019-09-25 | 삼성전자주식회사 | 실리콘게르마늄 식각 전의 전처리 조성물 및 이를 이용한 반도체 장치의 제조 방법 |
JP2020012951A (ja) * | 2018-07-17 | 2020-01-23 | 日産化学株式会社 | ポリカルボシラン含有組成物 |
WO2020152976A1 (ja) * | 2019-01-24 | 2020-07-30 | 信越化学工業株式会社 | オルガノポリシロキサン化合物を含有する組成物 |
WO2021060495A1 (ja) * | 2019-09-27 | 2021-04-01 | Jsr株式会社 | 組成物、膜、膜形成方法、パターン形成方法、有機下層膜反転パターン形成方法及び組成物の製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7238788B2 (ja) * | 2017-12-13 | 2023-03-14 | 株式会社ニコン | パターン形成方法、トランジスタの製造方法及びパターン形成用部材 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001033949A (ja) * | 1999-05-19 | 2001-02-09 | Fuji Photo Film Co Ltd | 平版印刷版用原版 |
JP2009128564A (ja) * | 2007-11-22 | 2009-06-11 | Nissan Chem Ind Ltd | レジスト下層膜形成組成物及び半導体装置の製造方法 |
JP2011118373A (ja) * | 2009-10-30 | 2011-06-16 | Jsr Corp | 反転パターン形成方法及びポリシロキサン樹脂組成物 |
JP2015038221A (ja) * | 2007-02-27 | 2015-02-26 | エイゼット・エレクトロニック・マテリアルズ・ユーエスエイ・コーポレイション | ケイ素に基づく反射防止膜用組成物 |
WO2016031563A1 (ja) * | 2014-08-25 | 2016-03-03 | 日産化学工業株式会社 | Socパターン上でのパターン反転のための被覆用組成物 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19934116A1 (de) * | 1999-04-07 | 2000-10-19 | S & C Polymer Silicon & Compos | Haftvermittler für Siliconmaterialien |
JP3848070B2 (ja) | 2000-09-27 | 2006-11-22 | 株式会社東芝 | パターン形成方法 |
WO2004083309A1 (ja) * | 2003-03-18 | 2004-09-30 | Jsr Corporation | 放射線硬化型組成物、光導波路およびその形成方法 |
JP2004363371A (ja) | 2003-06-05 | 2004-12-24 | Renesas Technology Corp | 電子デバイスの製造方法 |
JP5003279B2 (ja) | 2007-05-21 | 2012-08-15 | Jsr株式会社 | 反転パターン形成方法 |
JP5035151B2 (ja) | 2008-07-10 | 2012-09-26 | Jsr株式会社 | パターン反転用樹脂組成物及び反転パターン形成方法 |
US20110117746A1 (en) * | 2008-07-24 | 2011-05-19 | Nissan Chemical Industries, Ltd. | Coating composition and pattern forming method |
CN102439069B (zh) * | 2009-07-23 | 2014-11-05 | 道康宁公司 | 用于反向图案化的方法和材料 |
WO2011102470A1 (ja) * | 2010-02-19 | 2011-08-25 | 日産化学工業株式会社 | 窒素含有環を有するシリコン含有レジスト下層膜形成組成物 |
US9181402B2 (en) * | 2012-03-21 | 2015-11-10 | Dow Corning Corporation | Compositions of resin-linear organosiloxane block copolymers |
JP6070964B2 (ja) * | 2012-03-27 | 2017-02-01 | 日産化学工業株式会社 | 自己組織化膜の下層膜形成組成物 |
JP6176248B2 (ja) * | 2012-07-19 | 2017-08-09 | 東レ株式会社 | ポリシロキサン組成物、電子デバイスおよび光学デバイス |
US20150346601A1 (en) * | 2013-04-26 | 2015-12-03 | Chi Mei Corporation | Photosensitive polysiloxane composition, protective film and element having the protective film |
JP6587065B2 (ja) | 2014-02-26 | 2019-10-09 | 日産化学株式会社 | レジストパターンに塗布されるポリマー含有塗布液 |
-
2017
- 2017-10-02 KR KR1020197008063A patent/KR102478337B1/ko active IP Right Grant
- 2017-10-02 US US16/339,489 patent/US20190292403A1/en active Pending
- 2017-10-02 JP JP2018543893A patent/JP7011229B2/ja active Active
- 2017-10-02 WO PCT/JP2017/035827 patent/WO2018066515A1/ja active Application Filing
- 2017-10-02 CN CN201780061137.XA patent/CN109790414B/zh active Active
- 2017-10-03 TW TW106134160A patent/TWI818900B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001033949A (ja) * | 1999-05-19 | 2001-02-09 | Fuji Photo Film Co Ltd | 平版印刷版用原版 |
