WO2017188263A1 - 膜密度が向上したレジスト下層膜を形成するための組成物 - Google Patents
膜密度が向上したレジスト下層膜を形成するための組成物 Download PDFInfo
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- WO2017188263A1 WO2017188263A1 PCT/JP2017/016406 JP2017016406W WO2017188263A1 WO 2017188263 A1 WO2017188263 A1 WO 2017188263A1 JP 2017016406 W JP2017016406 W JP 2017016406W WO 2017188263 A1 WO2017188263 A1 WO 2017188263A1
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- underlayer film
- resist underlayer
- resist
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- 0 CC*(C)C(C1(C)C=C(C2=CCCC=C2N2)C2=CC1)C(CC1)=CC=C1[N+]([O-])=O Chemical compound CC*(C)C(C1(C)C=C(C2=CCCC=C2N2)C2=CC1)C(CC1)=CC=C1[N+]([O-])=O 0.000 description 8
- OLSHYOARVZZHGE-UHFFFAOYSA-N C1CC=C2C3=CCCC=C3NC2C1 Chemical compound C1CC=C2C3=CCCC=C3NC2C1 OLSHYOARVZZHGE-UHFFFAOYSA-N 0.000 description 1
- ZOHVZLSNUVHRKU-UHFFFAOYSA-N CC(C)C1C=C2NC3=CCCC=C3C2=CC1 Chemical compound CC(C)C1C=C2NC3=CCCC=C3C2=CC1 ZOHVZLSNUVHRKU-UHFFFAOYSA-N 0.000 description 1
- GPCZJXKMBDKDSH-UHFFFAOYSA-N CC1(C(CCCC2)C2N2)C2=CCC1 Chemical compound CC1(C(CCCC2)C2N2)C2=CCC1 GPCZJXKMBDKDSH-UHFFFAOYSA-N 0.000 description 1
- AHAHTZPRTFKFRX-UHFFFAOYSA-N CCC(C)(C)C(CC1C=C2NC3=CC(CC(C)(C)C)C=C3C2=C1)c(cc1)ccc1OCCO Chemical compound CCC(C)(C)C(CC1C=C2NC3=CC(CC(C)(C)C)C=C3C2=C1)c(cc1)ccc1OCCO AHAHTZPRTFKFRX-UHFFFAOYSA-N 0.000 description 1
- CJNHLCYDDDUNLU-UHFFFAOYSA-N CCC(C)(C)C1C=C2NC3=CCC=C3C2=CC1 Chemical compound CCC(C)(C)C1C=C2NC3=CCC=C3C2=CC1 CJNHLCYDDDUNLU-UHFFFAOYSA-N 0.000 description 1
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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- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
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- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic 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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
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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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- 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
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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
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70691—Handling of masks or workpieces
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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
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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
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers 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
Definitions
- the present invention relates to a composition for forming a resist underlayer film having an improved film density, and a method for manufacturing a semiconductor device using the composition.
- polymers having a ring structure such as novolak have been widely used from fine fields such as photoresists to general fields such as automobiles and housing members. .
- a monomer having a ring structure includes structures such as benzene, naphthalene, anthracene, pyrene, and fluorene, and these monomers are known to form a novolak with a monomer having an aldehyde group.
- carbazole having a structure similar to that of fluorene has similar characteristics, and it has been revealed that both monomers are polymerized by reaction of a part of the benzene ring adjacent to the five-membered ring.
- a thin film of a photoresist composition is formed on a substrate to be processed such as a silicon wafer, and irradiated with actinic rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developed.
- actinic rays such as ultraviolet rays
- This is a processing method for etching a substrate to be processed such as a silicon wafer using the obtained photoresist pattern as a protective film.
- Examples of polymers for the resist underlayer film include the following.
- Examples are resist underlayer film-forming compositions using carbazole (see Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4).
- the present invention provides a resist underlayer film forming composition for forming a resist underlayer film having high film density, hardness, Young's modulus, Wiggling resistance (pattern bending resistance), and having high etching resistance based on them. There is to do.
- the group A and the group B are each independently an organic group having an aromatic ring, a condensed aromatic ring, or a condensed aromatic heterocyclic ring, a), two or more monovalent or bivalent of the same or different selected from the group consisting of a chemical group (b) that causes cross-linking formation upon heating, and a chemical group (c) that induces phase separation during curing
- the chemical group has a structure in which a hydrogen atom bonded to a carbon atom on the aromatic ring, the condensed aromatic ring, or the condensed aromatic heterocycle in the group A or the group B or both is substituted.
- a resist underlayer film-forming composition comprising, As a second aspect, the organic group having an aromatic ring, a condensed aromatic ring, or a condensed aromatic heterocycle is an organic group having a condensed ring of one or more benzene rings, naphthalene rings, or benzene rings and hetero rings
- the resist underlayer film forming composition according to the first aspect As a third aspect, the novolak resin of the formula (1) has a chemical group (a), a chemical group (b), a chemical group (c), a combination of the chemical group (a) and the chemical group (b), a chemical group (a ) And a chemical group (c), a combination of a chemical group (b) and a chemical group (c), and a combination of a chemical group (a), a chemical group (b), and a chemical group (c).
- the resist underlayer film forming composition according to the first aspect or the second aspect which is a novolak resin having a structure in which a hydrogen atom of an aromatic ring, a condensed aromatic ring, or a condensed aromatic hetero ring is substituted with the above chemical group
- the novolak resin represented by the formula (1) is obtained from the same or different two kinds of chemical groups selected from the chemical group (b), or the chemical group (a) and the chemical group (b), respectively.
- the two selected chemical groups each have at least one hydrogen atom bonded to a carbon atom on the aromatic ring, fused aromatic ring, or fused aromatic heterocycle in both groups A and B;
- the resist underlayer film forming composition according to the third aspect which is substituted and has a structure in which two types of chemical groups are introduced into the unit structure,
- the resist underlayer film forming composition according to any one of the first to fourth aspects wherein the chemical group (a) is a methyl group, a sulfide group, or a combination thereof
- the chemical group (b) is an amino group, a carboxyl group, a carboxylic acid alkyl ester group, a nitro group, a hydroxy group, an ether group, or a combination thereof.
- the resist underlayer film forming composition as described, As a seventh aspect, the resist underlayer film forming composition according to any one of the first aspect to the sixth aspect, in which the chemical group (c) is a fluoroalkyl group, As an eighth aspect, the resist underlayer film forming composition according to any one of the first aspect to the seventh aspect, further including a crosslinking agent, As a ninth aspect, the resist underlayer film forming composition according to any one of the first to eighth aspects, further comprising an acid and / or an acid generator, As a tenth aspect, a method for producing a resist underlayer film obtained by applying and baking the resist underlayer film forming composition according to any one of the first to ninth aspects on a semiconductor substrate, As an eleventh aspect, a step of forming a resist underlayer film from the resist underlayer film forming composition according to any one of the first to ninth aspects on a semiconductor substrate, a step of forming a resist film thereon, light Alternatively, a method for manufacturing a semiconductor device includes a step of forming
- a good resist pattern shape can be formed without causing intermixing between the upper layer portion of the resist underlayer film and the layer coated thereon.
- the resist underlayer film forming composition of the present invention can be imparted with a performance of efficiently suppressing reflection from the substrate, and can also have an effect as an antireflection film for exposure light.
- the dry etching rate selectivity close to the resist, the dry etching rate selectivity lower than that of the resist, and the dry etching rate selectivity lower than that of the semiconductor substrate are excellent.
- a resist underlayer film can be provided.
- the resist is thinned.
- the resist pattern is transferred to the lower layer film by an etching process, the substrate processing is performed using the lower layer film as a mask, or the resist pattern is transferred to the lower layer film by an etching process, and further to the lower layer film.
- the resist underlayer film and the composition for forming the resist of the present invention are effective for this process.
- a processed substrate for example, a thermal silicon oxide film on the substrate, silicon nitride) Film, polysilicon film, etc. having sufficient etching resistance.
- the resist underlayer film of the present invention can be used as a planarizing film, a resist underlayer film, a resist layer antifouling film, or a film having dry etch selectivity. This makes it possible to easily and accurately form a resist pattern in a lithography process for manufacturing a semiconductor.
