WO2010074075A1 - Additive for composition for forming resist underlayer film and composition for forming resist underlayer film comprising the same - Google Patents

Additive for composition for forming resist underlayer film and composition for forming resist underlayer film comprising the same Download PDF

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WO2010074075A1
WO2010074075A1 PCT/JP2009/071320 JP2009071320W WO2010074075A1 WO 2010074075 A1 WO2010074075 A1 WO 2010074075A1 JP 2009071320 W JP2009071320 W JP 2009071320W WO 2010074075 A1 WO2010074075 A1 WO 2010074075A1
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underlayer film
resist underlayer
resist
film forming
forming composition
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PCT/JP2009/071320
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French (fr)
Japanese (ja)
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坂本　力丸
佳臣 広井
邦慶 何
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日産化学工業株式会社
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Priority to JP2010544080A priority Critical patent/JP5477593B2/en
Priority to KR1020117016774A priority patent/KR101530197B1/en
Publication of WO2010074075A1 publication Critical patent/WO2010074075A1/en

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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
    • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • 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
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
    • 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
    • G03F7/70425—Imaging strategies, e.g. for increasing throughput or resolution, printing product fields larger than the image field or compensating lithography- or non-lithography errors, e.g. proximity correction, mix-and-match, stitching or double patterning
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene

Definitions

  • the present invention relates to an additive added to the resist underlayer film forming composition.
  • the present invention relates to a modifier that allows a surface layer of a resist underlayer film to be formed to form a pattern having a desired shape on the resist underlayer film.
  • the present invention relates to a resist underlayer film forming composition containing the additive (modifier).
  • a composition for forming an antireflection film used in a lithography process is known (see, for example, Patent Document 1 and Patent Document 2 below).
  • a photoresist layer is formed on the antireflection film formed using this composition, and then a photoresist pattern is formed by performing at least exposure and development processing.
  • Patent Document 1 describes a polymer compound having a repeating unit structure containing a halogen atom, particularly a bromine atom, an iodine atom, or a combination thereof as a component contained in the composition.
  • concentration of the resin binder component having a phenyl group described in Patent Document 2 is about 50 to 95% by weight of the total dry components (all components excluding the solvent) of the antireflection coating composition (Patent Document 2). (See paragraph 0033).
  • Double patterning or double exposure is described in Patent Document 3 and Patent Document 4, for example.
  • 5 to 8 of Patent Document 3 show a first lithography process for forming a first photosensitive film pattern from a first photosensitive film laminated on an organic material layer used as an antireflection film, and the first photosensitive film pattern.
  • a second lithography step is shown forming between the layer patterns.
  • Example 1 of FIG. 1 and FIG. 1 a step of forming a positive resist film on an organic antireflection film, and at least exposure and development are performed on the positive resist film to form a first resist pattern.
  • a second lithography step for forming at a position different from the above position is shown.
  • Japanese Patent No. 4038688 JP 2000-187331 A Japanese Patent No. 2803999 JP 2008-078220 A
  • the surface of the organic antireflection film is used again for exposure radiation and development in the second lithography process performed after the first lithography process.
  • the skirt shape of the resist pattern formed in the second lithography process does not become a straight shape, but tends to be a so-called footing shape.
  • the footing shape represents a shape in which the skirt is widened, in other words, a state where a portion where the resist pattern is in contact with the lower layer film is thick. This footing shape is also expressed as a skirt shape.
  • Patent Document 4 describes a method for solving the problem that the resist pattern after development becomes a “T-Top” shape or a reduced film shape (round shape). However, it cannot be said that an improvement measure for the skirt shape of the resist pattern is described.
  • the present invention relates to an additive used for preventing a skirt shape of a resist pattern formed on an underlayer film from becoming a footing shape, a resist underlayer film forming composition for lithography using the additive, and the resist underlayer
  • An object of the present invention is to provide a resist pattern forming method using a film forming composition.
  • L represents a linking group constituting a part of the main chain of the polymer
  • M includes a direct bond or at least one selected from —C ( ⁇ O) —, —CH 2 —, and —O—).
  • the copolymer further comprises the following formula (3): (Wherein R 2 represents a hydrogen atom or a methyl group, M has the same definition as in the first aspect, and A represents a substituent containing an adamantane ring or a lactone ring.)
  • the present invention relates to a resist underlayer film forming composition for lithography comprising a resin binder, a crosslinkable compound, a solvent, and the additive for a resist underlayer film forming composition according to any one of the first to fourth aspects.
  • the resist underlayer film forming composition for lithography according to the fifth aspect further comprising a compound that promotes a crosslinking reaction
  • the resist underlayer film forming composition for lithography according to the fifth aspect or the sixth aspect wherein the crosslinkable compound is a nitrogen-containing compound having 2 to 4 nitrogen atoms to which a methylol group or an alkoxymethyl group is bonded.
  • the compound that promotes the crosslinking reaction is a sulfonic acid compound, and relates to the resist underlayer film forming composition for lithography according to the sixth aspect
  • the compound for promoting the crosslinking reaction relates to the resist underlayer film forming composition for lithography according to the sixth aspect, which is a combination of an acid generator and a sulfonic acid compound.
  • a step of applying the resist underlayer film forming composition according to any one of the fifth to ninth aspects onto a semiconductor substrate and baking to form a resist underlayer film a resist film on the resist underlayer film Forming a first pattern on the resist underlayer film by exposing the resist film formed on the resist underlayer film, developing the resist film using a developer after the exposure
  • a method of forming a resist pattern used for manufacturing a semiconductor device including a step of forming a second pattern on the resist underlayer film exposed by the development so as not to overlap the first pattern.
  • the said exposure is related with the formation method of the resist pattern as described in a 10th viewpoint performed using ArF excimer laser.
  • the additive component is segregated near the surface of the resist underlayer film to be formed.
  • a resist pattern having a desired shape with improved footing shape can be formed on the resist underlayer film. In double patterning or double exposure, This is effective for improving the skirt shape of the formed pattern from a footing shape to a straight shape.
  • the additive according to the present invention contains a copolymer having at least the structural unit represented by the formula (1).
  • the structural unit V is, for example, the following formula: (2): (Wherein R 2 represents a hydrogen atom or a methyl group, M represents a direct bond or a linking group containing at least one selected from —C ( ⁇ O) —, —CH 2 — and —O—, Represents an alkyl group in which at least one hydrogen atom may be substituted with a fluorine atom, and at least one of M and Q contains a fluorine atom.) It is represented by In the above formula (2), R 2 may not be limited to a methyl group or a hydrogen atom that does not contain a fluorine atom. For example, it may be a methyl group in which at least one hydrogen atom is substituted with a fluorine atom, such as a trifluoromethyl group.
  • Q in the formula (2) represents, for example, an alkyl group having 1 to 3 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.
  • alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a trifluoropropyl group.
  • the copolymer is further represented by the following formula (3): (Wherein R 2 represents a hydrogen atom or a methyl group, M represents a direct bond or a linking group containing at least one selected from —C ( ⁇ O) —, —CH 2 — and —O—, Represents a substituent containing an adamantane ring or a lactone ring.) It can have the structural unit X represented by these.
  • R 2 may not be limited to a methyl group or a hydrogen atom that does not contain a fluorine atom. For example, it may be a methyl group in which at least one hydrogen atom is substituted with a fluorine atom, such as a trifluoromethyl group.
  • the substituent containing the adamantane ring or lactone ring may have a methyl group, an ethyl group or a hydroxy group as a substituent of the adamantane ring or lactone ring.
  • the substituent containing the lactone ring may be a substituent containing an adamantane structure, a norbornane structure, or a norbornene structure.
  • the lactone ring is preferably a 5-membered ring such as ⁇ -butyrolactone, but is not limited to a 5-membered ring, and may be a 6-membered ring such as ⁇ -valerolactone or a 7-membered ring such as ⁇ -caprolactone.
