WO2021251481A1 - ジオール構造を含む保護膜形成用組成物 - Google Patents
ジオール構造を含む保護膜形成用組成物 Download PDFInfo
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- WO2021251481A1 WO2021251481A1 PCT/JP2021/022277 JP2021022277W WO2021251481A1 WO 2021251481 A1 WO2021251481 A1 WO 2021251481A1 JP 2021022277 W JP2021022277 W JP 2021022277W WO 2021251481 A1 WO2021251481 A1 WO 2021251481A1
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- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0275—Photolithographic processes using lasers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3083—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/3086—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
Definitions
- the present invention relates to a composition for forming a protective film having excellent resistance to a wet etching solution for semiconductors in a lithography process in semiconductor manufacturing.
- the present invention also relates to a method for manufacturing a substrate with a resist pattern to which the protective film is applied, and a method for manufacturing a semiconductor device.
- Patent Document 1 discloses a protective film-forming composition for a wet etching solution for semiconductors, which comprises a compound containing at least one set of two hydroxyl groups adjacent to each other in a molecule, or a polymer thereof, and a solvent.
- Patent Document 2 discloses a resist underlayer film composition having excellent embedding property, which contains a resin obtained by reacting a resin containing an epoxy group with a compound having a thiol group.
- the protective film When a protective film for a semiconductor substrate is formed using the protective film forming composition and the underlying substrate is processed by wet etching using the protective film as an etching mask, the protective film has a good mask function for a wet etching solution for semiconductors (that is,). , The masked part can protect the substrate). Further, there is also a demand for a protective film forming composition which has good coverage even on a so-called stepped substrate, has a small difference in film thickness after embedding, and can form a flat film.
- an object of the present invention is to solve the above-mentioned problems.
- the present invention includes the following.
- the protective film forming composition for a wet etching solution for semiconductors according to [1] which is excellent in embedding in a narrow gap on a semiconductor substrate.
- the compound (A) has a 1,2-ethanediol structure as a structure containing at least one set of two hydroxyl groups adjacent to each other in the molecule.
- the protective film-forming composition according to the above.
- Ar represents a benzene ring, a naphthalene ring or an anthracene ring which may be substituted with a substituent
- X 1 represents an ether bond or an ester bond
- X 2 represents an ether bond or an ester bond. It represents either a sulfide bond or -NX 3- , where X 3 represents a hydrogen atom or a methyl group.
- the compound (A) containing no heterocycle having a weight average molecular weight of 1500 or less, having a structure containing at least one set of two hydroxyl groups adjacent to each other in the molecule, and an organic solvent are contained. Includes particles with an average particle size of 3 nm or less by dynamic light scattering, Resist underlayer film forming composition.
- the resist underlayer film forming composition according to [9] which is excellent in embedding in a narrow gap on a semiconductor substrate.
- Ar represents a benzene ring, a naphthalene ring or an anthracene ring which may be substituted with a substituent
- X 1 represents an ether bond or an ester bond
- X 2 represents an ether bond or an ester bond. It represents either a sulfide bond or -NX 3- , where X 3 represents a hydrogen atom or a methyl group.
- For manufacturing a semiconductor which comprises a step of applying the protective film forming composition according to any one of [1] to [7] onto a semiconductor substrate having a step and firing to form a protective film.
- the protective film composition or resist underlayer film forming composition according to any one of [1] to [7] or [9] to [15] is applied onto a semiconductor substrate and fired to obtain a resist underlayer film.
- a substrate with a resist pattern which comprises a step of forming a protective film as a coating film, and then a step of forming a resist film on the protective film and then exposing and developing to form a resist pattern, which is used for manufacturing a semiconductor. Production method.
- a protective film is formed on a semiconductor substrate on which an inorganic film may be formed on the surface using the protective film forming composition according to any one of [1] to [7], and the protective film is formed.
- a resist pattern is formed on the film, the protective film is dry-etched using the resist pattern as a mask, the surface of the inorganic film or the semiconductor substrate is exposed, and the protective film after dry etching is used as a mask for semiconductor wet.
- a method for manufacturing a semiconductor device which comprises a step of wet etching and cleaning the inorganic film or the semiconductor substrate using an etching solution.
- a resist underlayer film is formed on a semiconductor substrate on which an inorganic film may be formed on the surface by using the resist underlayer film forming composition according to any one of [9] to [15].
- a resist pattern is formed on the resist underlayer film, the resist underlayer film is dry-etched using the resist pattern as a mask, the surface of the inorganic film or the semiconductor substrate is exposed, and the resist underlayer film after dry etching is used as a mask.
- a method for manufacturing a semiconductor device comprising a step of etching the inorganic film or the semiconductor substrate.
- the protective film forming composition of the present invention is required to have, for example, the following characteristics in a well-balanced manner in the lithography process in semiconductor manufacturing. (1) It has a good masking function against wet etching liquid when processing a base substrate, (2) It reduces damage to the protective film or resist underlayer film when processing a substrate due to a low dry etching rate, and (3) Steps. Excellent flatness of the substrate, (4) Excellent embedding property in the fine trench pattern substrate, and having the performances of (1) to (4) in a well-balanced manner facilitates fine processing of the semiconductor substrate. It can be carried out.
- the protective film-forming composition of the present application has a structure containing at least one set of two hydroxyl groups adjacent to each other in the molecule at the end, a weight average molecular weight of 1500 or less, a compound (A) containing no heterocycle, and an organic solvent.
- a composition for forming a protective film against a wet etching solution for semiconductors which comprises, and is characterized in that the average particle size of the particles present in the composition is 3 nm or less by a dynamic light scattering method.
- the particles are derived from a compound having a large molecular weight, as will be described later.
- the weight average molecular weight can be measured, for example, by the gel permeation chromatography described in Examples.
- ⁇ Average particle size by dynamic light scattering method> When a compound (polymer) having a large molecular weight is present in the protective film forming composition referred to in the present application, it can be measured as particles by a dynamic light scattering method (DLS). Since the compound (A) of the present application has a small molecular weight of 1500 or less as compared with the polymer described in the so-called existing technology, the average particle size by DLS is 3 nm or less. More preferably, the average particle size is less than 3 nm, 2 nm or less, and 1 nm or less. The number of the average particle size on the left indicates the number of the detection limit at the time of measurement by the above-mentioned DLS measuring device. Due to the small average particle size, the compound of the present application is excellent in embedding property in a semiconductor substrate having a step such as a fine trench pattern substrate.
- the compound (A) preferably contains an aromatic hydrocarbon or an alicyclic hydrocarbon.