- a resist underlayer film by the resist underlayer film forming composition according to the present invention is formed on a substrate, a hard mask is formed thereon, a resist film is formed thereon, a resist pattern is formed by exposure and development, and a resist pattern Is transferred to the hard mask, the resist pattern transferred to the hard mask is transferred to the resist underlayer film, and the semiconductor substrate is processed with the resist underlayer film.
- the hard mask may be formed by a coating type composition containing an organic polymer or inorganic polymer and a solvent, or by vacuum deposition of an inorganic substance. In the vacuum deposition of an inorganic material (for example, silicon nitride oxide), the deposited material is deposited on the resist underlayer film surface. At this time, the temperature of the resist underlayer film surface rises to around 400 ° C.
- the polymer used has extremely high heat resistance, and thermal degradation does not occur even when the deposited material is deposited.
- the resist underlayer film obtained from the resist underlayer film forming composition of the present invention has an aromatic ring, a condensed aromatic ring, or a condensed aromatic heterocycle (for example, a benzene ring) in the unit structure of the polymer contained therein. Since the hydrogen atom bonded to the upper carbon atom is substituted with a chemical group having a specific function, the aromatic ring, condensed aromatic ring, or condensed aromatic heterocycle not substituted with the chemical group is a unit. Compared to a resist underlayer film having a polymer included in the structure, the film density and hardness are improved, Wiggling resistance (pattern bending resistance) is high, and etching resistance is also improved.
- This invention is a resist underlayer film forming composition containing the novolak resin which has a repeating unit represented by Formula (1).
- the group A and the group B are each independently an organic group having an aromatic ring, a condensed aromatic ring, or a condensed aromatic heterocycle, and a chemical group (a ), Two or more kinds of monovalent or divalent chemical groups selected from the group consisting of a chemical group (b) that forms a crosslink by heating, and a chemical group (c) that induces phase separation during curing, An organic group having a structure in which a hydrogen atom bonded to a carbon atom on an aromatic ring, a condensed aromatic ring, or a condensed aromatic heterocycle in the group A and / or the group B is substituted.
- the chemical group is divalent, the rings may be bonded via the chemical group or condensed together with the chemical group.
- the aromatic ring, condensed aromatic ring, or condensed aromatic heterocycle may be one or more benzene rings, naphthalene rings, or a condensed ring of a benzene ring and a heterocycle. Therefore, the group A and the group B can be each independently an organic group having one or a plurality of benzene rings, naphthalene rings, or condensed rings of benzene rings and hetero rings.
- examples of the organic group A include organic groups having benzene, naphthalene, carbazole, diphenylamine, trishydroxyphenylethane, and the like.
- the amino group contained in carbazole or diphenylamine corresponds to the chemical group (b), and has a structure in which a secondary amino group is substituted with hydrogen atoms of two benzene rings.
- Trishydroxyphenylethane has a structure in which each benzene ring is substituted with a hydroxy group.
- examples of the organic group B include organic groups having benzene, naphthalene and the like.
- the two or more types of chemical groups described herein are two or more types from the chemical group (a), two or more types from the chemical group (b), two or more types from the chemical group (c), or the chemical group (a). And two or more types from both chemical group (b), two or more types from both chemical group (a) and chemical group (c), two or more types from both chemical group (b) and chemical group (c), chemical There are two or more types (ie, three or more types) of all of the group (a), the chemical group (b), and the chemical group (c).
- the novolak resin of the formula (1) includes a chemical group (a), a chemical group (b), a combination of the chemical group (a) and the chemical group (b), a combination of the chemical group (a) and the chemical group (c), a chemical group A novolak resin having a structure in which a hydrogen atom of an aromatic ring, a condensed aromatic ring, or a condensed aromatic heterocyclic ring is substituted with two or more kinds of chemical groups selected from a combination of the group (b) and the chemical group (c) It can be. That is, it can have a structure in which the hydrogen atom of the aromatic ring, condensed aromatic ring, or condensed aromatic heterocycle of the group A, the group B, or both is substituted.
- the novolak resin of the formula (1) is a chemical group (b) or two kinds of chemical groups each selected from the combination of the chemical group (a) and the chemical group (b), and all the ( That is, in the aromatic ring, fused aromatic ring, or fused aromatic heterocycle of both group A and group B, respectively, bonded to a carbon atom on the aromatic ring, fused aromatic ring, or fused aromatic heterocycle
- One hydrogen atom to be substituted can be substituted with one of the two types of chemical groups, and the unit structure can have a structure in which two types of chemical groups are introduced.
- Examples of the chemical group (a) include a methyl group, a sulfide group, or a combination thereof.
- Examples of the chemical group (b) include an amino group, a carboxyl group, a carboxylic acid alkyl ester group, a nitro group, a hydroxy group, an ether group, or a combination thereof.
- alkyl group of the carboxylic acid alkyl ester group examples include alkyl groups having 1 to 10 carbon atoms.
- alkyl groups having 1 to 10 carbon atoms For example, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i- Butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl- n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl -N-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group
- Examples of the chemical group (c) include a fluoroalkyl group.
- Examples of the fluoroalkyl group include a partially fluorinated alkyl group and a fully fluorinated alkyl group.
- An example is a trifluoromethyl group.
- a polymer is obtained by novolakization between an aromatic compound corresponding to the group A or a compound containing an aromatic group and an aromatic aldehyde corresponding to the group B.
- the chemical group (a), the chemical group (b), and the chemical group (c) may be introduced into the starting material for the novolak reaction or may be introduced into the novolak polymer by reaction.
- Examples of the acid catalyst used in the above condensation reaction include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate, Carboxylic acids such as formic acid and oxalic acid are used.
- the amount of the acid catalyst used is variously selected depending on the type of acids used. Usually, 0.001 to 10000 parts by weight, preferably 0.01 to 1000 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the compound corresponding to the group A of formula (1). It is.
- the above condensation reaction is carried out without solvent, but is usually carried out using a solvent. Any solvent that does not inhibit the reaction can be used. Examples thereof include cyclic ethers such as tetrahydrofuran and dioxane, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like.
- the acid catalyst used is a liquid such as formic acid, it can also serve as a solvent.
- the reaction temperature during the condensation is usually 40 ° C to 200 ° C.
- the reaction time is variously selected depending on the reaction temperature, but is usually about 30 minutes to 50 hours.
- the weight average molecular weight Mw of the polymer obtained as described above is usually 600 to 1000000, or 600 to 200000.
- the unit structure of Formula (1) can be illustrated below, for example.
- the said polymer can mix and use another polymer within 30 mass% in all the polymers.
- polymers examples include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride compounds, and polyacrylonitrile compounds.
- the resist underlayer film forming composition of the present invention contains the polymer and a solvent. And it can contain a crosslinking agent and an acid, and can contain additives, such as an acid generator and surfactant, as needed.
- the solid content of the composition is 0.1 to 70% by mass, or 0.1 to 60% by mass.
- the solid content is the content ratio of all components excluding the solvent from the resist underlayer film forming composition.
- the polymer can be contained in a solid content in a proportion of 1 to 100% by mass, or 1 to 99.9% by mass, or 50 to 99.9% by mass.
- the polymer used in the present invention has a weight average molecular weight of 600 to 1000000 or 600 to 200000.
- the resist underlayer film forming composition of the present invention can contain a crosslinking agent component.
- the cross-linking agent include melamine type, substituted urea type, or polymer type thereof.
- a cross-linking agent having at least two cross-linking substituents methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, Compounds such as methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea.
- the condensate of these compounds can also be used.
- crosslinking agent a crosslinking agent having high heat resistance
- a compound containing a crosslinking-forming substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be preferably used.
- this compound examples include a compound having a partial structure of the following formula (3) and a polymer or oligomer having a repeating unit structure of the following formula (4).
- R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, n1 is an integer of 1 to 4, and n2 Is an integer from 1 to (5-n1), and (n1 + n2) is an integer from 2 to 5.