  • the crosslinkable compound contained in the composition for forming a resist underlayer film according to the present invention is, for example, a nitrogen-containing compound having 2 to 4 nitrogen atoms bonded with methylol groups or alkoxymethyl groups.
  • it can be added at a ratio of 1% by mass to 30% by mass with respect to the solid content of the composition for forming the lower layer film.
  • the solid content is defined in this specification as a component obtained by removing the solvent from the composition.
  • nitrogen-containing compounds include hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycol.
  • Uril 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3 3-tetrakis (methoxymethyl) urea is mentioned.
  • the resist underlayer film forming composition according to the present invention may further contain a compound that promotes a crosslinking reaction.
  • stimulates this crosslinking reaction can be added, for example in the ratio of 0.1 to 10 mass% with respect to solid content of the composition for resist underlayer film formation concerning this invention.
  • the compound that promotes the crosslinking reaction is, for example, a sulfonic acid compound, and may be a combination of an acid generator and a sulfonic acid compound.
  • the sulfonic acid compound include, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid Benzenedisulfonic acid, 1-naphthalenesulfonic acid and pyridinium-1-naphthalenesulfonic acid.
  • the solvent contained in the resist underlayer film forming composition according to the present invention include, for example, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monopropyl ether, methyl ethyl ketone, ethyl lactate, Examples include cyclohexanone, ⁇ -butyrolactone and N-methylpyrrolidone. A combination of at least two of these solvents may be used. And the ratio of the solvent with respect to the composition for resist lower layer film formation which concerns on this invention is 50 to 99.5 mass%, for example.
  • the resin binder contained in the resist underlayer film forming composition according to the present invention for example, polymers obtained in Synthesis Examples 1 to 4 described later can be applied. Further, as the resin binder, a base polymer contained in a known antireflection film forming composition or a known resist underlayer film forming composition can be applied as a resin binder.
  • the ratio of the resin binder with respect to the solid content of the composition for forming a resist underlayer film according to the present invention is, for example, 50% by mass or more and 99.5% by mass or less, and preferably 60% by mass or more and 90% by mass or less.
  • the composition for forming a resist underlayer film according to the present invention contains the above-mentioned copolymer as an additive, and the ratio thereof is, for example, 0.1% with respect to the solid content of the composition for forming a resist underlayer film according to the present invention. It is 0.5 mass% or more and 20 mass% or less, Preferably, they are 0.5 mass% or more and 10 mass% or less. When the proportion of the copolymer exceeds 20% by mass with respect to the solid content, the bottom shape of the formed resist pattern becomes an undercut profile, which causes a problem of pattern collapse.
  • the semiconductor substrate used in the method for forming a resist pattern according to the present invention is typically a silicon wafer, but is an SOI (Silicon on Insulator) substrate, or gallium arsenide (GaAs), indium phosphide (InP), or phosphide.
  • a compound semiconductor wafer such as gallium (GaP) may be used.
  • An insulating film such as a silicon oxide film, a nitrogen-containing silicon oxide film (SiON film), a carbon-containing silicon oxide film (SiOC film), or a fluorine-containing silicon oxide film (SiOF film) is formed on the semiconductor substrate. It may be formed. In this case, the resist underlayer film is formed on the film to be processed.
  • an ArF excimer laser can be used for the exposure performed in the method for forming a resist pattern according to the present invention.
  • the resist solution for forming the resist film may be either a positive type or a negative type, and a chemically amplified resist that is sensitive to an ArF excimer laser can be used.
  • an alkaline developer such as an aqueous tetramethylammonium hydroxide (TMAH) solution can be used.
  • TMAH aqueous tetramethylammonium hydroxide
  • the resist underlayer film forming composition to which the additive according to the present invention is added is formed on the resist underlayer film that has been exposed and exposed to the developer to form the first pattern.
  • the resist underlayer film forming composition according to the present invention is not limited to double patterning or double exposure, but the bottom shape of the resist pattern is footed. It can also be applied to the case where it is easily formed into a shape.
  • the average molecular weights of the polymers shown in the following Synthesis Examples 1 to 9 in this specification are measurement results by gel permeation chromatography (hereinafter abbreviated as GPC).
  • the measurement conditions etc. are as follows using the Tosoh Co., Ltd. product GPC apparatus for a measurement.
  • GPC column Shodex (registered trademark) and Asahipak (registered trademark) (Showa Denko KK) Column temperature: 40 ° C Solvent: N, N-dimethylformamide (DMF) Flow rate: 0.6 ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)
  • ⁇ Synthesis Example 8> 4.50 g of 4-tertiarybutoxystyrene, 3.00 g of trifluoroethyl methacrylate, and 4.50 g of 2-ethyl-2-adamantyl methacrylate were dissolved in 50.6 g of propylene glycol monomethyl ether, and the temperature was raised to 70 ° C. A solution prepared by dissolving 0.15 g of azobisisobutyronitrile in 10 g of propylene glycol monomethyl ether was slowly added dropwise, followed by reaction at 80 ° C. for 24 hours to obtain a solution containing a polymer. When GPC analysis was performed, the weight average molecular weight was 30,000 in terms of standard polystyrene. The polymer obtained in this synthesis example corresponds to a copolymer contained in the additive according to the present invention.
  • Example 1 To 4 g of a solution containing 0.8 g of the polymer obtained in Synthesis Example 1, 0.2 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), pyridinium-p- 0.02 g of toluenesulfonic acid and 0.08 g of the polymer solution obtained in Synthesis Example 5 were mixed and dissolved in 25.02 g of propylene glycol monomethyl ether and 12.12 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
  • POWDERLINK registered trademark
  • Example 2 To 4 g of a solution containing 0.8 g of the polymer obtained in Synthesis Example 2, 0.2 g of tetramethoxymethylglycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), 5-sulfosalicylic acid 0.02 g and 0.08 g of the polymer solution obtained in Synthesis Example 5 were mixed and dissolved in 25.02 g of propylene glycol monomethyl ether and 12.12 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
  • POWDERLINK registered trademark
  • Example 3 To 4 g of the solution containing 1.2 g of the polymer obtained in Synthesis Example 3, 0.3 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), 5-sulfosalicylic acid 0.03 g and 0.12 g of the polymer solution obtained in Synthesis Example 5 were mixed and dissolved in 38.97 g of propylene glycol monomethyl ether and 17.90 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
  • tetramethoxymethyl glycoluril manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174
  • Example 4 To 4 g of the solution containing 1.2 g of the polymer obtained in Synthesis Example 1, 0.3 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), 5-sulfosalicylic acid 0.03 g and 0.12 g of the polymer solution obtained in Synthesis Example 6 were mixed and dissolved in 38.97 g of propylene glycol monomethyl ether and 17.90 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
  • tetramethoxymethyl glycoluril manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174
  • Example 5 To 4 g of a solution containing 1.2 g of the polymer obtained in Synthesis Example 4, 0.3 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), 5-sulfosalicylic acid 0.03 g and 0.12 g of the polymer solution obtained in Synthesis Example 8 were mixed and dissolved in 38.97 g of propylene glycol monomethyl ether and 17.90 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
  • tetramethoxymethyl glycoluril manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174
  • the target line width is set to 65 nm or 80 nm line and space, and the resist pattern dimensions at the optimum exposure and focus are measured with a length measuring SEM, and the sectional shape of the resist pattern in the direction perpendicular to the substrate (silicon wafer) is measured. By observing with a cross-sectional SEM, it can be confirmed whether or not a target resist pattern is formed.
  • the skirt shape of the first pattern and the second pattern was compared with a cross-sectional SEM, and evaluation was performed in three stages: skirt shape, pattern collapse, and straight shape.
  • the results are shown in Table 1. 1 and 2 show cross-sectional SEM images.