- the structure containing at least one set of two hydroxyl groups adjacent to each other in the molecule is preferably a 1,2-ethanediol structure.
- the compound preferably contains the following partial structure.
- Ar represents a benzene ring, a naphthalene ring or an anthracene ring which may be substituted with a substituent
- X 1 represents an ether bond or an ester bond
- X 2 represents an ether bond or an ester bond.
- X 1 represents an ether bond and X 2 represents a sulfide bond.
- the above-mentioned substituent may be substituted by means that a part or all of the hydrogen atoms present in the benzene ring, naphthalene ring or anthracene ring contained in Ar of the present application is, for example, a hydroxy group, a halogen atom or a carboxyl group. , Nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, amino group or alkoxy group having 1 to 9 carbon atoms may be substituted.
- alkoxy group having 1 to 9 carbon atoms examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group and a t-butoxy group.
- n-pentoxy group 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n -Propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-Methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n- Butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n -Butoxy group, 1,1,2-trimethyl-n
- Compound (A) having a structure containing at least one set of two hydroxyl groups adjacent to each other in the molecule, having a molecular weight of 1500 or less, and not containing a heterocycle is not limited as long as it is a compound having a structure containing at least one set of two hydroxyl groups adjacent to each other in the molecule at the terminal, having a molecular weight of 1500 or less and not containing a heterocycle, but is not limited to the formula (1). ) Is preferably included.
- the compound containing the partial structure of the compound formula (1) include the compounds represented by the following formulas (a-1) to (a-43) (that is, an ester bond, an ether bond, and a carbon atom in one molecule.
- alkyl group having 1 to 10 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, and t-.
- alkylene group having 1 to 10 carbon atoms examples include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group and a t-butylene group.
- Cyclobutylene group 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene Group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, cyclopentylene group, 1- Methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-Ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-
- alkenyl group having 3 to 6 carbon atoms examples include 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 2-methyl.
- the weight average molecular weight of the compound containing the partial structure of the formula (1) is 1500 or less, 1400 or less, 1200 or less, 1000 or less, 900 or less, 800 or less, 700 or less. It is preferably 600 or less.
- the protective film-forming composition of the present invention can be prepared by dissolving each of the above components in an organic solvent, and is used in a uniform solution state.
- the organic solvent of the protective film forming composition according to the present invention can be used without particular limitation as long as it is an organic solvent capable of dissolving the above compound or a solid component such as the acid catalyst described below.
- the protective film forming composition according to the present invention is used in a uniform solution state, it is recommended to use an organic solvent generally used in the lithography process in combination in consideration of its coating performance. ..
- organic solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
- propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone and the like are preferable.
- propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable.
- the protective film-forming composition of the present application may further contain an acid catalyst.
- an acid catalyst in addition to an acidic compound and a basic compound, a compound that generates an acid or a base by heat can be used.
- a sulfonic acid compound or a carboxylic acid compound can be used, and as the compound that generates an acid by heat, a thermal acid generator can be used.
- Nart salicylic acid, camphor sulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzene sulfonic acid, 4-phenol sulfonic acid, pyridinium-4-phenol sulfonate, benzene disulfonic acid, 1-naphthalene sulfonic acid, 4-nitrobenzene sulfonic acid, citric acid , Sulfonic acid, hydroxy sulphonic acid and the like.
- thermoacid generator examples include K-PURE [registered trademark] CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, and TAG2689 (all manufactured by King Industries). And SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).
- acid catalysts can be used alone or in combination of two or more. Further, as the basic compound, an amine compound or an ammonium hydroxide compound can be used, and as the compound for which a base is generated by heat, urea can be used.
- Examples of the amine compound include triethanolamine, tributanolamine, trimethylamine, triethylamine, trinormalpropylamine, triisopropylamine, trinormalbutylamine, tri-tert-butylamine, trinormaloctylamine, triisopropanolamine, phenyldiethanolamine and stearyl.
- Examples thereof include diethanolamine and tertiary amines such as diazabicyclooctane, and aromatic amines such as pyridine and 4-dimethylaminopyridine.
- primary amines such as benzylamine and normal butylamine, and secondary amines such as diethylamine and dinormal butylamine are also mentioned as amine compounds. These amine compounds can be used alone or in combination of two or more.
- ammonium hydroxide compound examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, and cetyltrimethylammonium hydroxide. Examples thereof include phenyltrimethylammonium hydroxide and phenyltriethylammonium hydroxide.
- the compound for which a base is generated by heat for example, a compound having a heat unstable group such as an amide group, a urethane group or an aziridine group and producing an amine by heating can be used.
- a compound having a heat unstable group such as an amide group, a urethane group or an aziridine group and producing an amine by heating
- urea benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyldimethylphenylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltributylammonium chloride, and choline chloride are also mentioned as compounds that generate a base by heat.
- the protective film-forming composition of the present application contains an acid catalyst
- the content thereof is 0.0001 to 20% by mass, preferably 0.01 to 15% by mass, based on the total solid content of the protective film-forming composition. More preferably, it is 0.1 to 10% by mass.
- the solid content of the protective film forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass.
- the solid content is the content ratio of all the components excluding the solvent from the protective film forming composition.
- the proportion of the polymer in the solid content is preferably 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass in this order.
- the resist underlayer film forming composition of the present application contains a compound having a structure containing at least one set of two hydroxyl groups adjacent to each other in the molecule at the end, having a weight average molecular weight of 1500 or less, and containing no heterocycle, and an organic solvent.
- a resist underlayer film forming composition characterized in that the average particle size of the particles present in the composition is 3 nm or less by a dynamic light scattering method.
- the weight average molecular weight measurement and the average particle size measurement by the dynamic light scattering method are as described above.
- the compound preferably contains an aromatic hydrocarbon or an alicyclic hydrocarbon.
- the structure containing at least one set of two hydroxyl groups adjacent to each other in the molecule is preferably a 1,2-ethanediol structure. It is preferable that the compound contains the following partial structure.
- Ar represents a benzene ring, a naphthalene ring or an anthracene ring which may be substituted with a substituent
- X 1 represents an ether bond or an ester bond
- X 2 represents an ether bond or an ester bond.
- X 1 represents an ether bond and X 2 represents a sulfide bond.
- the acid catalyst, the content of the acid catalyst and the organic solvent are the same as those of the above-mentioned protective film forming composition.
- the solid content of the resist underlayer film forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass.
- the solid content is the content ratio of all the components excluding the solvent from the protective film forming composition.
- the proportion of the polymer in the solid content is preferably 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass in this order.