- R 5 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 6 is an alkyl group having 1 to 10 carbon atoms
- n3 is an integer of 1 to 4
- n4 is 0 to (4-n3)
- (n3 + n4) is an integer of 1 to 4.
- the oligomer and polymer can be used in the range of 2 to 100 or 2 to 50 repeating unit structures.
- alkyl group having 1 to 10 carbon atoms include the above-mentioned examples.
- aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthryl group.
- the above compounds can be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Industry Co., Ltd.
- the compound of the formula (4-21) can be obtained as Asahi Organic Materials Co., Ltd., trade name TM-BIP-A.
- the amount of the crosslinking agent to be added varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80% by mass with respect to the total solid content, preferably The amount is 0.01 to 50% by mass, more preferably 0.05 to 40% by mass.
- These cross-linking agents may cause a cross-linking reaction by self-condensation, but when a cross-linkable substituent is present in the above-mentioned polymer of the present invention, it can cause a cross-linking reaction with those cross-linkable substituents.
- p-toluenesulfonic acid as a catalyst for promoting the crosslinking reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid Acidic compounds such as acids or / and thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters may be added. I can do it.
- the blending amount is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, preferably 0.01 to 3% by mass, based on the total solid content.
- a photoacid generator can be added in order to match the acidity with the photoresist coated on the upper layer in the lithography process.
- Preferred photoacid generators include, for example, onium salt photoacid generators such as bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, and phenyl-bis (trichloromethyl) -s.
- -Halogen-containing compound photoacid generators such as triazine, and sulfonic acid photoacid generators such as benzoin tosylate and N-hydroxysuccinimide trifluoromethanesulfonate.
- the photoacid generator is 0.2 to 10% by mass, preferably 0.4 to 5% by mass, based on the total solid content.
- further light absorbers examples include commercially available light absorbers described in “Technical dye technology and market” (published by CMC) and “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry), such as C.I. I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C.I. I.
- the above light-absorbing agent is usually blended at a ratio of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist underlayer film forming composition for lithography.
- the rheology modifier mainly improves the fluidity of the resist underlayer film forming composition, and improves the film thickness uniformity of the resist underlayer film and the fillability of the resist underlayer film forming composition inside the hole, particularly in the baking process. It is added for the purpose of enhancing.
- phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate
- maleic acid derivatives such as normal butyl maleate, diethyl maleate and dinonyl maleate
- oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate
- stearic acid derivatives such as normal butyl stearate and glyceryl stearate. it can.
- These rheology modifiers are usually blended at a ratio of less than 30% by mass with respect to the total solid content of the resist underlayer film forming
- the adhesion auxiliary agent is added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film forming composition, and preventing the resist from being peeled off particularly during development.
- Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltri Alkoxysilanes such as ethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, silazanes such as dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, ⁇ -chloropropy
- a surfactant can be blended in order to further improve the applicability to surface unevenness without occurrence of pinholes and setups.
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether.
- Polyoxyethylene alkyl allyl ethers Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc.
- Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (trade name, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, R-40, R-40N (product name) manufactured by DIC Corporation, Florard FC430, FC431 (Sumitomo 3M ( Co., Ltd., trade name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd., trade name) and other fluorosurfactants, organosiloxane polymers P341 (manufactured by
- the compounding amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film forming composition for lithography of the present invention.
- These surfactants may be added alone or in combination of two or more.
- the solvent for dissolving the polymer and the crosslinking agent component, the crosslinking catalyst and the like 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxypropionic acid Ethyl, 2-hydroxy- -Ethyl methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl
- a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate can be mixed and used.
- a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate
- propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone and the like are preferable for improving the leveling property.
- a spinner, a coater, etc. are suitably used on a substrate (for example, a transparent substrate such as a silicon / silicon dioxide coating, a glass substrate, an ITO substrate) used for manufacturing a precision integrated circuit device.
- a substrate for example, a transparent substrate such as a silicon / silicon dioxide coating, a glass substrate, an ITO substrate
- the resist underlayer film forming composition After applying the resist underlayer film forming composition by a simple coating method, it is baked and cured to form a coating type underlayer film.
- the thickness of the resist underlayer film is preferably 0.01 to 3.0 ⁇ m.
- the conditions for baking after coating are 80 to 350 ° C. and 0.5 to 120 minutes.
- a resist is applied and irradiated with light or an electron beam through a predetermined mask.
- a good resist pattern can be obtained by performing, developing, rinsing and drying. If necessary, post-irradiation heating (PEB: Post Exposure Bake) may be performed. Then, the resist underlayer film where the resist has been developed and removed by the above process is removed by dry etching, and a desired pattern can be formed on the substrate.
- PEB Post Exposure Bake
- the resist used in the present invention is a photoresist or an electron beam resist.
- the photoresist applied on the upper part of the resist underlayer film for lithography in the present invention either negative type or positive type can be used, and a positive type photoresist composed of a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, depending on the acid.
- Chemically amplified photoresist comprising a binder having a group that decomposes to increase the alkali dissolution rate and a photoacid generator, a low molecular weight compound and photoacid that increases the alkali dissolution rate of the photoresist by decomposition with an alkali-soluble binder and acid
- Chemically amplified photoresist comprising a generator, comprising a binder having a group that decomposes with acid to increase the alkali dissolution rate, a low-molecular compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator Chemically amplified photoresist with Si atoms in the skeleton
- a photoresist or the like which, for example, Rohm & Hearts Co., Ltd., and trade name APEX-E.
- an acid is generated by irradiation of a resin containing an Si-Si bond in the main chain and an aromatic ring at the terminal and an electron beam.
- examples include a composition comprising an acid generator, or a composition comprising a poly (p-hydroxystyrene) having a hydroxyl group substituted with an organic group containing N-carboxyamine and an acid generator that generates an acid upon irradiation with an electron beam. It is done.
- the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyaminoxy group of the polymer side chain, and the polymer side chain decomposes into a hydroxyl group and exhibits alkali solubility, thereby exhibiting alkali solubility.
- the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyaminoxy group of the polymer side chain, and the polymer side chain decomposes into a hydroxyl group and exhibits alkali solubility, thereby exhibiting alkali solubility.
- Acid generators that generate an acid upon irradiation with this electron beam are 1,1-bis [p-chlorophenyl] -2,2,2-trichloroethane, 1,1-bis [p-methoxyphenyl] -2,2,2 -Halogenated organic compounds such as trichloroethane, 1,1-bis [p-chlorophenyl] -2,2-dichloroethane, 2-chloro-6- (trichloromethyl) pyridine, and onium salts such as triphenylsulfonium salt and diphenyliodonium salt Sulfonic acid esters such as nitrobenzyl tosylate and dinitrobenzyl tosylate.
- the resist solution is applied and then fired at a baking temperature of 70 to 150 ° C. and a baking time of 0.5 to 5 minutes.
- the resist film thickness is obtained in the range of 10 to 1000 nm.
- the resist solution, the developer, and the coating materials shown below can be coated by spin coating, dipping, spraying, or the like, but the spin coating method is particularly preferable.
- the resist is exposed through a predetermined mask.
- a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), EUV light (wavelength 13.5 nm), an electron beam, or the like can be used.
- post-exposure heating PEB: Post Exposure Bake
- the post-exposure heating is appropriately selected from a heating temperature of 70 ° C. to 150 ° C. and a heating time of 0.3 to 10 minutes.
- sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia Inorganic amines such as ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine Alcohol amines such as alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, and cyclic amines such as pyrrole and piperidine, and alkaline aqueous solutions can be used.
- aqueous ammonia Inorganic amines such as ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-buty
- an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.
- preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.
- an organic solvent can be used as a developer for developing the resist. Development is performed with a developer (solvent) after exposure of the resist. 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, 2-methoxybutyl Cetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-me
- a step of forming a resist underlayer film from a resist underlayer film forming composition on a semiconductor substrate, a step of forming a resist film thereon, a step of forming a resist pattern by light or electron beam irradiation and development, and formation A semiconductor device can be manufactured through a step of etching the resist underlayer film with the patterned resist pattern and a step of processing the semiconductor substrate with the patterned resist underlayer film.