Abstract

Provided is an additive for a composition for forming a resist underlayer film with which footing of the resist pattern formed on the resist underlayer film is prevented. The additive comprises a copolymer having at least structural units V and W represented by formula (1) (1) (where L is a bond group that forms part of the polymer chain; M is a direct bond or linking group that contains at least one selected from -C(=O)-, -CH2-, and -O-; Q is an alkyl group wherein at least one of the hydrogen atoms is optionally substituted by a fluorine atom; at least one of L, M, and Q contains fluorine atoms; and R1 is an acetyl group, alkoxyalkyl group, tertiary alkyl group, or hydrogen atom).

Description

レジスト下層膜形成組成物用添加剤及びそれを含むレジスト下層膜形成用組成物Additive for resist underlayer film forming composition and resist underlayer film forming composition containing the same
　本発明は、レジスト下層膜形成用組成物に添加される添加剤に関する。特に、形成されるレジスト下層膜の表層を、当該レジスト下層膜上に所望の形状のパターンが形成されるようにする改質剤に関する。更に、当該添加剤（改質剤）を含むレジスト下層膜形成用組成物に関する。 The present invention relates to an additive added to the resist underlayer film forming composition. In particular, the present invention relates to a modifier that allows a surface layer of a resist underlayer film to be formed to form a pattern having a desired shape on the resist underlayer film. Furthermore, the present invention relates to a resist underlayer film forming composition containing the additive (modifier).
　リソグラフィープロセスに用いられる反射防止膜を形成するための組成物が知られている（例えば、下記特許文献１及び特許文献２参照）。この組成物を用いて形成された反射防止膜上に、フォトレジスト層が形成され、その後少なくとも露光及び現像処理を行うことによってフォトレジストパターンが形成される。 A composition for forming an antireflection film used in a lithography process is known (see, for example, Patent Document 1 and Patent Document 2 below). A photoresist layer is formed on the antireflection film formed using this composition, and then a photoresist pattern is formed by performing at least exposure and development processing.
　特許文献１には、上記組成物に含まれる成分として、ハロゲン原子、特に臭素原子、ヨウ素原子又はその組み合わせを含有する繰り返し単位構造を有する高分子化合物が記載されている。特許文献２に記載された、フェニル基を有する樹脂バインダー成分の濃度は、反射防止コーティング組成物の全乾燥成分（溶媒を除いた全成分）の約５０～９５重量％である（特許文献２の段落００３３参照）。 Patent Document 1 describes a polymer compound having a repeating unit structure containing a halogen atom, particularly a bromine atom, an iodine atom, or a combination thereof as a component contained in the composition. The concentration of the resin binder component having a phenyl group described in Patent Document 2 is about 50 to 95% by weight of the total dry components (all components excluding the solvent) of the antireflection coating composition (Patent Document 2). (See paragraph 0033).
　一方、近年微細なパターンを形成する方法として、ダブルパターニング又はダブル露光と称するリソグラフィープロセスが検討されている。ダブルパターニング又はダブル露光は、例えば下記特許文献３及び特許文献４に記載されている。特許文献３の図５乃至図８には、反射防止膜として用いられる有機物質層上に積層された第１感光膜から第１感光膜パターンを形成する第１リソグラフィー工程、その第１感光膜パターンをマスクとして有機物質層パターンを形成するエッチング工程、その有機物質層パターンを被覆する第２感光膜を形成する工程、その第２感光膜から第２感光膜パターンを、隣り合う２つの前記有機物質層パターン間に形成する第２リソグラフィー工程が示されている。 On the other hand, in recent years, a lithography process called double patterning or double exposure has been studied as a method for forming a fine pattern. Double patterning or double exposure is described in Patent Document 3 and Patent Document 4, for example. 5 to 8 of Patent Document 3 show a first lithography process for forming a first photosensitive film pattern from a first photosensitive film laminated on an organic material layer used as an antireflection film, and the first photosensitive film pattern. An etching process for forming an organic material layer pattern using the mask as a mask, a process for forming a second photosensitive film covering the organic material layer pattern, and a second photosensitive film pattern from the second photosensitive film to the two adjacent organic substances A second lithography step is shown forming between the layer patterns.
　特許文献４の実施例１及び図１には、有機系反射防止膜上にポジ型レジスト膜を形成する工程、そのポジ型レジスト膜に対し少なくとも露光及び現像を行い、第１レジストパターンを形成する１回目のリソグラフィー工程、その第１レジストパターンを被覆するネガ型レジスト膜を形成する工程、そのネガ型レジスト膜に対し少なくとも露光及び現像を行い、第２レジストパターンを前記第１レジストパターンが形成された位置とは異なる位置に形成する２回目のリソグラフィー工程が示されている。
特許第４０３８６８８号公報 特開２０００－１８７３３１号公報 特許第２８０３９９９号公報 特開２００８－０７８２２０号公報 In Example 1 of FIG. 1 and FIG. 1, a step of forming a positive resist film on an organic antireflection film, and at least exposure and development are performed on the positive resist film to form a first resist pattern. The first lithography process, the step of forming a negative resist film covering the first resist pattern, the negative resist film is at least exposed and developed, and the second resist pattern is formed on the first resist pattern. A second lithography step for forming at a position different from the above position is shown.
Japanese Patent No. 4038688 JP 2000-187331 A Japanese Patent No. 2803999 JP 2008-078220 A
　前述の特許文献４に記載されているリソグラフィープロセスでは、前記有機系反射防止膜の表面は、１回目のリソグラフィー工程後に行われる２回目のリソグラフィー工程において、再び露光用の放射線及び現像処理で使用される現像液に曝される。このような場合、２回目のリソグラフィー工程で形成されるレジストパターンは、その裾形状がストレート形状にならず、いわゆるフッティング形状になりやすい。フッティング形状とは、裾が広がった形状、換言すると、レジストパターンが下層膜に接する部分が太くなっている状態を表す。このフッティング形状は、裾引き形状とも表現される。 In the lithography process described in the above-mentioned Patent Document 4, the surface of the organic antireflection film is used again for exposure radiation and development in the second lithography process performed after the first lithography process. Exposed to the developer. In such a case, the skirt shape of the resist pattern formed in the second lithography process does not become a straight shape, but tends to be a so-called footing shape. The footing shape represents a shape in which the skirt is widened, in other words, a state where a portion where the resist pattern is in contact with the lower layer film is thick. This footing shape is also expressed as a skirt shape.
　この特許文献４には、現像後のレジストパターンが、“Ｔ－Ｔｏｐ”形状又は膜減り形状（丸まり形状）になる問題を解決するための方法が記載されている。しかしながら、レジストパターンの裾形状に対する改善策が記載されているとはいえない。 This Patent Document 4 describes a method for solving the problem that the resist pattern after development becomes a “T-Top” shape or a reduced film shape (round shape). However, it cannot be said that an improvement measure for the skirt shape of the resist pattern is described.
　本発明は、下層膜上に形成されるレジストパターンの裾形状がフッティング形状となることを防止するために用いる添加剤、その添加剤を用いたリソグラフィー用レジスト下層膜形成組成物及び該レジスト下層膜形成組成物を使用したレジストパターン形成方法を提供することを目的とする。 The present invention relates to an additive used for preventing a skirt shape of a resist pattern formed on an underlayer film from becoming a footing shape, a resist underlayer film forming composition for lithography using the additive, and the resist underlayer An object of the present invention is to provide a resist pattern forming method using a film forming composition.