- the resist underlayer film forming composition of the present invention can contain a cross-linking agent.
- the cross-linking agent include melamine-based, substituted urea-based, and polymers thereof.
- it is a cross-linking agent having at least two cross-linking substituents, such as methoxymethylated glycol uryl, butoxymethylated glycol uryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine.
- It is a compound such as methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Further, a condensate of these compounds can also be used.
- a cross-linking agent having high heat resistance can be used as the cross-linking agent.
- a compound containing a cross-linking substituent having an aromatic ring for example, a benzene ring or a naphthalene ring
- examples of such a compound include a compound having a partial structure of the following formula (5-1) and a polymer or oligomer having a repeating unit of the following formula (5-2).
- R 11 , R 12 , R 13 and R 14 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and specific examples of these alkyl groups are as described above.
- m1 is 1 ⁇ m1 ⁇ 6-m2
- m2 is 1 ⁇ m2 ⁇ 5
- m3 is 1 ⁇ m3 ⁇ 4-m2
- m4 is 1 ⁇ m4 ⁇ 3.
- the compounds, polymers and oligomers of formula (5-1) and formula (5-2) are exemplified below.
- the above compounds can be obtained as products of Asahi Organic Materials Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd.
- the compound of the formula (6-22) can be obtained by Asahi Organic Materials Industry Co., Ltd. under the trade name TMOM-BP.
- the amount of the cross-linking agent added varies depending on the coating solvent used, the underlying substrate used, the required solution viscosity, the required film shape, etc., but is usually 0.001 with respect to the total solid content of the protective film forming composition. It is -80% by mass, preferably 0.01 to 50% by mass, and more preferably 0.1 to 40% by mass.
- These cross-linking agents may cause a cross-linking reaction by self-condensation, but if cross-linking substituents are present in the above-mentioned polymer of the present invention, they can cause a cross-linking reaction with those cross-linking substituents.
- the substrate with a resist pattern according to the present invention can be manufactured by applying the above-mentioned protective film forming composition (resist underlayer film forming composition) onto a semiconductor substrate and firing it.
- protective film forming composition resist underlayer film forming composition
- Examples of the semiconductor substrate to which the protective film forming composition (resist underlayer film forming composition) of the present invention is applied include silicon wafers, germanium wafers, and gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride. Examples thereof include compound semiconductor wafers such as.
- the inorganic film can be, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum deposition. It is formed by a method, a spin coating method (spin-on-glass: SOG).
- the inorganic film examples include a polysilicon film, a silicon oxide film, a silicon nitride film, a silicon nitride film, a BPSG (Boro-Phospho Silicone Glass) film, a titanium nitride film, a titanium oxynitride film, a tungsten nitride film, and a gallium arsenide film. , And a gallium arsenide film.
- the semiconductor substrate may be a stepped substrate on which so-called vias (holes), trenches (grooves) and the like are formed.
- the via has a substantially circular shape when viewed from the upper surface, and the diameter of the circle is, for example, 1 nm to 20 nm and the depth is 50 nm to 500 nm. Is 50 nm to 500 nm.
- the protective film-forming composition (resist underlayer film-forming composition) of the present application has a small weight average molecular weight and average particle size of the compounds contained in the composition, voids (voids) and the like can be formed on the stepped substrate as described above.
- the composition can be embedded without defects. It is an important characteristic that there are no defects such as voids for the next process of semiconductor manufacturing (wet etching / dry etching of semiconductor substrate, resist pattern formation).
- the protective film forming composition (resist underlayer film forming composition) of the present invention is applied onto such a semiconductor substrate by an appropriate coating method such as a spinner or a coater. Then, a protective film (resist underlayer film) is formed by baking using a heating means such as a hot plate.
- the baking conditions are appropriately selected from a baking temperature of 100 ° C. to 400 ° C. and a baking time of 0.3 minutes to 60 minutes.
- the bake temperature is preferably 120 ° C. to 350 ° C. and the bake time is 0.5 minutes to 30 minutes, and more preferably the bake temperature is 150 ° C. to 300 ° C. and the bake time is 0.8 minutes to 10 minutes.
- the film thickness of the protective film formed is, for example, 0.001 ⁇ m to 10 ⁇ m, preferably 0.002 ⁇ m to 1 ⁇ m, and more preferably 0.005 ⁇ m to 0.5 ⁇ m. If the temperature at the time of baking is lower than the above range, the cross-linking becomes insufficient, and it is difficult to obtain the resistance of the formed protective film ((resist underlayer film forming composition) to the resist solvent or the basic hydrogen peroxide aqueous solution). On the other hand, if the temperature at the time of baking is higher than the above range, the protective film (resist underlayer film) may be decomposed by heat.
- the exposure is performed through a mask (reticle) for forming a predetermined pattern, and for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used.
- An alkaline developer is used for development, and the development temperature is appropriately selected from 5 ° C. to 50 ° C. and the development time is 10 seconds to 300 seconds.
- the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and the like.
- Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and the like.
- An aqueous solution of an alkali such as a quaternary ammonium salt, cyclic amines such as pyrrole and piperidine can be used.
- an alcohol such as isopropyl alcohol and a surfactant such as a nonionic surfactant can be added to the aqueous solution of the alkalis in an appropriate amount for use.
- the preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline.
- a surfactant or the like can be added to these developers.
- a method of developing with an organic solvent such as butyl acetate to develop a portion of the photoresist in which the alkali dissolution rate has not been improved can also be used.
- the protective film (resist underlayer film forming composition) is dry-etched using the formed resist pattern as a mask. At that time, when the inorganic film is formed on the surface of the used semiconductor substrate, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the used semiconductor substrate, the semiconductor substrate is exposed. Expose the surface.
- a wet etching solution for semiconductors is applied. By wet etching using, the desired pattern is formed.
- etching solution for semiconductors a general chemical solution for etching a wafer for semiconductors can be used, and for example, a substance showing acidity and a substance showing basicity can be used.
- Examples of the substance showing acidity include hydrogen peroxide, phosphoric acid, ammonium fluoride, acidic ammonium fluoride, ammonium hydrogenfluoride, buffered ammonium fluoride, hydrochloric acid, nitrate, sulfuric acid, phosphoric acid or a mixture thereof. ..
- organic amines such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, and triethanolamine are mixed with hydrogen peroxide solution to make the pH basic.
- Ammonia solution can be mentioned. Specific examples include SC-1 (ammonia-hydrogen peroxide solution).
- SC-1 ammonia-hydrogen peroxide solution
- those that can make the pH basic for example, those that mix urea and hydrogen peroxide solution and cause thermal decomposition of urea by heating to generate ammonia, and finally make the pH basic.