- the resist underlayer film for lithography which has a selection ratio of dry etching rates close to that of resist, is selected as a resist underlayer film for such processes, and a lower dry etching rate than resist.
- resist underlayer film for lithography having a higher ratio and a resist underlayer film for lithography having a lower dry etching rate selection ratio than a semiconductor substrate.
- a resist underlayer film can be provided with an antireflection ability, and can also have a function of a conventional antireflection film.
- a process of making the resist pattern and the resist underlayer film narrower than the pattern width at the time of developing the resist during dry etching of the resist underlayer film has begun to be used.
- a resist underlayer film having a selectivity of a dry etching rate close to that of the resist has been required as a resist underlayer film for such a process.
- such a resist underlayer film can be provided with an antireflection ability, and can also have a function of a conventional antireflection film.
- the substrate after forming the resist underlayer film of the present invention on a substrate, directly or optionally forming one to several layers of coating material on the resist underlayer film, A resist can be applied. As a result, the pattern width of the resist becomes narrow, and even when the resist is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas.
- a semiconductor device can be manufactured through a step of etching the resist underlayer film with an oxygen-based gas or a hydrogen-based gas using the formed hard mask, and a step of processing the semiconductor substrate with a halogen-based gas using the patterned resist underlayer film. it can.
- the resist underlayer film forming composition for lithography of the present invention has a light absorption site incorporated into the skeleton, so there is no diffused material in the photoresist during heating and drying. Moreover, since the light absorption site has a sufficiently large light absorption performance, the effect of preventing reflected light is high.
- composition for forming a resist underlayer film for lithography of the present invention has high thermal stability, can prevent contamination of the upper layer film by decomposition products during baking, and can provide a margin for the temperature margin of the baking process. is there.
- the resist underlayer film forming composition for lithography of the present invention has a function of preventing reflection of light depending on process conditions, and further prevents the interaction between the substrate and the photoresist or the material used for the photoresist or the photo resist.
- the film can be used as a film having a function of preventing an adverse effect on a substrate of a substance generated upon exposure of the resist.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 12.2g of powdered resin was obtained.
- the obtained polymer corresponded to Formula (1-1).
- the weight average molecular weight Mw measured by GPC in terms of polystyrene was 82,700, and the polydispersity Mw / Mn was 13.5.
- the reaction mixture was diluted with 22.25 g of propylene glycol monomethyl ether acetate. This solution was dropped into a methanol solution and reprecipitated. The obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 13.7g of powder resin was obtained.
- the obtained polymer corresponded to Formula (1-2).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 24,800, and the polydispersity Mw / Mn was 4.30.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 9.02g of powdered resin was obtained.
- the obtained polymer corresponded to the formula (1-4).
- the weight average molecular weight Mw measured by GPC in terms of polystyrene was 3,800, and the polydispersity Mw / Mn was 2.58.
- the obtained polymer corresponded to the formula (1-7).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 4,100, and the polydispersity Mw / Mn was 3.01.
- the obtained polymer corresponded to the formula (1-9).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 12,700, and the polydispersity Mw / Mn was 3.82.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 8.11g of powder resin was obtained.
- the obtained polymer corresponded to the formula (1-10).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 15,300, and the polydispersity Mw / Mn was 3.52.
- the reaction mixture was diluted with 26.48 g of cyclohexanone. This solution was dropped into a methanol solution and reprecipitated. The obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 10.7g of powdery resin was obtained.
- the obtained polymer corresponded to the formula (1-12).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 6,300, and the polydispersity Mw / Mn was 2.90.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. Then, 9.54 g of powdered resin was obtained.
- the obtained polymer corresponded to the formula (1-13).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 2,500, and the polydispersity Mw / Mn was 1.95.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 4.76g of powder resin was obtained.
- the obtained polymer corresponded to the formula (1-14).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 103,000, and the polydispersity Mw / Mn was 2.32.
- the obtained polymer corresponded to the formula (1-15).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 2,100, and the polydispersity Mw / Mn was 1.61.
- the obtained polymer corresponded to the formula (1-16).
- the weight average molecular weight Mw measured by GPC in terms of polystyrene was 4,000, and the polydispersity Mw / Mn was 2.17.
- the obtained polymer corresponded to the formula (1-17).
- the weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,000, and the polydispersity Mw / Mn was 1.73.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 11.6g of powder resin was obtained.
- the obtained polymer corresponded to the formula (1-18).
- the weight average molecular weight Mw measured by GPC in terms of polystyrene was 4,300, and the polydispersity Mw / Mn was 2.14.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 11.1 g of powdered resin was obtained.
- the obtained polymer corresponded to the formula (1-19).
- the weight average molecular weight Mw measured by GPC in terms of polystyrene was 4,000, and the polydispersity Mw / Mn was 1.53.
- the obtained polymer corresponded to the formula (1-20).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 6,300, and the polydispersity Mw / Mn was 1.78.
- the reaction mixture was diluted with 22.51 g of cyclohexanone. This solution was dropped into a methanol solution and reprecipitated. The obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 11.5g of powder resin was obtained.
- the obtained polymer corresponded to the formula (1-21).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 52,700, and the polydispersity Mw / Mn was 8.86.
- the obtained polymer corresponded to the formula (2-1).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 32,200, and the polydispersity Mw / Mn was 2.14.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 8.58 g of powdered resin was obtained.
- the obtained polymer corresponded to the formula (2-2).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 8,400, and the polydispersity Mw / Mn was 2.38.
- the obtained polymer corresponded to Formula (2-3).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 4,600, and the polydispersity Mw / Mn was 1.64.
- the reaction mixture was diluted with 23.21 g of propylene glycol monomethyl ether acetate. This solution was dropped into a methanol solution and reprecipitated. The obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 13.3g of powder resin was obtained.
- the obtained polymer corresponded to the formula (2-4).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 25,800, and the polydispersity Mw / Mn was 4.44.
- the obtained precipitate was suction filtered, and the filtrate was dried under reduced pressure at 60 ° C. overnight. And 9.65g of powder resin was obtained.
- the obtained polymer corresponded to the formula (2-5).
- the weight average molecular weight Mw measured in terms of polystyrene by GPC was 6,300, and the polydispersity Mw / Mn was 2.03.
- the obtained polymer corresponded to the formula (2-6).
- the weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,000, and the polydispersity Mw / Mn was 1.97.
- Each resin of the above synthesis examples and comparative synthesis examples was dissolved in a solvent, and then a cation exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and an anion exchange resin (product name: Amberlite [ (Registered Trademark) 15 JWET, Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours to separate the ion exchange resin, and a purified resin was obtained.
- a cation exchange resin product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.
- an anion exchange resin product name: Amberlite [ (Registered Trademark) 15 JWET, Organo Co., Ltd.
- Example 1 0.001 g of Megafac R-40 as a surfactant is mixed with 1.0 g of the resin obtained in Synthesis Example 1, and dissolved in 5.66 g of propylene glycol monomethyl ether acetate and 2.42 g of propylene glycol monomethyl ether. Filtration was performed using a polytetrafluoroethylene microfilter having a pore diameter of 0.02 ⁇ m to prepare a resist underlayer film forming composition solution for use in a lithography process using a multilayer film.
- Examples 2 to 21 and Comparative Examples 1 to 6 were similarly performed.
- the compounding quantity of a polymer, surfactant, and a solvent is as Tables 1 thru
- the used polymer describes the synthesis example number.
- the resist underlayer film forming composition solutions prepared in Examples 1 to 21 and Comparative Examples 1 to 6 were each applied onto a silicon wafer using a spin coater, and baked on a hot plate at 400 ° C. for 90 seconds. A film (film thickness 0.20 ⁇ m) was formed. In order to determine the hardness and Young's modulus of these resist underlayer films, they were evaluated using an indentation tester (manufactured by Toyo Technica). The results are shown in the table below.
- the solutions of the resist underlayer film forming compositions prepared in Examples 2, 4, and 9 and Comparative Examples 4 to 6 were each applied onto a silicon oxide-coated silicon wafer using a spin coater.
- the resist underlayer film (thickness 200 nm) was formed by baking at 400 ° C. for 90 seconds on a hot plate.