　本発明は、第１観点として、下記式（１）：
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｌはポリマーの主鎖の一部を構成する結合基を表し、Ｍは直接結合又は－Ｃ（＝Ｏ）－、－ＣＨ2－及び－Ｏ－から選ばれる少なくとも１種を含む連結基を表し、Ｑは少なくとも１つの水素原子がフッ素原子で置換されていてもよいアルキル基を表し、前記Ｌ、Ｍ及びＱのうち少なくとも１つはフッ素原子を含み、Ｒ1はアセチル基、アルコキシアルキル基、３級アルキル基又は水素原子を表す。）
で表される構造単位Ｖ及びＷを少なくとも有する共重合体を含有するレジスト下層膜形成組成物用添加剤に関する、
　第２観点として、前記式（１）において前記構造単位Ｖは、下記式（２）：
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ2は水素原子又はメチル基を表し、Ｍ及びＱは第１観点における定義と同義である。）
で表される、第１観点に記載のレジスト下層膜形成組成物用添加剤に関する、
　第３観点として、前記式（２）中、Ｑは、少なくとも１つの水素原子がフッ素原子で置換された炭素原子数１乃至３のアルキル基を表す、第２観点に記載のレジスト下層膜形成組成物用添加剤に関する、
　第４観点として、前記共重合体は更に下記式（３）：
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ2は水素原子又はメチル基を表し、Ｍは第１観点における定義と同義であり、Ａはアダマンタン環又はラクトン環を含む置換基を表す。）
で表される構造単位Ｘを有する、第１観点乃至第３観点のいずれかに記載のレジスト下層膜形成組成物用添加剤に関する、
　第５観点として、樹脂バインダー、架橋性化合物、溶剤及び第１観点乃至第４観点のいずれかに記載のレジスト下層膜形成組成物用添加剤を含むリソグラフィー用レジスト下層膜形成組成物に関する、
　第６観点として、架橋反応を促進させる化合物を更に含む第５観点に記載のリソグラフィー用レジスト下層膜形成組成物に関する、
　第７観点として、前記架橋性化合物はメチロール基又はアルコキシメチル基が結合した窒素原子を２つ乃至４つ有する含窒素化合物である第５観点又は第６観点に記載のリソグラフィー用レジスト下層膜形成組成物に関する、
　第８観点として、前記架橋反応を促進させる化合物はスルホン酸化合物である第６観点に記載のリソグラフィー用レジスト下層膜形成組成物に関する、
　第９観点として、前記架橋反応を促進させる化合物は酸発生剤とスルホン酸化合物との組み合わせである第６観点に記載のリソグラフィー用レジスト下層膜形成組成物に関する、
　第１０観点として、第５観点乃至第９観点のいずれか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ベークしてレジスト下層膜を形成する工程、前記レジスト下層膜上にレジスト膜を形成する工程、前記レジスト下層膜上に層形成された前記レジスト膜を露光する工程、露光後に現像液を用いて前記レジスト膜を現像することによって第１のパターンを前記レジスト下層膜上に形成する工程、及び前記第１のパターンと重ならないように、前記現像により露出した前記レジスト下層膜上に第２のパターンを形成する工程を含む、半導体装置の製造に用いるレジストパターンの形成方法に関する、
　第１１観点として、前記露光は、ＡｒＦエキシマレーザーを用いて行われる、第１０観点に記載のレジストパターンの形成方法に関する。 As a first aspect of the present invention, the following formula (1):
Figure JPOXMLDOC01-appb-C000004
 (In the formula, L represents a linking group constituting a part of the main chain of the polymer, and M includes a direct bond or at least one selected from —C (═O) —, —CH 2 —, and —O—). Represents a linking group, Q represents an alkyl group in which at least one hydrogen atom may be substituted with a fluorine atom, at least one of L, M and Q includes a fluorine atom, R 1 represents an acetyl group, Represents an alkoxyalkyl group, a tertiary alkyl group or a hydrogen atom.)
The additive for a resist underlayer film forming composition containing a copolymer having at least structural units V and W represented by
As a second aspect, in the formula (1), the structural unit V is represented by the following formula (2):
Figure JPOXMLDOC01-appb-C000005
 (In the formula, R 2 represents a hydrogen atom or a methyl group, and M and Q are as defined in the first aspect.)
Represented by the additive for resist underlayer film forming composition according to the first aspect,
As a third aspect, the resist underlayer film forming composition according to the second aspect, wherein Q in the formula (2) represents an alkyl group having 1 to 3 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. For food additives,
As a fourth aspect, the copolymer further comprises the following formula (3):
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 2 represents a hydrogen atom or a methyl group, M has the same definition as in the first aspect, and A represents a substituent containing an adamantane ring or a lactone ring.)
The additive for a resist underlayer film forming composition according to any one of the first to third aspects, having a structural unit X represented by:
As a fifth aspect, the present invention relates to a resist underlayer film forming composition for lithography comprising a resin binder, a crosslinkable compound, a solvent, and the additive for a resist underlayer film forming composition according to any one of the first to fourth aspects.
As a sixth aspect, the resist underlayer film forming composition for lithography according to the fifth aspect, further comprising a compound that promotes a crosslinking reaction,
As a seventh aspect, the resist underlayer film forming composition for lithography according to the fifth aspect or the sixth aspect, wherein the crosslinkable compound is a nitrogen-containing compound having 2 to 4 nitrogen atoms to which a methylol group or an alkoxymethyl group is bonded. About things,
As an eighth aspect, the compound that promotes the crosslinking reaction is a sulfonic acid compound, and relates to the resist underlayer film forming composition for lithography according to the sixth aspect,
As a ninth aspect, the compound for promoting the crosslinking reaction relates to the resist underlayer film forming composition for lithography according to the sixth aspect, which is a combination of an acid generator and a sulfonic acid compound.
As a tenth aspect, a step of applying the resist underlayer film forming composition according to any one of the fifth to ninth aspects onto a semiconductor substrate and baking to form a resist underlayer film, a resist film on the resist underlayer film Forming a first pattern on the resist underlayer film by exposing the resist film formed on the resist underlayer film, developing the resist film using a developer after the exposure And a method of forming a resist pattern used for manufacturing a semiconductor device, including a step of forming a second pattern on the resist underlayer film exposed by the development so as not to overlap the first pattern.
As an 11th viewpoint, the said exposure is related with the formation method of the resist pattern as described in a 10th viewpoint performed using ArF excimer laser.
　本発明に係る添加剤が添加されたレジスト下層膜形成用組成物をリソグラフィープロセスに適用することによって、形成されるレジスト下層膜の表面近傍に添加剤成分が偏析する。これにより、該レジスト下層膜形成用組成物を用いたレジストパターン形成方法では、該レジスト下層膜上に、フッティング形状が改善された所望の形状のレジストパターンを形成でき、ダブルパターニング又はダブル露光において形成されるパターンの裾形状が、フッティング形状からストレート形状になるよう改善することに有効である。 By applying the composition for forming a resist underlayer film to which the additive according to the present invention is added to a lithography process, the additive component is segregated near the surface of the resist underlayer film to be formed. Thus, in the resist pattern forming method using the resist underlayer film forming composition, a resist pattern having a desired shape with improved footing shape can be formed on the resist underlayer film. In double patterning or double exposure, This is effective for improving the skirt shape of the formed pattern from a footing shape to a straight shape.
　本発明に係る添加剤は前記式（１）で表される構造単位を少なくとも有する共重合体を含有するが、当該式（１）で表される構造単位のうち構造単位Ｖは、例えば下記式（２）：
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ2は水素原子又はメチル基を表し、Ｍは直接結合又は－Ｃ（＝Ｏ）－、－ＣＨ2－及び－Ｏ－から選ばれる少なくとも１種を含む連結基を表し、Ｑは少なくとも１つの水素原子がフッ素原子で置換されていてもよいアルキル基を表し、前記Ｍ及びＱのうち少なくとも１つはフッ素原子を含む。）
で表される。
　上記式（２）において、Ｒ2はフッ素原子を含まないメチル基又は水素原子に限定されなくてもよい。例えばトリフルオロメチル基のように、少なくとも１つの水素原子がフッ素原子で置換されたメチル基でもよい。 The additive according to the present invention contains a copolymer having at least the structural unit represented by the formula (1). Among the structural units represented by the formula (1), the structural unit V is, for example, the following formula: (2):
Figure JPOXMLDOC01-appb-C000007
 (Wherein R 2 represents a hydrogen atom or a methyl group, M represents a direct bond or a linking group containing at least one selected from —C (═O) —, —CH 2 — and —O—, Represents an alkyl group in which at least one hydrogen atom may be substituted with a fluorine atom, and at least one of M and Q contains a fluorine atom.)