- acidic hydrogen peroxide solution or basic hydrogen peroxide solution is preferable.
- These chemicals may contain additives such as surfactants.
- the operating temperature of the wet etching solution for semiconductors is preferably 25 ° C to 90 ° C, and more preferably 40 ° C to 80 ° C.
- the wet etching time is preferably 0.5 minutes to 30 minutes, and more preferably 1 minute to 20 minutes.
- the weight average molecular weight of the compounds shown in the following synthetic examples of the present specification is a measurement result by gel permeation chromatography (hereinafter, abbreviated as GPC).
- GPC gel permeation chromatography
- a GPC device manufactured by Tosoh Corporation is used for the measurement, and the measurement conditions and the like are as follows.
- GPC column Shodex [registered trademark] (Showa Denko KK) Column temperature: 40 ° C
- Solvent Tetrahydrofuran (THF)
- Flow rate 1.0 ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)
- ⁇ Synthesis example 1 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane (manufactured by DIC Corporation, product name EPICLON HP-4700) 8.00 g, thioglycerol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- the obtained reaction product is represented by the formula (D-1).
- GPC analysis of the obtained reaction product revealed a weight average molecular weight of 546 in terms of standard polystyrene.
- the obtained reaction product is represented by the formula (D-2).
- GPC analysis of the obtained reaction product revealed a weight average molecular weight of 552 in terms of standard polystyrene.
- Got The obtained reaction product is represented by the formula (D-7).
- GPC analysis of the obtained reaction product revealed a weight average molecular weight of 456 in terms of standard polystyrene.
- Example 1 To 3.20 g of the solution containing the reaction product obtained in Synthesis Example 1, 0.0036 g of pyridinium trifluoromethanesulfonic acid, 0.96 g of propylene glycol monomethyl ether acetate and 5.83 g of propylene glycol monomethyl ether were added to prepare the solution. did. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
- Example 2 To 2.28 g of the solution containing the reaction product obtained in Synthesis Example 2, 0.0036 g of pyridinium trifluoromethanesulfonic acid, 0.96 g of propylene glycol monomethyl ether acetate and 6.75 g of propylene glycol monomethyl ether were added to the solution. did. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
- Example 3 To 4.97 g of the solution containing the reaction product obtained in Synthesis Example 3, 0.0053 g of pyridinium trifluoromethanesulfonic acid, 1.45 g of propylene glycol monomethyl ether acetate and 8.58 g of propylene glycol monomethyl ether were added to prepare the solution. did. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
- Example 4 To 2.61 g of the solution containing the reaction product obtained in Synthesis Example 4, 0.0036 g of pyridinium trifluoromethanesulfonic acid, 0.96 g of propylene glycol monomethyl ether acetate and 6.42 g of propylene glycol monomethyl ether were added to prepare the solution. did. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
- Example 5 To 2.39 g of the solution containing the reaction product obtained in Synthesis Example 5, 0.0036 g of pyridinium trifluoromethanesulfonic acid, 0.96 g of propylene glycol monomethyl ether acetate and 6.65 g of propylene glycol monomethyl ether were added to prepare the solution. did. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
- Example 6 To 3.63 g of the solution containing the reaction product obtained in Synthesis Example 6, 0.0041 g of pyridinium trifluoromethanesulfonic acid, 1.11 g of propylene glycol monomethyl ether acetate and 6.76 g of propylene glycol monomethyl ether were added to the solution. did. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
- Example 7 To 3.46 g of the solution containing the reaction product obtained in Synthesis Example 7, 0.0041 g of pyridinium trifluoromethanesulfonic acid, 1.11 g of propylene glycol monomethyl ether acetate and 6.93 g of propylene glycol monomethyl ether were added to prepare the solution. did. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
- Example 8 To 3.46 g of the solution containing the reaction product obtained in Synthesis Example 8, 0.0041 g of pyridinium trifluoromethanesulfonic acid, 1.11 g of propylene glycol monomethyl ether acetate and 6.93 g of propylene glycol monomethyl ether were added to the solution. did. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
- Each of the protective film-forming composition prepared in Examples 1 to 8 and the protective film-forming composition prepared in Comparative Example 1 was applied by spin coating on a silicon substrate having a titanium nitride film formed on the surface. By baking at 250 ° C. for 60 seconds, a coating film having a film thickness of 100 nm was prepared.
- the protective film-forming compositions prepared in Examples 1 to 8 have particles in the protective film-forming composition (varnish) as compared with the protective film-forming composition prepared in Comparative Example 1. It was shown that the diameter was small.
- the silicon oxide film formed by depositing a silicon oxide film of about 20 nm on a silicon substrate having a 50 nm trench (L (line) / S (space)) formed as a schematic diagram in FIG. 1 by the CVD method is the trench surface.
- Each of the protective film forming compositions prepared in Examples 1 to 8 is spun on a silicon processed substrate (after silicon oxide film deposition: 10 nm trench (L (line) / S (space)))) formed in the portion.
- a coating film having a film thickness of 100 nm was prepared by applying with a coat and baking at 250 ° C. for 60 seconds.
- the protective film forming composition of the comparative example can be applied to a substrate having a fine trench having a line width of 3 nm or less, for example. It can be expected that the implantability is good in comparison with.
- the coating film prepared by using the protective film forming composition prepared in Examples 1 to 8 has sufficient resistance to the basic hydrogen peroxide aqueous solution. That is, it was found that these coating films can serve as a protective film against a basic aqueous hydrogen peroxide solution. On the other hand, it was found that the coating film prepared by using the film-forming composition prepared in Comparative Example 1 was insufficient as a protective film against a basic hydrogen peroxide aqueous solution.
- the protective film-forming composition (resist underlayer film-forming composition) prepared in Examples 1 to 8 and Comparative Example 1 described in the present specification was applied onto a silicon wafer by a spinner, respectively. It was baked on a hot plate at 250 ° C. for 1 minute to form a resist underlayer film (film thickness 50 nm). Then, for these protective film forming compositions, a spectroscopic ellipsometer (JA Woollam, VUV-VASE VU-302) was used, and the n value (refractive index) and k value (attenuation coefficient or) at wavelengths of 193 nm and 248 nm were used. Absorption coefficient) was measured. The results are shown in Table 4.
- the protective film-forming composition (resist underlayer film-forming composition) prepared in Examples 1 to 8 and Comparative Example 1 described in the present specification was applied onto a silicon wafer by a spin coater, respectively. It was baked on a hot plate at 250 ° C. for 1 minute to form a resist underlayer film. Then, using a dry etching apparatus (RIE-10NR) manufactured by SAMCO, the dry etching rate (decrease in film thickness per unit time) was measured under the condition that CF 4 was used as the dry etching gas.