- a silicon hard mask forming composition solution was applied on the resist underlayer film and baked at 240 ° C. for 1 minute to form a silicon hard mask layer (film thickness 30 nm).
- a resist solution was applied thereon and baked at 100 ° C. for 1 minute to form a resist layer (thickness 150 nm).
- Exposure was performed using a mask at a wavelength of 193 nm, post-exposure heating PEB (1 minute at 105 ° C.) was performed, and development was performed to obtain a resist pattern. Thereafter, dry etching was performed with a fluorine-based gas (component is CF 4 ), and the resist pattern was transferred to a hard mask. Thereafter, dry etching was performed with an oxygen-based gas (component is O 2 ), and the resist pattern was transferred to the resist underlayer film of the present invention. Thereafter, dry etching was performed with a fluorine-based gas (component is C 4 F 8 ) to remove the silicon oxide film on the silicon wafer. Each pattern shape at that time was observed.
- a fluorine-based gas component is CF 4
- O 2 oxygen-based gas
- dry etching was performed with a fluorine-based gas (component is C 4 F 8 ) to remove the silicon oxide film on the silicon wafer.
- the pattern width narrows, irregular pattern bending called wiggling is likely to occur, but the above steps are performed using the resist underlayer film forming composition of the above example and the pattern width at which wiggling starts to occur is observed with an electron microscope. did. Since the substrate processing based on the faithful pattern cannot be performed due to the occurrence of wiggling, it is necessary to process the substrate with a pattern width (limit pattern width) immediately before the generation of wiggling. The narrower the limit pattern width at which wiggling begins to occur, the finer the substrate can be processed. A length-measuring scanning electron microscope (manufactured by Hitachi, Ltd.) was used for measuring the resolution. The measurement results are shown in the following table.
- the minimum pattern size at which wiggling occurs is approximately the same or smaller in proportion to these numerical values.
- the carbazole novolak resin (Comparative Example 4) has the above-mentioned tendency, and the diphenylamine novolak resin (Comparative Example 5) and the polyhydric phenol novolak resin (Comparative Example 6) are similarly two types in the benzene ring constituting the novolac resin.
- the film density, hardness, and Young's modulus are improved, and the minimum pattern size at which Wiggling occurs in proportion to these values is reduced. , Wiggling resistance is improved and etching resistance is also improved.
- a resist underlayer film forming composition for forming a resist underlayer film having a high film density, hardness, Young's modulus, and Wiggling resistance (high bending resistance) and thereby high etching resistance can be obtained.
Abstract
Description
(式(1)において、基A及び基Bはそれぞれ独立して、芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環を有する有機基であって、酸化により質量増を生じる化学基(a)、加熱により架橋形成を生じる化学基(b)、及び硬化中に相分離を誘発する化学基(c)からなる群より選ばれた同種又は異種の2つ以上の1価又は2価の化学基が、該基Aもしくは基B又はその両方の基中の、芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環上の炭素原子に結合する水素原子と、それぞれ置換した構造を有する有機基であり、前記化学基が2価の場合、前記環同士は該化学基を介して結合もしくは該化学基とともに縮合していてもよい。)で表される繰り返し単位構造を有するノボラック樹脂を含むレジスト下層膜形成組成物、
第2観点として、芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環を有する有機基が、1又は複数のベンゼン環、ナフタレン環、又はベンゼン環とヘテロ環との縮合環を有する有機基である第1観点に記載のレジスト下層膜形成組成物、
第3観点として、式(1)のノボラック樹脂が、化学基(a)、化学基(b)、化学基(c)、化学基(a)と化学基(b)の組み合わせ、化学基(a)と化学基(c)の組み合わせ、化学基(b)と化学基(c)の組み合わせ、化学基(a)と化学基(b)と化学基(c)の組み合わせ、から選ばれた2種類以上の化学基で芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環の水素原子をそれぞれ置換した構造を有するノボラック樹脂である第1観点又は第2観点に記載のレジスト下層膜形成組成物、
第4観点として、式(1)で表されるノボラック樹脂は、化学基(b)から選ばれた同種又は異種の2種の化学基、又は化学基(a)と化学基(b)からそれぞれ選ばれた2種類の化学基が、基A及び基Bの両方の基中の芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環上の炭素原子に結合する少なくとも1つの水素原子とそれぞれ置換して、単位構造中に2種類の化学基が導入された構造を有するものである第3観点に記載のレジスト下層膜形成組成物、
第5観点として、化学基(a)がメチル基、スルフィド基、又はその組み合わせである第1観点乃至第4観点のいずれか一つに記載のレジスト下層膜形成組成物、
第6観点として、化学基(b)がアミノ基、カルボキシル基、カルボン酸アルキルエステル基、ニトロ基、ヒドロキシ基、エーテル基、又はその組み合わせである第1観点乃至第5観点のいずれか一つに記載のレジスト下層膜形成組成物、
第7観点として、化学基(c)がフルオロアルキル基である第1観点乃至第6観点のいずれか一つに記載のレジスト下層膜形成組成物、
第8観点として、更に架橋剤を含む第1観点乃至第7観点のいずれか一つに記載のレジスト下層膜形成組成物、
第9観点として、更に酸及び/又は酸発生剤を含む第1観点乃至第8観点のいずれか一つに記載のレジスト下層膜形成組成物、
第10観点として、第1観点乃至第9観点のいずれか一つに記載の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することによって得られるレジスト下層膜の製造方法、
第11観点として、半導体基板上に第1観点乃至第9観点のいずれか一つに記載のレジスト下層膜形成組成物からレジスト下層膜を形成する工程、その上にレジスト膜を形成する工程、光又は電子線の照射と現像によりレジストパターンを形成する工程、形成されたレジストパターンにより該下層膜をエッチングする工程、及びパターン化された下層膜により半導体基板を加工する工程を含む半導体装置の製造方法、及び
第12観点として、半導体基板上に第1観点乃至第9観点のいずれか一つに記載のレジスト下層膜形成組成物からレジスト下層膜を形成する工程、その上にハードマスクを形成する工程、更にその上にレジスト膜を形成する工程、光又は電子線の照射と現像によりレジストパターンを形成する工程、形成されたレジストパターンによりハードマスクをエッチングする工程、パターン化されたハードマスクにより該下層膜をエッチングする工程、及びパターン化されたレジスト下層膜により半導体基板を加工する工程を含む半導体装置の製造方法である。
好ましくは、式(1)において有機基Aとしてはベンゼン、ナフタレン、カルバゾール、ジフェニルアミン、トリスヒドロキシフェニルエタン等を有する有機基が挙げられる。カルバゾールや、ジフェニルアミンに含まれるアミノ基は上記化学基(b)に相当し、2級アミノ基が2つのベンゼン環の水素原子と置換した構造である。トリスヒドロキシフェニルエタンではそれぞれのベンゼン環にヒドロキシ基が置換した構造である。
式(1)において有機基Bとしてはベンゼン、ナフタレン等を有する有機基が挙げられる。
本発明に用いられるポリマーは、重量平均分子量が600乃至1000000、又は600乃至200000である。