It is represented by
In the above formula (2), R 2 may not be limited to a methyl group or a hydrogen atom that does not contain a fluorine atom. For example, it may be a methyl group in which at least one hydrogen atom is substituted with a fluorine atom, such as a trifluoromethyl group.
　前記式（２）のＱは、例えば、少なくとも１つの水素原子がフッ素原子で置換された炭素原子数１乃至３のアルキル基を表す。当該アルキル基として、例えばフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、トリフルオロエチル基及びトリフルオロプロピル基が挙げられる。 Q in the formula (2) represents, for example, an alkyl group having 1 to 3 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Examples of the alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a trifluoropropyl group.
　下記式（１ａ）乃至式（１ｅ）は、前記式（１）で表される構造単位Ｖ及びＷを少なくとも有する共重合体の例である。
Figure JPOXMLDOC01-appb-C000008
 The following formulas (1a) to (1e) are examples of copolymers having at least the structural units V and W represented by the formula (1).
Figure JPOXMLDOC01-appb-C000008
　前記共重合体は更に下記式（３）：
Figure JPOXMLDOC01-appb-C000009
 （式中、Ｒ2は水素原子又はメチル基を表し、Ｍは直接結合又は－Ｃ（＝Ｏ）－、－ＣＨ2－及び－Ｏ－から選ばれる少なくとも１種を含む連結基を表し、Ａはアダマンタン環又はラクトン環を含む置換基を表す。）
で表される構造単位Ｘを有することができる。
　上記式（３）において、Ｒ2はフッ素原子を含まないメチル基又は水素原子に限定されなくてもよい。例えばトリフルオロメチル基のように、少なくとも１つの水素原子がフッ素原子で置換されたメチル基でもよい。 The copolymer is further represented by the following formula (3):
Figure JPOXMLDOC01-appb-C000009
 (Wherein R 2 represents a hydrogen atom or a methyl group, M represents a direct bond or a linking group containing at least one selected from —C (═O) —, —CH 2 — and —O—, Represents a substituent containing an adamantane ring or a lactone ring.)
It can have the structural unit X represented by these.
In the above formula (3), R 2 may not be limited to a methyl group or a hydrogen atom that does not contain a fluorine atom. For example, it may be a methyl group in which at least one hydrogen atom is substituted with a fluorine atom, such as a trifluoromethyl group.
　下記式（３ａ）乃至式（３ｆ）は、前記式（３）で表される構造単位の例である。
Figure JPOXMLDOC01-appb-C000010
 The following formulas (3a) to (3f) are examples of the structural unit represented by the formula (3).
Figure JPOXMLDOC01-appb-C000010
　前記アダマンタン環又はラクトン環を含む置換基は、アダマンタン環又はラクトン環の置換基としてメチル基、エチル基又はヒドロキシ基を有してもよい。前記ラクトン環を含む置換基はさらに、アダマンタン構造又はノルボルナン構造若しくはノルボルネン構造を含む置換基としてもよい。ラクトン環は、γ－ブチロラクトンのような５員環が好ましいが、５員環に限定されず、δ－バレロラクトンのような６員環、ε－カプロラクトンのような７員環でもよい。 The substituent containing the adamantane ring or lactone ring may have a methyl group, an ethyl group or a hydroxy group as a substituent of the adamantane ring or lactone ring. The substituent containing the lactone ring may be a substituent containing an adamantane structure, a norbornane structure, or a norbornene structure. The lactone ring is preferably a 5-membered ring such as γ-butyrolactone, but is not limited to a 5-membered ring, and may be a 6-membered ring such as δ-valerolactone or a 7-membered ring such as ε-caprolactone.
　本発明に係るレジスト下層膜形成用組成物に含まれる架橋性化合物は、例えば、メチロール基又はアルコキシメチル基が結合した窒素原子を２つ乃至４つ有する含窒素化合物であり、本発明に係るレジスト下層膜形成用組成物の固形分に対し例えば１質量％以上３０質量％以下の割合で添加することができる。ここで、固形分とは、組成物から溶剤を除いた成分であると本明細書では定義する。このような含窒素化合物として、例えば、ヘキサメトキシメチルメラミン、テトラメトキシメチルベンゾグアナミン、１，３，４，６－テトラキス（メトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ブトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ヒドロキシメチル）グリコールウリル、１，３－ビス（ヒドロキシメチル）尿素、１，１，３，３－テトラキス（ブトキシメチル）尿素及び１，１，３，３－テトラキス（メトキシメチル）尿素が挙げられる。 The crosslinkable compound contained in the composition for forming a resist underlayer film according to the present invention is, for example, a nitrogen-containing compound having 2 to 4 nitrogen atoms bonded with methylol groups or alkoxymethyl groups. For example, it can be added at a ratio of 1% by mass to 30% by mass with respect to the solid content of the composition for forming the lower layer film. Here, the solid content is defined in this specification as a component obtained by removing the solvent from the composition. Examples of such nitrogen-containing compounds include hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycol. Uril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3 3-tetrakis (methoxymethyl) urea is mentioned.
　本発明に係るレジスト下層膜形成用組成物は、架橋反応を促進させる化合物を更に含むことができる。本発明に係るレジスト下層膜形成用組成物の固形分に対し、例えば０．１質量％以上１０質量％以下の割合で、この架橋反応を促進させる化合物を添加することができる。当該架橋反応を促進させる化合物は、例えばスルホン酸化合物であり、酸発生剤とスルホン酸化合物との組み合わせでもよい。スルホン酸化合物の具体例として、例えば、ｐ－トルエンスルホン酸、トリフルオロメタンスルホン酸、ピリジニウム－ｐ－トルエンスルホン酸、カンファースルホン酸、５－スルホサリチル酸、４－クロロベンゼンスルホン酸、４－ヒドロキシベンゼンスルホン酸、ベンゼンジスルホン酸、１－ナフタレンスルホン酸及びピリジニウム－１－ナフタレンスルホン酸が挙げられる。 The resist underlayer film forming composition according to the present invention may further contain a compound that promotes a crosslinking reaction. The compound which accelerates | stimulates this crosslinking reaction can be added, for example in the ratio of 0.1 to 10 mass% with respect to solid content of the composition for resist underlayer film formation concerning this invention. The compound that promotes the crosslinking reaction is, for example, a sulfonic acid compound, and may be a combination of an acid generator and a sulfonic acid compound. Specific examples of the sulfonic acid compound include, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid Benzenedisulfonic acid, 1-naphthalenesulfonic acid and pyridinium-1-naphthalenesulfonic acid.
　本発明に係るレジスト下層膜形成用組成物に含まれる溶剤の具体例として、例えば、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノプロピルエーテル、メチルエチルケトン、乳酸エチル、シクロヘキサノン、γ－ブチロラクトン及びＮ－メチルピロリドンが挙げられる。これらの溶剤を少なくとも２種組み合わせて用いてもよい。そして、本発明に係るレジスト下層膜形成用組成物に対する溶剤の割合は、例えば５０質量％以上９９．５質量％以下である。 Specific examples of the solvent contained in the resist underlayer film forming composition according to the present invention include, for example, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monopropyl ether, methyl ethyl ketone, ethyl lactate, Examples include cyclohexanone, γ-butyrolactone and N-methylpyrrolidone. A combination of at least two of these solvents may be used. And the ratio of the solvent with respect to the composition for resist lower layer film formation which concerns on this invention is 50 to 99.5 mass%, for example.