- the dry etching rate of the protective film forming composition prepared in Examples 1 to 8 described in the present specification was compared with the dry etching rate of Comparative Example 1. Table 4 shows the dry etching rate of the protective film forming composition of each example as a selection ratio when the dry etching rate of Comparative Example 1 is 1.00.
- the protective film forming composition according to the present invention has excellent resistance when a wet etching solution is applied to substrate processing and has a low dry etching rate, so that it provides a protective film with low damage to the protective film during substrate processing. It is something to do.
- the resist underlayer film forming composition according to the present invention has excellent resistance when a wet etching solution is applied to substrate processing, has a low dry etching rate, and is excellent in resistance when applying a wet etching solution to substrate processing. ..
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Abstract
Description
さらには、いわゆる段差基板に対しても被覆性が良好で、埋め込み後の膜厚差が小さく、平坦な膜を形成し得る保護膜形成組成物も求められている。
従来、ウエットエッチング薬液の一種であるSC-1(アンモニア-過酸化水素溶液)に対する耐性を発現させるためには、低分子化合物(例えば没食子酸)を添加剤として適用する手法が用いられていたが、上記の課題を解決するには限界があった。
さらに上記目的で用いられる保護膜は、いわゆるレジストパターン形成時のトラブル(形状不良等)を解決するためのレジスト下層膜としての機能を有することが期待される。
本発明の目的は、上記の課題を解決することである。
[1] 分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造を末端に有する、重量平均分子量が1500以下の、複素環を含まない化合物(A)、及び有機溶剤を含み、
動的光散乱法による平均粒子径が3nm以下である粒子を含む、
半導体用ウエットエッチング液に対する保護膜形成組成物。
[2] 半導体基板上の狭ギャップへの埋め込み性に優れる、[1]に記載の半導体用ウエットエッチング液に対する保護膜形成組成物。
[3] 前記化合物(A)が、芳香族炭化水素又は脂環式炭化水素を含む、[1]又は[2]に記載の保護膜形成組成物。
[4] 前記化合物(A)が、前記分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造として、1,2-エタンジオール構造を有する、[1]~[3]何れか1項に記載の保護膜形成組成物。
[5] 前記化合物(A)が下記の部分構造を含む、[1]~[4]いずれか1項に記載の半導体用ウエットエッチング液に対する保護膜形成組成物。
(式(1)中、Arは、置換基で置換されていてもよいベンゼン環、ナフタレン環又はアントラセン環を表し、X1はエーテル結合又はエステル結合を表し、X2はエーテル結合、エステル結合、スルフィド結合又は-NX3-のいずれかを表し、X3は水素原子又はメチル基を表す。)
[6] 上記式(1)のX1がエーテル結合を表し、X2がスルフィド結合を表す、[5]に記載の半導体用ウエットエッチング液に対する保護膜形成組成物。
[7] 酸触媒をさらに含む、[1]~[6]のいずれか1項に記載の保護膜形成組成物。
[8] [1]~[7]のいずれか1項に記載の保護膜形成組成物からなる塗布膜の焼成物であることを特徴とする保護膜。
[9] 分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造を末端に有する、重量平均分子量が1500以下の、複素環を含まない化合物(A)、及び有機溶剤を含み、
動的光散乱法による平均粒子径が3nm以下である粒子を含む、
レジスト下層膜形成組成物。
[10] 半導体基板上の狭ギャップへの埋め込み性に優れる、[9]に記載のレジスト下層膜形成組成物。
[11] 前記化合物(A)が、芳香族炭化水素又は脂環式炭化水素を含む、[9]又は[10]に記載のレジスト下層膜形成組成物。
[12] 前記化合物(A)が、前記分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造として、1,2-エタンジオール構造を有する、[9]~[11]何れか1項に記載のレジスト下層膜形成組成物。
[13] 前記化合物(A)が下記の部分構造を含む、[9]~[12]何れか1項に記載のレジスト下層膜形成組成物。
(式(1)中、Arは、置換基で置換されていてもよいベンゼン環、ナフタレン環又はアントラセン環を表し、X1はエーテル結合又はエステル結合を表し、X2はエーテル結合、エステル結合、スルフィド結合又は-NX3-のいずれかを表し、X3は水素原子又はメチル基を表す。)
[14] 上記式(1)のX1がエーテル結合を表し、X2がスルフィド結合を表す、[13]に記載のレジスト下層膜形成組成物。
[15] 酸触媒及び/又は架橋剤をさらに含む、[9]~[14]何れか1項に記載のレジスト下層膜形成組成物。
[16] [9]~[15]のいずれか1項に記載のレジスト下層膜形成組成物からなる塗布膜の焼成物であることを特徴とするレジスト下層膜。
[17] [1]~[7]のいずれか1項に記載の保護膜形成組成物を、段差を有する半導体基板上に塗布し焼成して保護膜を形成する工程を含む、半導体の製造に用いることを特徴とする保護膜付き基板の製造方法。
[18] [1]~[7]又は[9]~[15]のいずれか1項に記載の保護膜組成物又はレジスト下層膜形成組成物を半導体基板上に塗布し焼成してレジスト下層膜としての保護膜を形成する工程、該保護膜上にレジスト膜を形成し、次いで露光、現像してレジストパターンを形成する工程を含み、半導体の製造に用いることを特徴とするレジストパターン付き基板の製造方法。
[19] 表面に無機膜が形成されていてもよい半導体基板上に、[1]~[7]のいずれか1項に記載の保護膜形成組成物を用いて保護膜を形成し、前記保護膜上にレジストパターンを形成し、前記レジストパターンをマスクとして前記保護膜をドライエッチングし、前記無機膜又は前記半導体基板の表面を露出させ、ドライエッチング後の前記保護膜をマスクとして、半導体用ウエットエッチング液を用いて前記無機膜又は前記半導体基板をウエットエッチング及び洗浄する工程を含む半導体装置の製造方法。
[20] 表面に無機膜が形成されていてもよい半導体基板上に、[9]~[15]いずれか1項に記載のレジスト下層膜形成組成物を用いてレジスト下層膜を形成し、前記レジスト下層膜上にレジストパターンを形成し、前記レジストパターンをマスクとして前記レジスト下層膜をドライエッチングし、前記無機膜又は前記半導体基板の表面を露出させ、ドライエッチング後の前記レジスト下層膜をマスクとして、前記無機膜又は前記半導体基板をエッチングする工程を含む半導体装置の製造方法。