式(4)中、R5はそれぞれ水素原子又は炭素原子数1乃至10のアルキル基であり、R6は炭素原子数1乃至10のアルキル基であり、n3は1乃至4の整数であり、n4は0乃至(4-n3)であり、(n3+n4)は1乃至4の整数を示す。オリゴマー及びポリマーは繰り返し単位構造の数が2乃至100、又は2乃至50の範囲で用いることができる。
上記炭素原子数1乃至10のアルキル基としては、上述の例示を挙げることができる。上記炭素原子数6乃至20のアリール基としては、例えばフェニル基、ナフチル基、アントリル基等が挙げられる。
更なる吸光剤としては例えば、「工業用色素の技術と市場」(CMC出版)や「染料便覧」(有機合成化学協会編)に記載の市販の吸光剤、例えば、C.I.Disperse Yellow 1,3,4,5,7,8,13,23,31,49,50,51,54,60,64,66,68,79,82,88,90,93,102,114及び124;C.I.Disperse Orange1,5,13,25,29,30,31,44,57,72及び73;C.I.Disperse Red 1,5,7,13,17,19,43,50,54,58,65,72,73,88,117,137,143,199及び210;C.I.Disperse Violet 43;C.I.Disperse Blue 96;C.I.Fluorescent Brightening Agent 112,135及び163;C.I.Solvent Orange2及び45;C.I.Solvent Red 1,3,8,23,24,25,27及び49;C.I.Pigment Green 10;C.I.Pigment Brown 2等を好適に用いることができる。上記吸光剤は通常、リソグラフィー用レジスト下層膜形成組成物の全固形分に対して10質量%以下、好ましくは5質量%以下の割合で配合される。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)9.00g、p-トルアルデヒド(東京化成工業株式会社製)6.47g、プロピレングリコールモノメチルエーテルアセテート38.52g、メタンスルホン酸(東京化成工業株式会社製)1.04gを入れた。その後150℃まで加熱し、約1.5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート18.73gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を12.2g得た。得られたポリマーは式(1-1)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは82,700、多分散度Mw/Mnは13.5であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、テレフタルアルデヒド酸(東京化成工業株式会社製)7.19g、プロピレングリコールモノメチルエーテルアセテート18.79g、プロピレングリコールモノメチルエーテル 18.79g、メタンスルホン酸(東京化成工業株式会社製)0.92gを入れた。その後150℃まで加熱し、約3.5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート22.25gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を13.7g得た。得られたポリマーは式(1-2)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは24,800、多分散度Mw/Mnは4.30であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、テレフタルアルデヒド酸メチルエステル(東京化成工業株式会社製)7.86g、プロピレングリコールモノメチルエーテルアセテート24.14g、メタンスルホン酸(東京化成工業株式会社製)0.23gを入れた。その後150℃まで加熱し、約2時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート39.08gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を13.3g得た。得られたポリマーは式(1-3)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは4,600、多分散度Mw/Mnは3.16であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、4-メチルチオベンズアルデヒド(東京化成工業株式会社製)7.28g、プロピレングリコールモノメチルエーテルアセテート36.20g、メタンスルホン酸(東京化成工業株式会社製)0.23gを入れた。その後150℃まで加熱し、約3.5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート24.71gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を9.02g得た。得られたポリマーは式(1-4)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは3,800、多分散度Mw/Mnは2.58であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、4-ニトロベンズアルデヒド(東京化成工業株式会社製)7.24g、プロピレングリコールモノメチルエーテルアセテート36.09g、メタンスルホン酸(東京化成工業株式会社製)0.23gを入れた。その後150℃まで加熱し、約1.25時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート24.63gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を12.1g得た。得られたポリマーは式(1-5)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは1,900、多分散度Mw/Mnは1.43であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、4-トリフルオロメチルベンズアルデヒド(東京化成工業株式会社製)8.34g、プロピレングリコールモノメチルエーテルアセテート40.27g、メタンスルホン酸(東京化成工業株式会社製)0.92gを入れた。その後150℃まで加熱し、約4時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート24.16gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を6.45g得た。得られたポリマーは式(1-6)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは4,000、多分散度Mw/Mnは2.05であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、4-ヒドロキシベンズアルデヒド(東京化成工業株式会社製)5.85g、プロピレングリコールモノメチルエーテルアセテート17.23g、プロピレングリコールモノメチルエーテル17.23g、メタンスルホン酸(東京化成工業株式会社製)0.92gを入れた。その後150℃まで加熱し、約2.5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート20.10gで希釈した。この溶液をメタノール/水=50/50(vol%/vol%)溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を9.90g得た。得られたポリマーは式(1-7)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは4,100、多分散度Mw/Mnは3.01であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、4-(2-ヒドロキシエトキシ)ベンズアルデヒド(東京化成工業株式会社製)8.95g、プロピレングリコールモノメチルエーテルアセテート43.68g、メタンスルホン酸(東京化成工業株式会社製)0.78gを入れた。その後150℃まで加熱し、約2.5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート27.32gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を10.8g得た。得られたポリマーは式(1-8)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは3,400、多分散度Mw/Mnは1.85であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、2,4,6-トリメチルベンズアルデヒド(東京化成工業株式会社製)7.10g、プロピレングリコールモノメチルエーテルアセテート37.37g、メタンスルホン酸(東京化成工業株式会社製)0.92gを入れた。その後150℃まで加熱し、約21.5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート22.09gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を9.20g得た。得られたポリマーは式(1-9)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは12,700、多分散度Mw/Mnは3.82であった。
100mL二口フラスコにジフェニルアミン(東京化成工業株式会社製)7.04g、p-トルアルデヒド(東京化成工業株式会社製)5.00g、プロピレングリコールモノメチルエーテルアセテート20.65g、プロピレングリコールモノメチルエーテル8.85g、メタンスルホン酸(東京化成工業株式会社製)0.60gを入れた。その後150℃まで加熱し、約1.5時間還流撹拌した。反応終了後、シクロヘキサノン18.07gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を8.11g得た。得られたポリマーは式(1-10)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは15,300、多分散度Mw/Mnは3.52であった。
100mL二口フラスコにジフェニルアミン(東京化成工業株式会社製)9.02g、テレフタルアルデヒド酸(東京化成工業株式会社製)8.00g、プロピレングリコールモノメチルエーテルアセテート28.63g、プロピレングリコールモノメチルエーテル12.27g、メタンスルホン酸(東京化成工業株式会社製)0.51gを入れた。その後150℃まで加熱し、約30分還流撹拌した。反応終了後、シクロヘキサノン26.66gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を10.6g得た。得られたポリマーは式(1-11)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは82,200、多分散度Mw/Mnは5.57であった。