　本発明に係るレジスト下層膜形成用組成物に含まれる樹脂バインダーとして、例えば、後述する合成例１乃至合成例４によって得られるポリマーを適用することができる。また、当該樹脂バインダーとして、公知の反射防止膜形成用組成物又は公知のレジスト下層膜形成用組成物に含まれるベースポリマーを、樹脂バインダーとして適用することができる。本発明に係るレジスト下層膜形成用組成物の固形分に対し、樹脂バインダーの割合は例えば５０質量％以上９９．５質量％以下、好ましくは、６０質量％以上９０質量％以下である。 As the resin binder contained in the resist underlayer film forming composition according to the present invention, for example, polymers obtained in Synthesis Examples 1 to 4 described later can be applied. Further, as the resin binder, a base polymer contained in a known antireflection film forming composition or a known resist underlayer film forming composition can be applied as a resin binder. The ratio of the resin binder with respect to the solid content of the composition for forming a resist underlayer film according to the present invention is, for example, 50% by mass or more and 99.5% by mass or less, and preferably 60% by mass or more and 90% by mass or less.
　本発明に係るレジスト下層膜形成用組成物は、添加剤として前述の共重合体を含むが、その割合は、本発明に係るレジスト下層膜形成用組成物の固形分に対し、例えば０．１質量％以上２０質量％以下、好ましくは、０．５質量％以上１０質量％以下である。共重合体の割合が固形分に対し２０質量％を超える場合、形成されるレジストパターンの裾形状がアンダーカットプロファイルとなるため、パターン倒れを起こすという問題がある。 The composition for forming a resist underlayer film according to the present invention contains the above-mentioned copolymer as an additive, and the ratio thereof is, for example, 0.1% with respect to the solid content of the composition for forming a resist underlayer film according to the present invention. It is 0.5 mass% or more and 20 mass% or less, Preferably, they are 0.5 mass% or more and 10 mass% or less. When the proportion of the copolymer exceeds 20% by mass with respect to the solid content, the bottom shape of the formed resist pattern becomes an undercut profile, which causes a problem of pattern collapse.
　本発明に係るレジストパターンの形成方法において用いられる半導体基板は、代表的にはシリコンウエハーであるが、ＳＯＩ（Ｓｉｌｉｃｏｎ　ｏｎ　Ｉｎｓｕｌａｔｏｒ）基板、又は砒化ガリウム（ＧａＡｓ）、リン化インジウム（ＩｎＰ）、リン化ガリウム（ＧａＰ）などの化合物半導体ウエハーを用いてもよい。前記半導体基板上には、被加工膜、例えば酸化珪素膜、窒素含有酸化珪素膜（ＳｉＯＮ膜）、炭素含有酸化珪素膜（ＳｉＯＣ膜）、フッ素含有酸化珪素膜（ＳｉＯＦ膜）などの絶縁膜が形成されていてもよい。この場合、レジスト下層膜は被加工膜上に形成される。 The semiconductor substrate used in the method for forming a resist pattern according to the present invention is typically a silicon wafer, but is an SOI (Silicon on Insulator) substrate, or gallium arsenide (GaAs), indium phosphide (InP), or phosphide. A compound semiconductor wafer such as gallium (GaP) may be used. An insulating film such as a silicon oxide film, a nitrogen-containing silicon oxide film (SiON film), a carbon-containing silicon oxide film (SiOC film), or a fluorine-containing silicon oxide film (SiOF film) is formed on the semiconductor substrate. It may be formed. In this case, the resist underlayer film is formed on the film to be processed.
　本発明に係るレジストパターンの形成方法において行われる露光には、例えばＡｒＦエキシマレーザーを用いることができる。レジスト膜を形成するためのレジスト溶液は、ポジ型、ネガ型いずれでもよく、ＡｒＦエキシマレーザーに感光する化学増幅型レジストを用いることができる。 For the exposure performed in the method for forming a resist pattern according to the present invention, for example, an ArF excimer laser can be used. The resist solution for forming the resist film may be either a positive type or a negative type, and a chemically amplified resist that is sensitive to an ArF excimer laser can be used.
　本発明に係るレジストパターンの形成方法において用いられる現像液として、例えばテトラメチルアンモニウムヒドロキサイド（ＴＭＡＨ）水溶液のようなアルカリ現像液を用いることができる。 As the developer used in the method for forming a resist pattern according to the present invention, for example, an alkaline developer such as an aqueous tetramethylammonium hydroxide (TMAH) solution can be used.
　また、本発明に係る添加剤が添加されたレジスト下層膜形成用組成物は、特に、第１のパターンを形成するために、露光され、現像液に曝されたレジスト下層膜上に、更に第２のパターンを形成する、ダブルパターニング又はダブル露光に有効に適用されるが、本発明に係るレジスト下層膜形成用組成物は、ダブルパターニング又はダブル露光に限らず、レジストパターンの裾形状がフッティング形状に形成されやすい場合にも適用できる。 In addition, the resist underlayer film forming composition to which the additive according to the present invention is added, in particular, is formed on the resist underlayer film that has been exposed and exposed to the developer to form the first pattern. The resist underlayer film forming composition according to the present invention is not limited to double patterning or double exposure, but the bottom shape of the resist pattern is footed. It can also be applied to the case where it is easily formed into a shape.
　以下、本発明について具体的に説明する。ただし、本発明は下記合成例及び実施例の記載に限定されるものではない。 Hereinafter, the present invention will be specifically described. However, the present invention is not limited to the description of the following synthesis examples and examples.
　本明細書の下記合成例１乃至合成例９に示すポリマーの平均分子量は、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〕・Ａｓａｈｉｐａｋ〔登録商標〕（昭和電工（株））
カラム温度：４０℃
溶媒：Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）
流量：０．６ｍｌ／分
標準試料：ポリスチレン（東ソー（株）製） The average molecular weights of the polymers shown in the following Synthesis Examples 1 to 9 in this specification are measurement results by gel permeation chromatography (hereinafter abbreviated as GPC). The measurement conditions etc. are as follows using the Tosoh Co., Ltd. product GPC apparatus for a measurement.
GPC column: Shodex (registered trademark) and Asahipak (registered trademark) (Showa Denko KK)
Column temperature: 40 ° C
Solvent: N, N-dimethylformamide (DMF)
Flow rate: 0.6 ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)
＜合成例１＞
　１，４－ブタンジオールジグリシジルエーテル（四日市合成（株）製）８．００ｇ、テレフタル酸ジグリシジルエステル（ナガセケムテックス（株）製）１１．６２ｇ、モノアリルイソシアヌル酸（四国化成工業（株）製）１３．５５ｇ、及びベンジルトリエチルアンモニウムクロリド０．９１ｇをプロピレングリコールモノメチルエーテル３４．０９ｇに溶解させた後、１３０℃で４時間反応させ、ポリマーを含有する溶液を得た。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１０，０００であった。本合成例で得られたポリマーは、本発明に係るレジスト下層膜形成用組成物に含まれる樹脂バインダーに相当する。 <Synthesis Example 1>
1,4-butanediol diglycidyl ether (manufactured by Yokkaichi Chemical Co., Ltd.) 8.00 g, diglycidyl terephthalate ester (manufactured by Nagase ChemteX Corp.) 11.62 g, monoallyl isocyanuric acid (Shikoku Chemical Industries, Ltd.) (Product made) 13.55 g and benzyltriethylammonium chloride 0.91 g were dissolved in 34.09 g of propylene glycol monomethyl ether, and reacted at 130 ° C. for 4 hours to obtain a solution containing a polymer. When GPC analysis was performed, the weight average molecular weight was 10,000 in terms of standard polystyrene. The polymer obtained in this synthesis example corresponds to the resin binder contained in the resist underlayer film forming composition according to the present invention.