本願の保護膜形成組成物は、分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造を末端に有する、重量平均分子量が1500以下の、複素環を含まない化合物(A)、及び有機溶剤を含む、半導体用ウエットエッチング液に対する保護膜形成組成物であり、該組成物中に存在する粒子の、動的光散乱法による平均粒子径が3nm以下であることを特徴とする。上記粒子は、後述するように分子量が大きい化合物に由来する。
上記重量平均分子量は、例えば実施例に記載のゲルパーミエーションクロマトグラフィーにより測定することが出来る。
本願でいう保護膜形成組成物中に、分子量が大きい化合物(重合体)が存在する場合、動的光散乱法(DLS)により粒子として測定できる。本願の上記化合物(A)は、いわゆる既存技術に記載の重合体と比較し、分子量が1500以下と小さいため、DLSによる平均粒子径が3nm以下である。さらに好ましくは平均粒子径が3nm未満であり、2nm以下であり、1nm以下である。左記の平均粒子径の数字は、上記のDLSの測定装置で、測定時点における検出限界の数字を示すことになる。平均粒子径が小さいことにより、本願の前記化合物は、微細なトレンチパターン基板等、段差を有する半導体基板への埋め込み性に優れる。
前記分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造が、1,2-エタンジオール構造であることが好ましい。
上記化合物が、下記の部分構造を含むことが好ましい。
(式(1)中、Arは、置換基で置換されていてもよいベンゼン環、ナフタレン環又はアントラセン環を表し、X1はエーテル結合又はエステル結合を表し、X2はエーテル結合、エステル結合、スルフィド結合又は-NX3-のいずれかを表し、X3は水素原子又はメチル基を表す。)
上記X1がエーテル結合を表し、X2がスルフィド結合を表すことが好ましい。
本願の化合物(A)は、分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造を末端に有する、分子量が1500以下の、複素環を含まない化合物であれば限定されないが、式(1)の部分構造を含むことが好ましい。化合物式(1)の部分構造を含む化合物の具体例としては、下記式(a-1)~(a-43)で表される化合物(すなわち1分子内に、エステル結合、エーテル結合、炭素原子数1~10のアルキレン基及び/又は窒素原子で連結されたエポキシ基を2~4個有する、水素原子が炭素原子数1~10のアルキル基、炭素原子数3~6のアルケニル基及び/又はケトン基で置換されていてもよい芳香族炭化水素又は脂環式炭化水素を含む化合物、該エポキシ基はグリシジルエーテル基であってもよい)と、下記式(b-1)~(b-4)で表される化合物(すなわち、分子内にチオール基、アミノ基、メチルアミノ基及び/又はカルボキシ基等のエポキシ基と反応する有機基を有する、その末端に1,2-エタンジオール構造を有する化合物)とを公知の方法で反応させて得た反応生成物であることが好ましい。
本発明の保護膜形成組成物は、上記各成分を、有機溶剤に溶解させることによって調製でき、均一な溶液状態で用いられる。
当該酸触媒としては、酸性化合物、塩基性化合物に加え、熱により酸又は塩基が発生する化合物を用いることができる。酸性化合物としては、スルホン酸化合物又はカルボン酸化合物を用いることができ、熱により酸が発生する化合物としては、熱酸発生剤を用いることができる。
本願のレジスト下層膜形成組成物は、分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造を末端に有する、重量平均分子量が1500以下の、複素環を含まない化合物及び、有機溶剤を含む、レジスト下層膜形成組成物であり、該組成物中に存在する粒子の、動的光散乱法による平均粒子径が3nm以下であることを特徴とする。
前記分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造が、1,2-エタンジオール構造であることが好ましい。
前記化合物が下記の部分構造を含むことが好ましい。
(式(1)中、Arは、置換基で置換されていてもよいベンゼン環、ナフタレン環又はアントラセン環を表し、X1はエーテル結合又はエステル結合を表し、X2はエーテル結合、エステル結合、スルフィド結合又は-NX3-のいずれかを表し、X3は水素原子又はメチル基を表す。)
上記X1がエーテル結合を表し、X2がスルフィド結合を表すことが好ましい。
本発明のレジスト下層膜形成組成物は架橋剤を含むことができる。その架橋剤としては、メラミン系、置換尿素系、またはそれらのポリマー系等が挙げられる。好ましくは、少なくとも2個の架橋形成置換基を有する架橋剤であり、メトキシメチル化グリコールウリル、ブトキシメチル化グリコールウリル、メトキシメチル化メラミン、ブトキシメチル化メラミン、メトキシメチル化ベンゾグワナミン、ブトキシメチル化ベンゾグワナミン、メトキシメチル化尿素、ブトキシメチル化尿素、メトキシメチル化チオ尿素、またはメトキシメチル化チオ尿素等の化合物である。また、これらの化合物の縮合体も使用することができる。
このような化合物としては、下記式(5-1)の部分構造を有する化合物や、下記式(5-2)の繰り返し単位を有するポリマー又はオリゴマーが挙げられる。
m1は1≦m1≦6-m2、m2は1≦m2≦5、m3は1≦m3≦4-m2、m4は1≦m4≦3である。
式(5-1)及び式(5-2)の化合物、ポリマー、オリゴマーは以下に例示される。
以下、本発明に係る保護膜形成組成物(レジスト下層膜形成組成物)を用いたレジストパターン付き基板の製造方法及び半導体装置の製造方法について説明する。
本明細書の下記合成例に示す化合物の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(以下、GPCと略称する)による測定結果である。測定には東ソー(株)製GPC装置を用い、測定条件等は次のとおりである。
GPCカラム:Shodex〔登録商標〕(昭和電工(株))
カラム温度:40℃
溶媒:テトラヒドロフラン(THF)
流量:1.0ml/分
標準試料:ポリスチレン(東ソー(株)製)
1,1-ビス(2,7-ジグリシジルオキシ-1-ナフチル)メタン(DIC(株)製、製品名EPICLON HP-4700)8.00g、チオグリセロール(富士フイルム和光純薬(株)製)8.00g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))0.63gを、プロピレングリコールモノメチルエーテル78.44gに溶解させた後、110℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物は式(D-1)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量546であった。
1,1’―メチレンビス(2-グリシジルオキシナフタレン)(DIC(株)製、製品名EPICLON HP-4770)11.00g、チオグリセロール(富士フイルム和光純薬(株)製)6.12g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))0.69gを、プロピレングリコールモノメチルエーテル71.23gに溶解させた後、110℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物は式(D-2)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量552であった。