100mL二口フラスコにジフェニルアミン(東京化成工業株式会社製)8.90g、4-メチルチオベンズアルデヒド(東京化成工業株式会社製)8.00g、プロピレングリコールモノメチルエーテルアセテート28.43g、プロピレングリコールモノメチルエーテル12.28g、メタンスルホン酸(東京化成工業株式会社製)0.51gを入れた。その後150℃まで加熱し、約1時間還流撹拌した。反応終了後、シクロヘキサノン26.48gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を10.7g得た。得られたポリマーは式(1-12)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは6,300、多分散度Mw/Mnは2.90であった。
100mL二口フラスコにジフェニルアミン(東京化成工業株式会社製)8.95g、4-ニトロベンズアルデヒド(東京化成工業株式会社製)8.00g、プロピレングリコールモノメチルエーテルアセテート40.74g、メタンスルホン酸(東京化成工業株式会社製)0.51gを入れた。その後150℃まで加熱し、約15分還流撹拌した。反応終了後、シクロヘキサノン26.56gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を9.54g得た。得られたポリマーは式(1-13)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは2,500、多分散度Mw/Mnは1.95であった。
100mL二口フラスコにジフェニルアミン(東京化成工業株式会社製)6.80g、4-トリフルオロメチルベンズアルデヒド(東京化成工業株式会社製)7.00g、プロピレングリコールモノメチルエーテルアセテート23.49g、プロピレングリコールモノメチルエーテル10.07g、メタンスルホン酸(東京化成工業株式会社製)0.58gを入れた。その後150℃まで加熱し、約1.5時間還流撹拌した。反応終了後、シクロヘキサノン21.07gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を4.76g得た。得られたポリマーは式(1-14)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは103,000、多分散度Mw/Mnは2.32であった。
100mL二口フラスコに1,1,1-トリス(4-ヒドロキシフェニル)エタン(東京化成工業株式会社製)12.00g、p-トルアルデヒド(東京化成工業株式会社製)4.71g、プロピレングリコールモノメチルエーテルアセテート20.81g、プロピレングリコールモノメチルエーテル20.81g、メタンスルホン酸(東京化成工業株式会社製)1.13gを入れた。その後150℃まで加熱し、約24時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート24.08gで希釈した。この溶液をメタノール/水=60/40(vol%/vol%)に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を7.03g得た。得られたポリマーは式(1-15)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは2,100、多分散度Mw/Mnは1.61であった。
100mL二口フラスコに1,1,1-トリス(4-ヒドロキシフェニル)エタン(東京化成工業株式会社製)10.20g、テレフタルアルデヒド酸(東京化成工業株式会社製) 5.00g、プロピレングリコールモノメチルエーテルアセテート 18.30g、プロピレングリコールモノメチルエーテル 18.30g、メタンスルホン酸(東京化成工業株式会社製)0.48gを入れた。その後150℃まで加熱し、約24時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート23.74gで希釈した。この溶液をメタノール/水=50/50(vol%/vol%)に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を7.84g得た。得られたポリマーは式(1-16)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは4,000、多分散度Mw/Mnは2.17であった。
100mL二口フラスコに1,1,1-トリス(4-ヒドロキシフェニル)エタン(東京化成工業株式会社製)12.00g、4-メチルチオベンズアルデヒド(東京化成工業株式会社製)5.96g、プロピレングリコールモノメチルエーテルアセテート29.95g、プロピレングリコールモノメチルエーテル12.83g、メタンスルホン酸(東京化成工業株式会社製)0.38gを入れた。その後150℃まで加熱し、約44時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート28.67gで希釈した。この溶液をメタノール/水=50/50(vol%/vol%)に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を11.9g得た。得られたポリマーは式(1-17)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは2,000、多分散度Mw/Mnは1.73であった。
100mL二口フラスコに1,1,1-トリス(4-ヒドロキシフェニル)エタン(東京化成工業株式会社製)10.14g、4-ニトロベンズアルデヒド(東京化成工業株式会社製) 5.00g、プロピレングリコールモノメチルエーテルアセテート18.22g、プロピレングリコールモノメチルエーテル18.22g、メタンスルホン酸(東京化成工業株式会社製)0.48gを入れた。その後150℃まで加熱し、約24時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート23.64gで希釈した。この溶液をメタノール/水=50/50(vol%/vol%)に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を11.6g得た。得られたポリマーは式(1-18)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは4,300、多分散度Mw/Mnは2.14であった。
100mL二口フラスコに1,1,1-トリス(4-ヒドロキシフェニル)エタン(東京化成工業株式会社製)12.00g、4-トリフルオロメチルベンズアルデヒド(東京化成工業株式会社製)6.82g、プロピレングリコールモノメチルエーテルアセテート23.27g、プロピレングリコールモノメチルエーテル23.27g、メタンスルホン酸(東京化成工業株式会社製)1.13gを入れた。その後150℃まで加熱し、約5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート27.60gで希釈した。この溶液をメタノール/水=50/50(vol%/vol%)に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を11.1g得た。得られたポリマーは式(1-19)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは4,000、多分散度Mw/Mnは1.53であった。
100mL二口フラスコにN-フェニルアントラニル酸(東京化成工業株式会社製)10.05g、ベンズアルデヒド(東京化成工業株式会社製)5.00g、プロピレングリコールモノメチルエーテルアセテート18.35g、プロピレングリコールモノメチルエーテル 18.35g、メタンスルホン酸(東京化成工業株式会社製)0.68gを入れた。その後150℃まで加熱し、約2時間還流撹拌した。反応終了後、シクロヘキサノン22.81gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を7.81g得た。得られたポリマーは式(1-20)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは6,300、多分散度Mw/Mnは1.78であった。
100mL二口フラスコに3-メチルジフェニルアミン(東京化成工業株式会社製)9.50g、ベンズアルデヒド(東京化成工業株式会社製)5.50g、プロピレングリコールモノメチルエーテルアセテート18.37g、プロピレングリコールモノメチルエーテル 18.37g、メタンスルホン酸(東京化成工業株式会社製)0.75gを入れた。その後150℃まで加熱し、約45分還流撹拌した。反応終了後、シクロヘキサノン22.51gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を11.5g得た。得られたポリマーは式(1-21)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは52,700、多分散度Mw/Mnは8.86であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、ベンズアルデヒド(東京化成工業株式会社製)5.08g、プロピレングリコールモノメチルエーテルアセテート32.36g、メタンスルホン酸(東京化成工業株式会社製)0.92gを入れた。その後150℃まで加熱し、約1.5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート23.43gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を8.92g得た。得られたポリマーは式(2-1)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは32,200、多分散度Mw/Mnは2.14であった。
100mL二口フラスコにジフェニルアミン(東京化成工業株式会社製)8.77g、ベンズアルデヒド(東京化成工業株式会社製)5.50g、プロピレングリコールモノメチルエーテルアセテート24.53g、プロピレングリコールモノメチルエーテル10.51g、メタンスルホン酸(東京化成工業株式会社製)0.75gを入れた。その後150℃まで加熱し、約15分還流撹拌した。反応終了後、シクロヘキサノン 92.65gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を8.58g得た。得られたポリマーは式(2-2)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは8,400、多分散度Mw/Mnは2.38であった。
100mL二口フラスコに1,1,1-トリス(4-ヒドロキシフェニル)エタン(東京化成工業株式会社製)12.00g、ベンズアルデヒド(東京化成工業株式会社製)4.16g、プロピレングリコールモノメチルエーテルアセテート19.51g、プロピレングリコールモノメチルエーテル19.51g、メタンスルホン酸(東京化成工業株式会社製)0.56gを入れた。その後150℃まで加熱し、約19時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート24.08gで希釈した。この溶液をメタノール/水=50/50(vol%/vol%)溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を11.0g得た。得られたポリマーは式(2-3)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは4,600、多分散度Mw/Mnは1.64であった。