＜合成例２＞
　モノアリルジグリシジルイソシアヌル酸（四国化成工業（株）製）１０．００ｇ、５－ヒドロキシイソフタル酸６．６４ｇ、及びベンジルトリエチルアンモニウムクロリド０．４１ｇをプロピレングリコールモノメチルエーテル６４．１１ｇに溶解させた後、１３０℃で４時間反応させ、ポリマーを含有する溶液を得た。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１５，０００であった。本合成例で得られたポリマーは、本発明に係るレジスト下層膜形成用組成物に含まれる樹脂バインダーに相当する。 <Synthesis Example 2>
After dissolving 10.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 6.64 g of 5-hydroxyisophthalic acid, and 0.41 g of benzyltriethylammonium chloride in 64.11 g of propylene glycol monomethyl ether, The reaction was carried out at 130 ° C. for 4 hours to obtain a solution containing the polymer. When GPC analysis was performed, the weight average molecular weight was 15,000 in terms of standard polystyrene. The polymer obtained in this synthesis example corresponds to the resin binder contained in the resist underlayer film forming composition according to the present invention.
＜合成例３＞
　モノアリルジグリシジルイソシアヌル酸（四国化成工業（株）製）５０ｇ、２，４－ジヒドロキシ安息香酸２８．０７ｇ、及びエチルトリフェニルホスホニウムブロミド３．３８ｇをプロピレングリコールモノメチルエーテル１９０．０６ｇに溶解させた後、１３０℃で４時間反応させ、ポリマーを含有する溶液を得た。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８，６００であった。本合成例で得られたポリマーは、本発明に係るレジスト下層膜形成用組成物に含まれる樹脂バインダーに相当する。 <Synthesis Example 3>
After dissolving 50 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 28.07 g of 2,4-dihydroxybenzoic acid and 3.38 g of ethyltriphenylphosphonium bromide in 190.06 g of propylene glycol monomethyl ether , And reacted at 130 ° C. for 4 hours to obtain a polymer-containing solution. When GPC analysis was performed, it was the weight average molecular weight 8,600 in standard polystyrene conversion. The polymer obtained in this synthesis example corresponds to the resin binder contained in the resist underlayer film forming composition according to the present invention.
＜合成例４＞
　モノアリルジグリシジルイソシアヌル酸（四国化成工業（株）製）３６．５０ｇ、２，４－ジヒドロキシ安息香酸４０．４９ｇ、１，２－シクロヘキサンジカルボン酸ジグリシジルエステル４０．００ｇ、及びエチルトリフェニルホスホニウムブロミド４．８８ｇをプロピレングリコールモノメチルエーテル１２１．８７ｇに溶解させた後、１３０℃で４時間反応させ、ポリマーを含有する溶液を得た。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７，０００であった。本合成例で得られたポリマーは、本発明に係るレジスト下層膜形成用組成物に含まれる樹脂バインダーに相当する。 <Synthesis Example 4>
36.50 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 40.49 g of 2,4-dihydroxybenzoic acid, 40.00 g of 1,2-cyclohexanedicarboxylic acid diglycidyl ester, and ethyltriphenylphosphonium bromide 4.88 g was dissolved in 121.87 g of propylene glycol monomethyl ether and then reacted at 130 ° C. for 4 hours to obtain a solution containing a polymer. When GPC analysis was performed, it was weight average molecular weight 7,000 in standard polystyrene conversion. The polymer obtained in this synthesis example corresponds to the resin binder contained in the resist underlayer film forming composition according to the present invention.
＜合成例５＞
　４－ターシャリブトキシスチレン１２．００ｇ及びトリフルオロエチルメタクリレート３．００ｇをプロピレングリコールモノメチルエーテル５０．６ｇに溶解させ、７０℃へ昇温した。アゾビスイソブチロニトリル０．１５ｇをプロピレングリコールモノメチルエーテル１０ｇに溶解させた溶液をゆっくり滴下し、滴下後８０℃で２４時間反応させ、ポリマーを含有する溶液を得た。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３２，０００であった。本合成例で得られたポリマーは、本発明に係る添加剤に含まれる共重合体に相当する。 <Synthesis Example 5>
4-tert-ributoxystyrene (12.00 g) and trifluoroethyl methacrylate (3.00 g) were dissolved in propylene glycol monomethyl ether (50.6 g), and the temperature was raised to 70 ° C. A solution prepared by dissolving 0.15 g of azobisisobutyronitrile in 10 g of propylene glycol monomethyl ether was slowly added dropwise, followed by reaction at 80 ° C. for 24 hours to obtain a solution containing a polymer. When GPC analysis was performed, the weight average molecular weight was 32,000 in terms of standard polystyrene. The polymer obtained in this synthesis example corresponds to a copolymer contained in the additive according to the present invention.
＜合成例６＞
　ｐ－（１－エトキシエトキシ）スチレン１２．００ｇ及びトリフルオロエチルメタクリレート３．００ｇをプロピレングリコールモノメチルエーテル５０．６ｇに溶解させ、７０℃へ昇温した。アゾビスイソブチロニトリル０．１５ｇをプロピレングリコールモノメチルエーテル１０ｇに溶解させた溶液をゆっくり滴下し、滴下後８０℃で２４時間反応させ、ポリマーを含有する溶液を得た。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３４，０００であった。本合成例で得られたポリマーは、本発明に係る添加剤に含まれる共重合体に相当する。 <Synthesis Example 6>
12.00 g of p- (1-ethoxyethoxy) styrene and 3.00 g of trifluoroethyl methacrylate were dissolved in 50.6 g of propylene glycol monomethyl ether, and the temperature was raised to 70 ° C. A solution prepared by dissolving 0.15 g of azobisisobutyronitrile in 10 g of propylene glycol monomethyl ether was slowly added dropwise, followed by reaction at 80 ° C. for 24 hours to obtain a solution containing a polymer. When GPC analysis was performed, it was weight average molecular weight 34,000 in standard polystyrene conversion. The polymer obtained in this synthesis example corresponds to a copolymer contained in the additive according to the present invention.
＜合成例７＞
　４－ターシャリブトキシスチレン７．５０ｇ、トリフルオロエチルメタクリレート３．００ｇ、及びガンマブチロラクトンメタクリレート４．５０ｇをプロピレングリコールモノメチルエーテル５０．６ｇに溶解させ、７０℃へ昇温した。アゾビスイソブチロニトリル０．１５ｇをプロピレングリコールモノメチルエーテル１０ｇに溶解させた溶液をゆっくり滴下し、滴下後８０℃で２４時間反応させ、ポリマーを含有する溶液を得た。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３５，０００であった。本合成例で得られたポリマーは、本発明に係る添加剤に含まれる共重合体に相当する。 <Synthesis Example 7>
7.50 g of 4-tertiarybutoxystyrene, 3.00 g of trifluoroethyl methacrylate, and 4.50 g of gamma butyrolactone methacrylate were dissolved in 50.6 g of propylene glycol monomethyl ether, and the temperature was raised to 70 ° C. A solution prepared by dissolving 0.15 g of azobisisobutyronitrile in 10 g of propylene glycol monomethyl ether was slowly added dropwise, followed by reaction at 80 ° C. for 24 hours to obtain a solution containing a polymer. When GPC analysis was performed, it was weight average molecular weight 35,000 in standard polystyrene conversion. The polymer obtained in this synthesis example corresponds to a copolymer contained in the additive according to the present invention.