テトラフェニルオールエタンテトラグリシジルエーテル(日本化薬(株)製、製品名1031S)6.00g、チオグリセロール(富士フイルム和光純薬(株)製)4.84g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))0.37gを、プロピレングリコールモノメチルエーテル44.81gに溶解させた後、110℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物は式(D-3)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量1385であった。
2-[4-(2,3-エポキシプロポキシ)フェニル]-2-(4-[1,1-ビス[4-([2,3-エポキシプロポキシ]フェニル)エチル]フェニル]プロパン(三菱ケミカル(株)製、製品名NC-6000)6.00g、チオグリセロール(富士フイルム和光純薬(株)製)4.84g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))0.37gを、プロピレングリコールモノメチルエーテル44.81gに溶解させた後、110℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物の式(D-4)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量950であった。
市販のエポキシ樹脂(DIC(株)製、製品名EPICLON HP-6000)12.13g、チオグリセロール(富士フイルム和光純薬(株)製)1.73g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))0.19gを、プロピレングリコールモノメチルエーテル56.20gに溶解させた後、110℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物は式(D-5)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量613であった。
1,3-ジグリシジルオキシベンゼン(ナガセケムテックス(株)製、製品名EX-201)9.97g、チオグリセロール(富士フイルム和光純薬(株)製)10.01g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))1.12gを、プロピレングリコールモノメチルエーテル84.41gに溶解させた後、110℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物は式(D-6)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量482であった。
1,6-ナフタレンジオールグリシジルエーテル(DIC(株)製、製品名EPICRON(登録商標)HP-4032D)9.51g、チオグリセロール(富士フイルム和光純薬(株)製)7.36g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))0.82gを、プロピレングリコールモノメチルエーテル84.64gに溶解させた後、110℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物は式(D-7)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量456であった。
ハイドロキノン型結晶性エポキシ樹脂(日鉄ケミカル&マテリアル株式会社(株)製、製品名YDC-1312)10.00g、チオグリセロール(富士フイルム和光純薬(株)製)6.45g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))0.72gを、プロピレングリコールモノメチルエーテル68.70gに溶解させた後、110℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物は式(D-8)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量588であった。
1,3-ジグリシジルオキシベンゼン(ナガセケムテックス(株)製、製品名EX-201)59.80g、コハク酸(東京化成工業(株))14.00g、チオグリセロール(富士フイルム和光純薬(株)製)2.85g及び触媒としてテトラブチルホスホニウム ブロミド(北興化学(株))3.35gを、プロピレングリコールモノメチルエーテル320.00gに溶解させた後、100℃で24時間反応させ、反応生成物を含有する溶液(固形分20質量%)を得た。得られた反応生成物は式(D-9)で表される。得られた反応生成物のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量4772であった。
合成例1で得られた反応生成物を含有する溶液3.20gに、ピリジニウムトリフルオロメタンスルホン酸0.0036g、プロピレングリコールモノメチルエーテルアセテート0.96g及びプロピレングリコールモノメチルエーテル5.83gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
合成例2で得られた反応生成物を含有する溶液2.28gに、ピリジニウムトリフルオロメタンスルホン酸0.0036g、プロピレングリコールモノメチルエーテルアセテート0.96g及びプロピレングリコールモノメチルエーテル6.75gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
合成例3で得られた反応生成物を含有する溶液4.97gに、ピリジニウムトリフルオロメタンスルホン酸0.0053g、プロピレングリコールモノメチルエーテルアセテート1.45g及びプロピレングリコールモノメチルエーテル8.58gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
合成例4で得られた反応生成物を含有する溶液2.61gに、ピリジニウムトリフルオロメタンスルホン酸0.0036g、プロピレングリコールモノメチルエーテルアセテート0.96g及びプロピレングリコールモノメチルエーテル6.42gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
合成例5で得られた反応生成物を含有する溶液2.39gに、ピリジニウムトリフルオロメタンスルホン酸0.0036g、プロピレングリコールモノメチルエーテルアセテート0.96g及びプロピレングリコールモノメチルエーテル6.65gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
合成例6で得られた反応生成物を含有する溶液3.63gに、ピリジニウムトリフルオロメタンスルホン酸0.0041g、プロピレングリコールモノメチルエーテルアセテート1.11g及びプロピレングリコールモノメチルエーテル6.76gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
合成例7で得られた反応生成物を含有する溶液3.46gに、ピリジニウムトリフルオロメタンスルホン酸0.0041g、プロピレングリコールモノメチルエーテルアセテート1.11g及びプロピレングリコールモノメチルエーテル6.93gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
合成例8で得られた反応生成物を含有する溶液3.46gに、ピリジニウムトリフルオロメタンスルホン酸0.0041g、プロピレングリコールモノメチルエーテルアセテート1.11g及びプロピレングリコールモノメチルエーテル6.93gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
合成例9で得られた反応生成物を含有する溶液59.65gに、ピリジニウムトリフルオロメタンスルホン酸0.48g、プロピレングリコールモノメチルエーテルアセテート24.00g及びプロピレングリコールモノメチルエーテル165.86gを添加し、溶液とした。その溶液を、孔径0.02μmのポリエチレン製ミクロフィルターを用いてろ過することで、保護膜形成組成物を調製した。