100mL二口フラスコにカルバゾール(東京化成工業株式会社製)8.00g、4-tert-ブチルベンズアルデヒド(東京化成工業株式会社製)7.77g、プロピレングリコールモノメチルエーテルアセテート38.94g、メタンスルホン酸(東京化成工業株式会社製)0.92gを入れた。その後150℃まで加熱し、約1.5時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート23.21gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を13.3g得た。得られたポリマーは式(2-4)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは25,800、多分散度Mw/Mnは4.44であった。
100mL二口フラスコにジフェニルアミン(東京化成工業株式会社製)8.34g、4-tert-ブチルベンズアルデヒド(東京化成工業株式会社製)8.34g、プロピレングリコールモノメチルエーテルアセテート39.24g、メタンスルホン酸(東京化成工業株式会社製)0.47gを入れた。その後150℃まで加熱し、約3時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート25.66gで希釈した。この溶液をメタノール溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を9.65g得た。得られたポリマーは式(2-5)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは6,300、多分散度Mw/Mnは2.03であった。
100mL二口フラスコに1,1,1-トリス(4-ヒドロキシフェニル)エタン(東京化成工業株式会社製)10.39g、4-tert-ブチルベンズアルデヒド(東京化成工業株式会社製)5.50g、プロピレングリコールモノメチルエーテルアセテート19.10g、プロピレングリコールモノメチルエーテル19.10g、メタンスルホン酸(東京化成工業株式会社製)0.49gを入れた。その後150℃まで加熱し、約24時間還流撹拌した。反応終了後、プロピレングリコールモノメチルエーテルアセテート24.85gで希釈した。この溶液をメタノール/水=50/50(vol%/vol%)溶液中に滴下し、再沈殿させた。得られた沈殿物を吸引ろ過し、ろ物を60℃で一晩減圧乾燥した。そして、粉末の樹脂を10.3g得た。得られたポリマーは式(2-6)に相当した。GPCによりポリスチレン換算で測定される重量平均分子量Mwは2,000、多分散度Mw/Mnは1.97であった。
(実施例1)
合成例1で得た樹脂1.0gに対して、界面活性剤としてメガファックR-40を0.001g混合し、プロピレングリコールモノメチルエーテルアセテート5.66g、プロピレングリコールモノメチルエーテル2.42gに溶解させ、孔径0.02μmのポリテトラフルオロエチレン製ミクロフィルターを用いて濾過して、多層膜によるリソグラフィープロセスに用いるレジスト下層膜形成組成物の溶液を調製した。
なお、ポリマーと界面活性剤と溶剤の配合量は以下表1乃至3の通りである。
実施例1乃至21及び比較例1乃至6で調製したレジスト下層膜形成組成物の溶液を、それぞれスピンコーターを用いてシリコンウエハー上に塗布し、ホットプレート上で400℃90秒間焼成し、レジスト下層膜(膜厚0.20μm)を形成した。これらレジスト下層膜をレジストに使用する溶剤である、乳酸エチル、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メチルエーテルアセテート、及びシクロヘキサノンに浸漬した。これらレジスト下層膜はこれら溶剤に不溶であった。
(膜密度の測定)
実施例1乃至21及び比較例1乃至6で調製したレジスト下層膜形成組成物の溶液を、それぞれスピンコーターを用いてシリコンウエハー上に塗布し、ホットプレート上で400℃90秒間焼成し、レジスト下層膜(膜厚0.20μm)を形成した。これらのレジスト下層膜の密度を求めるために、X線反射率測定装置(Bruker製)を用いて評価した。結果を下記表に示した。
実施例1乃至21及び比較例1乃至6で調製したレジスト下層膜形成組成物の溶液を、それぞれスピンコーターを用いてシリコンウエハー上に塗布し、ホットプレート上で400℃90秒間焼成し、レジスト下層膜(膜厚0.20μm)を形成した。これらのレジスト下層膜の硬度とヤング率を求めるために押し込み試験機(東陽テクニカ製)を用いて評価した。結果を下記表に示した。
実施例2、4、9及び比較例4乃至6で調製した各レジスト下層膜形成組成物の溶液を、スピンコーターを用いてそれぞれ酸化ケイ素被膜付きシリコンウエハー上に塗布した。ホットプレート上で400℃90秒間焼成しレジスト下層膜(膜厚200nm)を形成した。レジスト下層膜上にシリコンハードマスク形成組成物溶液を塗布し、240℃で1分間焼成しシリコンハードマスク層(膜厚30nm)を形成した。その上にレジスト溶液を塗布し、100℃で1分間焼成しレジスト層(膜厚150nm)を形成した。マスクを用いて波長193nmで露光し、露光後加熱PEB(105℃で1分間)を行った後、現像してレジストパターンを得た。その後、フッ素系ガス(成分はCF4)でドライエッチングを行い、レジストパターンをハードマスクに転写した。その後、酸素系ガス(成分はO2)でドライエッチングを行い、レジストパターンを本発明のレジスト下層膜に転写した。その後、フッ素系ガス(成分はC4F8)でドライエッチングを行い、シリコンウエハー上の酸化ケイ素被膜の除去を行った。その時のそれぞれのパターン形状を観察した。
パターン幅が狭まるにしたがいwigglingという不規則なパターンの曲がりが発生しやすくなるが、上記の実施例のレジスト下層膜形成組成物を用いて上述工程を行いwigglingを生じ始めるパターン幅を電子顕微鏡で観測した。
wigglingが発生することで忠実なパターンに基づく基板加工ができなくなるため、wigglingが発生する直前のパターン幅(限界パターン幅)により基板加工をする必要がある。wigglingが発生し始める限界パターン幅は、その値が狭ければ狭いほど微細な基板の加工が可能となる。
解像度の測定には測長走査型電子顕微鏡(日立製作所製)を用いた。測定結果を下記表に示した。
また、比較例4乃至6で対比すると、カルバゾールノボラック樹脂(比較例4)はジフェニルアミンノボラック樹脂(比較例5)と、多価フェノールノボラック樹脂(比較例6)に比べて膜密度、硬度、ヤング率において高く、それらの数値に比例してWigglingが発生する最小パターンサイズもほぼ同等か又は小さくなっている。カルバゾールノボラック樹脂(比較例4)について上述の傾向があり、ジフェニルアミンノボラック樹脂(比較例5)と、多価フェノールノボラック樹脂(比較例6)についても同様に、ノボラック樹脂を構成するベンゼン環に2種類以上の特定の化学基(a)、(b)、(c)が置換することで膜密度、硬度、ヤング率の向上と、それらの数値に比例してWigglingが発生する最小パターンサイズは小さくなり、Wiggling耐性が向上しエッチング耐性も向上する。
以上のことから、ベンゼン環に2種類以上の上記特定の化学基が置換することにより、膜密度、硬度、ヤング率の向上と、それに伴うWiggling耐性が向上しエッチング耐性が向上する。これはカルバゾールノボラック樹脂を用いたレジスト下層膜だけでなく、ノボラック樹脂を用いたレジスト下層膜に共通する効果と考えられる。
Claims (12)
- 下記式(1):
(式(1)において、基A及び基Bはそれぞれ独立して、芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環を有する有機基であって、酸化により質量増を生じる化学基(a)、加熱により架橋形成を生じる化学基(b)、及び硬化中に相分離を誘発する化学基(c)からなる群より選ばれた同種又は異種の2つ以上の1価又は2価の化学基が、該基Aもしくは基B又はその両方の基中の、芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環上の炭素原子に結合する水素原子と、それぞれ置換した構造を有する有機基であり、前記化学基が2価の場合、前記環同士は該化学基を介して結合もしくは該化学基とともに縮合していてもよい。)で表される繰り返し単位構造を有するノボラック樹脂を含むレジスト下層膜形成組成物。 - 芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環を有する有機基が、1又は複数のベンゼン環、ナフタレン環、又はベンゼン環とヘテロ環との縮合環を有する有機基である請求項1に記載のレジスト下層膜形成組成物。
- 式(1)のノボラック樹脂が、化学基(a)、化学基(b)、化学基(c)、化学基(a)と化学基(b)の組み合わせ、化学基(a)と化学基(c)の組み合わせ、化学基(b)と化学基(c)の組み合わせ、化学基(a)と化学基(b)と化学基(c)の組み合わせ、から選ばれた2種類以上の化学基で芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環の水素原子をそれぞれ置換した構造を有するノボラック樹脂である請求項1又は請求項2に記載のレジスト下層膜形成組成物。
- 式(1)で表されるノボラック樹脂は、化学基(b)から選ばれた同種又は異種の2つの化学基、又は化学基(a)と化学基(b)からそれぞれ選ばれた2種類の化学基が、基A及び基Bの両方の基中の芳香族環、縮合芳香族環、又は縮合芳香族ヘテロ環上の炭素原子に結合する少なくとも1つの水素原子とそれぞれ置換して、単位構造中に2種類の化学基が導入された構造を有するものである請求項3に記載のレジスト下層膜形成組成物。
- 化学基(a)がメチル基、スルフィド基、又はその組み合わせである請求項1乃至請求項4のいずれか1項に記載のレジスト下層膜形成組成物。
- 化学基(b)がアミノ基、カルボキシル基、カルボン酸アルキルエステル基、ニトロ基、ヒドロキシ基、エーテル基、又はその組み合わせである請求項1乃至請求項5のいずれか1項に記載のレジスト下層膜形成組成物。
- 化学基(c)がフルオロアルキル基である請求項1乃至請求項6のいずれか1項に記載のレジスト下層膜形成組成物。
- 更に架橋剤を含む請求項1乃至請求項7のいずれか1項に記載のレジスト下層膜形成組成物。
- 更に酸及び/又は酸発生剤を含む請求項1乃至請求項8のいずれか1項に記載のレジスト下層膜形成組成物。
- 請求項1乃至請求項9のいずれか1項に記載の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することによって得られるレジスト下層膜の製造方法。
- 半導体基板上に請求項1乃至請求項9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レジスト下層膜を形成する工程、その上にレジスト膜を形成する工程、光又は電子線の照射と現像によりレジストパターンを形成する工程、形成されたレジストパターンにより該下層膜をエッチングする工程、及びパターン化された下層膜により半導体基板を加工する工程を含む半導体装置の製造方法。
- 半導体基板上に請求項1乃至請求項9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レジスト下層膜を形成する工程、その上にハードマスクを形成する工程、更にその上にレジスト膜を形成する工程、光又は電子線の照射と現像によりレジストパターンを形成する工程、形成されたレジストパターンによりハードマスクをエッチングする工程、パターン化されたハードマスクにより該下層膜をエッチングする工程、及びパターン化されたレジスト下層膜により半導体基板を加工する工程を含む半導体装置の製造方法。
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