JP2015038221A (ja) * | 2007-02-27 | 2015-02-26 | エイゼット・エレクトロニック・マテリアルズ・ユーエスエイ・コーポレイション | ケイ素に基づく反射防止膜用組成物 |
JP2009128564A (ja) * | 2007-11-22 | 2009-06-11 | Nissan Chem Ind Ltd | レジスト下層膜形成組成物及び半導体装置の製造方法 |
JP2011118373A (ja) * | 2009-10-30 | 2011-06-16 | Jsr Corp | 反転パターン形成方法及びポリシロキサン樹脂組成物 |
WO2016031563A1 (ja) * | 2014-08-25 | 2016-03-03 | 日産化学工業株式会社 | Socパターン上でのパターン反転のための被覆用組成物 |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190108828A (ko) * | 2018-03-15 | 2019-09-25 | 삼성전자주식회사 | 실리콘게르마늄 식각 전의 전처리 조성물 및 이를 이용한 반도체 장치의 제조 방법 |
KR102480348B1 (ko) | 2018-03-15 | 2022-12-23 | 삼성전자주식회사 | 실리콘게르마늄 식각 전의 전처리 조성물 및 이를 이용한 반도체 장치의 제조 방법 |
JP2020012951A (ja) * | 2018-07-17 | 2020-01-23 | 日産化学株式会社 | ポリカルボシラン含有組成物 |
JP7263708B2 (ja) | 2018-07-17 | 2023-04-25 | 日産化学株式会社 | ポリカルボシラン含有組成物 |
WO2020152976A1 (ja) * | 2019-01-24 | 2020-07-30 | 信越化学工業株式会社 | オルガノポリシロキサン化合物を含有する組成物 |
JP2020117632A (ja) * | 2019-01-24 | 2020-08-06 | 信越化学工業株式会社 | オルガノポリシロキサン化合物を含有する組成物 |
JP7120045B2 (ja) | 2019-01-24 | 2022-08-17 | 信越化学工業株式会社 | オルガノポリシロキサン化合物を含有する組成物 |
WO2021060495A1 (ja) * | 2019-09-27 | 2021-04-01 | Jsr株式会社 | 組成物、膜、膜形成方法、パターン形成方法、有機下層膜反転パターン形成方法及び組成物の製造方法 |
JPWO2021060495A1 (ja) * | 2019-09-27 | 2021-04-01 | ||
JP7405147B2 (ja) | 2019-09-27 | 2023-12-26 | Jsr株式会社 | 組成物、膜、膜形成方法、パターン形成方法、有機下層膜反転パターン形成方法及び組成物の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201823390A (zh) | 2018-07-01 |
KR20190059902A (ko) | 2019-05-31 |
CN109790414B (zh) | 2022-07-12 |
TWI818900B (zh) | 2023-10-21 |
JP7011229B2 (ja) | 2022-02-10 |
JPWO2018066515A1 (ja) | 2019-07-18 |
CN109790414A (zh) | 2019-05-21 |
KR102478337B1 (ko) | 2022-12-19 |
US20190292403A1 (en) | 2019-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102426414B1 (ko) | Soc 패턴 상에서의 패턴반전을 위한 피복용 조성물 | |
JP6319580B2 (ja) | スルホン酸オニウム塩を含有するケイ素含有euvレジスト下層膜形成組成物 | |
JP6436301B2 (ja) | エステル基を有するシリコン含有レジスト下層膜形成組成物 | |
JP6597980B2 (ja) | ハロゲン化スルホニルアルキル基を有するシリコン含有レジスト下層膜形成組成物 | |
JP6835062B2 (ja) | シリコン含有組成物を用いた半導体基板の平坦化方法 | |
JP7011229B2 (ja) | パターン反転のための被覆組成物 | |
JP6754098B2 (ja) | カーボネート骨格を有する加水分解性シランを含むリソグラフィー用レジスト下層膜形成組成物 | |
WO2016009965A1 (ja) | 脂肪族多環構造含有有機基を有するシリコン含有レジスト下層膜形成組成物 | |
JP6738049B2 (ja) | シリコン含有平坦化性パターン反転用被覆剤 | |
WO2016093172A1 (ja) | ハロゲン含有カルボン酸アミド基を有する加水分解性シランを含むリソグラフィー用レジスト下層膜形成組成物 | |
WO2020138092A1 (ja) | 水素ガスを用いた前処理によるレジスト下層膜のエッチング耐性を向上する方法 | |
JPWO2018181989A1 (ja) | カルボニル構造を有するシリコン含有レジスト下層膜形成組成物 | |
JP2023175874A (ja) | 保護されたフェノール基と硝酸を含むシリコン含有レジスト下層膜形成組成物 | |
JP7143763B2 (ja) | シリコン含有パターン反転用被覆剤 | |
JP7157392B2 (ja) | アルカリ性現像液可溶性シリコン含有レジスト下層膜形成組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17858353 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2018543893 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20197008063 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17858353 Country of ref document: EP Kind code of ref document: A1 |