窒化チタン膜が表面に形成されたシリコン基板上に、実施例1~実施例8で調製した保護膜形成組成物及び比較例1で調製した保護膜形成組成物の各々をスピンコートにて塗布し、250℃で60秒ベークすることで、100nmの膜厚の塗膜を作製した。
実施例1~実施例8で調製した保護膜形成組成物及び比較例1で調製した保護膜形成組成物の各々について、動的光散乱法(DLS法)による粒子径測定装置(大塚電子(株)製 多検体ナノ粒子径測定システムnanoSAQLA)(検出限界:3nm以下)を用いて、保護膜形成組成物の平均粒子径を測定した。
図1に模式図で示す、50nmトレンチ(L(ライン)/S(スペース))を形成したシリコン基板に、CVD法にてシリコン酸化膜を20nm程度堆積させて作製した、シリコン酸化膜がトレンチ表面部に形成されたシリコン加工基板(シリコン酸化膜堆積後:10nmトレンチ(L(ライン)/S(スペース))上に、実施例1~実施例8で調製した保護膜形成組成物の各々をスピンコートにて塗布し、250℃で60秒ベークすることで、100nmの膜厚の塗膜を作製した。断面SEM(S-4800、(株)日立ハイテクノロジーズ製)を用いて埋め込み性の確認を行った。
断面SEM観察結果を(図2)に示す。実施例の保護膜形成組成物においては、SEM写真上白く見えるシリコン酸化膜の間隙である10nmトレンチ(L(ライン)/S(スペース))基板へ、該組成物がボイド(空隙等)を生じることなく埋め込まれていることが分かる(SEM写真で黒っぽく見える部分)。この埋め込み性評価の結果から、本願組成物中に含まれる化合物の大きさが3nm以下であるため、例えば3nm以下の線幅を有する微細トレンチを有する基板にも、比較例の保護膜形成組成物と比較し、埋め込み性が良好であることが予想できる。
実施例1~実施例8で調製した保護膜形成組成物及び比較例1で調製した保護膜形成組成物を用いて窒化チタン膜が表面に形成されたシリコン基板上に作製した塗膜を、下記表1で示した組成の塩基性過酸化水素水溶液に、同表に示す温度で4分間浸し、その後水洗、乾燥後の塗膜の状態を目視で観察した。その結果を下記表2に示す。表2中の“○”は4分処理後も塗膜に剥がれが見られない状態 “×”は4分処理後に塗膜の一部又は全てにおいて剥がれが観察された状態を示している。
本明細書に記載の実施例1~8及び比較例1で調製された保護膜形成組成物(レジスト下層膜形成組成物)を、それぞれスピナーによりシリコンウエハ上に塗布した。ホットプレート上、250℃で1分間ベークし、レジスト下層膜(膜厚50nm)を形成した。そして、これらの保護膜形成組成物について分光エリプソメーター(J.A.Woollam社、VUV-VASE VU-302)を用い、波長193nm及び248nmでのn値(屈折率)及びk値(減衰係数又は吸光係数)を測定した。その結果を表4に示す。
本明細書に記載の実施例1~8及び比較例1で調製された保護膜形成組成物(レジスト下層膜形成組成物)を、それぞれスピンコーターによりシリコンウエハ上に塗布した。ホットプレート上、250℃で1分間ベークし、レジスト下層膜を形成した。そして、サムコ(株)製ドライエッチング装置(RIE-10NR)を用い、ドライエッチングガスとしてCF4を使用する条件下でドライエッチング速度(単位時間当たりの膜厚の減少量)を測定した。
本明細書に記載の実施例1~8で調製された保護膜形成組成物のドライエッチング速度と比較例1のドライエッチング速度との比較を行った。表4に、前記比較例1のドライエッチング速度を1.00としたときの、各実施例の保護膜形成組成物のドライエッチング速度を、選択比として示す。
Claims (20)
- 分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造を末端に有する、重量平均分子量が1500以下の、複素環を含まない化合物(A)、及び有機溶剤を含み、
動的光散乱法による平均粒子径が3nm以下である粒子を含む、
半導体用ウエットエッチング液に対する保護膜形成組成物。 - 半導体基板上の狭ギャップへの埋め込み性に優れる、請求項1に記載の半導体用ウエットエッチング液に対する保護膜形成組成物。
- 前記化合物(A)が、芳香族炭化水素又は脂環式炭化水素を含む、請求項1又は2に記載の保護膜形成組成物。
- 前記化合物(A)が、前記分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造として、1,2-エタンジオール構造を有する、請求項1~3何れか1項に記載の保護膜形成組成物。
- 上記式(1)のX1がエーテル結合を表し、X2がスルフィド結合を表す、請求項5に記載の半導体用ウエットエッチング液に対する保護膜形成組成物。
- 酸触媒をさらに含む、請求項1~6のいずれか1項に記載の保護膜形成組成物。
- 請求項1~7のいずれか1項に記載の保護膜形成組成物からなる塗布膜の焼成物であることを特徴とする保護膜。
- 分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造を末端に有する、重量平均分子量が1500以下の、複素環を含まない化合物(A)、及び有機溶剤を含み、
動的光散乱法による平均粒子径が3nm以下である粒子を含む、
レジスト下層膜形成組成物。 - 半導体基板上の狭ギャップへの埋め込み性に優れる、請求項9に記載のレジスト下層膜形成組成物。
- 前記化合物(A)が、芳香族炭化水素又は脂環式炭化水素を含む、請求項9又は10に記載のレジスト下層膜形成組成物。
- 前記化合物(A)が、前記分子内に互いに隣接する2つの水酸基を少なくとも1組含む構造として、1,2-エタンジオール構造を有する、請求項9~11何れか1項に記載のレジスト下層膜形成組成物。
- 上記式(1)のX1がエーテル結合を表し、X2がスルフィド結合を表す、請求項13に記載のレジスト下層膜形成組成物。
- 酸触媒及び/又は架橋剤をさらに含む、請求項9~14何れか1項に記載のレジスト下層膜形成組成物。
- 請求項9~15のいずれか1項に記載のレジスト下層膜形成組成物からなる塗布膜の焼成物であることを特徴とするレジスト下層膜。
- 請求項1~7のいずれか1項に記載の保護膜形成組成物を、段差を有する半導体基板上に塗布し焼成して保護膜を形成する工程を含む、半導体の製造に用いることを特徴とする保護膜付き基板の製造方法。
- 請求項1~7又は請求項9~15のいずれか1項に記載の保護膜組成物又はレジスト下層膜形成組成物を半導体基板上に塗布し焼成してレジスト下層膜としての保護膜を形成する工程、該保護膜上にレジスト膜を形成し、次いで露光、現像してレジストパターンを形成する工程を含み、半導体の製造に用いることを特徴とするレジストパターン付き基板の製造方法。
- 表面に無機膜が形成されていてもよい半導体基板上に、請求項1~7のいずれか1項に記載の保護膜形成組成物を用いて保護膜を形成し、前記保護膜上にレジストパターンを形成し、前記レジストパターンをマスクとして前記保護膜をドライエッチングし、前記無機膜又は前記半導体基板の表面を露出させ、ドライエッチング後の前記保護膜をマスクとして、半導体用ウエットエッチング液を用いて前記無機膜又は前記半導体基板をウエットエッチング及び洗浄する工程を含む半導体装置の製造方法。
- 表面に無機膜が形成されていてもよい半導体基板上に、請求項9~15いずれか1項に記載のレジスト下層膜形成組成物を用いてレジスト下層膜を形成し、前記レジスト下層膜上にレジストパターンを形成し、前記レジストパターンをマスクとして前記レジスト下層膜をドライエッチングし、前記無機膜又は前記半導体基板の表面を露出させ、ドライエッチング後の前記レジスト下層膜をマスクとして、前記無機膜又は前記半導体基板をエッチングする工程を含む半導体装置の製造方法。
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