＜合成例８＞
　４－ターシャリブトキシスチレン７．５０ｇ、トリフルオロエチルメタクリレート３．００ｇ、及び２－エチル－２－アダマンチルメタクリレート４．５０ｇをプロピレングリコールモノメチルエーテル５０．６ｇに溶解させ、７０℃へ昇温した。アゾビスイソブチロニトリル０．１５ｇをプロピレングリコールモノメチルエーテル１０ｇに溶解させた溶液をゆっくり滴下し、滴下後８０℃で２４時間反応させ、ポリマーを含有する溶液を得た。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３０，０００であった。本合成例で得られたポリマーは、本発明に係る添加剤に含まれる共重合体に相当する。 <Synthesis Example 8>
4.50 g of 4-tertiarybutoxystyrene, 3.00 g of trifluoroethyl methacrylate, and 4.50 g of 2-ethyl-2-adamantyl methacrylate were dissolved in 50.6 g of propylene glycol monomethyl ether, and the temperature was raised to 70 ° C. A solution prepared by dissolving 0.15 g of azobisisobutyronitrile in 10 g of propylene glycol monomethyl ether was slowly added dropwise, followed by reaction at 80 ° C. for 24 hours to obtain a solution containing a polymer. When GPC analysis was performed, the weight average molecular weight was 30,000 in terms of standard polystyrene. The polymer obtained in this synthesis example corresponds to a copolymer contained in the additive according to the present invention.
＜合成例９＞
　４－ターシャリブトキシスチレン７．５０ｇ、トリフルオロエチルメタクリレート３．００ｇ、及び３－ヒドロキシ－１－アダマンチルメタクリレート４．５０ｇをプロピレングリコールモノメチルエーテル５０．６ｇに溶解させ、７０℃へ昇温した。アゾビスイソブチロニトリル０．１５ｇをプロピレングリコールモノメチルエーテル１０ｇに溶解させた溶液をゆっくり滴下し、滴下後８０℃で２４時間反応させ、ポリマーを含有する溶液を得た。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３１，０００であった。本合成例で得られたポリマーは、本発明に係る添加剤に含まれる共重合体に相当する。 <Synthesis Example 9>
4.50 g of 4-tertiarybutoxystyrene, 3.00 g of trifluoroethyl methacrylate, and 4.50 g of 3-hydroxy-1-adamantyl methacrylate were dissolved in 50.6 g of propylene glycol monomethyl ether, and the temperature was raised to 70 ° C. A solution prepared by dissolving 0.15 g of azobisisobutyronitrile in 10 g of propylene glycol monomethyl ether was slowly added dropwise, followed by reaction at 80 ° C. for 24 hours to obtain a solution containing a polymer. When GPC analysis was performed, the weight average molecular weight was 31,000 in terms of standard polystyrene. The polymer obtained in this synthesis example corresponds to a copolymer contained in the additive according to the present invention.
〔実施例１〕
　上記合成例１で得られたポリマー０．８ｇを含有する溶液４ｇにテトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、商品名：ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）０．２ｇ、ピリジニウム－ｐ－トルエンスルホン酸０．０２ｇ、及び合成例５で得られたポリマー溶液０．０８ｇを混合し、プロピレングリコールモノメチルエーテル２５．０２ｇ及びプロピレングリコールモノメチルエーテルアセテート１２．１２ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、レジスト下層膜形成用組成物（溶液）を調製した。 [Example 1]
To 4 g of a solution containing 0.8 g of the polymer obtained in Synthesis Example 1, 0.2 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), pyridinium-p- 0.02 g of toluenesulfonic acid and 0.08 g of the polymer solution obtained in Synthesis Example 5 were mixed and dissolved in 25.02 g of propylene glycol monomethyl ether and 12.12 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
〔実施例２〕
　上記合成例２で得られたポリマー０．８ｇを含有する溶液４ｇにテトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、商品名：ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）０．２ｇ、５－スルホサリチル酸０．０２ｇ、及び合成例５で得られたポリマー溶液０．０８ｇを混合し、プロピレングリコールモノメチルエーテル２５．０２ｇ及びプロピレングリコールモノメチルエーテルアセテート１２．１２ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、レジスト下層膜形成用組成物（溶液）を調製した。 [Example 2]
To 4 g of a solution containing 0.8 g of the polymer obtained in Synthesis Example 2, 0.2 g of tetramethoxymethylglycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), 5-sulfosalicylic acid 0.02 g and 0.08 g of the polymer solution obtained in Synthesis Example 5 were mixed and dissolved in 25.02 g of propylene glycol monomethyl ether and 12.12 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
〔実施例３〕
　上記合成例３で得られたポリマー１．２ｇを含有する溶液４ｇにテトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、商品名：ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）０．３ｇ、５－スルホサリチル酸０．０３ｇ、及び合成例５で得られたポリマー溶液０．１２ｇを混合し、プロピレングリコールモノメチルエーテル３８．９７ｇ及びプロピレングリコールモノメチルエーテルアセテート１７．９０ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、レジスト下層膜形成用組成物（溶液）を調製した。 Example 3
To 4 g of the solution containing 1.2 g of the polymer obtained in Synthesis Example 3, 0.3 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), 5-sulfosalicylic acid 0.03 g and 0.12 g of the polymer solution obtained in Synthesis Example 5 were mixed and dissolved in 38.97 g of propylene glycol monomethyl ether and 17.90 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
〔実施例４〕
　上記合成例１で得られたポリマー１．２ｇを含有する溶液４ｇにテトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、商品名：ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）０．３ｇ、５－スルホサリチル酸０．０３ｇ、及び合成例６で得られたポリマー溶液０．１２ｇを混合し、プロピレングリコールモノメチルエーテル３８．９７ｇ及びプロピレングリコールモノメチルエーテルアセテート１７．９０ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、レジスト下層膜形成用組成物（溶液）を調製した。 Example 4
To 4 g of the solution containing 1.2 g of the polymer obtained in Synthesis Example 1, 0.3 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), 5-sulfosalicylic acid 0.03 g and 0.12 g of the polymer solution obtained in Synthesis Example 6 were mixed and dissolved in 38.97 g of propylene glycol monomethyl ether and 17.90 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
〔実施例５〕
　上記合成例４で得られたポリマー１．２ｇを含有する溶液４ｇにテトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、商品名：ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）０．３ｇ、５－スルホサリチル酸０．０３ｇ、及び合成例８で得られたポリマー溶液０．１２ｇを混合し、プロピレングリコールモノメチルエーテル３８．９７ｇ及びプロピレングリコールモノメチルエーテルアセテート１７．９０ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、レジスト下層膜形成用組成物（溶液）を調製した。 Example 5
To 4 g of a solution containing 1.2 g of the polymer obtained in Synthesis Example 4, 0.3 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174), 5-sulfosalicylic acid 0.03 g and 0.12 g of the polymer solution obtained in Synthesis Example 8 were mixed and dissolved in 38.97 g of propylene glycol monomethyl ether and 17.90 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
〔比較例１〕
　上記合成例１で得られたポリマー０．８ｇを含有する溶液４ｇにテトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、商品名：ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）０．２ｇ及びピリジニウム－ｐ－トルエンスルホン酸０．０２ｇを混合し、プロピレングリコールモノメチルエーテル２５．０２ｇ及びプロピレングリコールモノメチルエーテルアセテート１２．１２ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、レジスト下層膜形成用組成物（溶液）を調製した。 [Comparative Example 1]
To 4 g of the solution containing 0.8 g of the polymer obtained in Synthesis Example 1, 0.2 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Ltd., trade name: POWDERLINK [registered trademark] 1174) and pyridinium-p- 0.02 g of toluenesulfonic acid was mixed and dissolved in 25.02 g of propylene glycol monomethyl ether and 12.12 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
〔比較例２〕
　上記合成例２で得られたポリマー０．８ｇを含有する溶液４ｇにテトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、商品名：ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）０．２ｇ及び５－スルホサリチル酸０．０２ｇを混合し、プロピレングリコールモノメチルエーテル２５．０２ｇ及びプロピレングリコールモノメチルエーテルアセテート１２．１２ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、レジスト下層膜形成用組成物（溶液）を調製した。 [Comparative Example 2]
To 4 g of the solution containing 0.8 g of the polymer obtained in Synthesis Example 2, 0.2 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Inc., trade name: POWDERLINK [registered trademark] 1174) and 5-sulfosalicylic acid 0.02 g was mixed and dissolved in 25.02 g of propylene glycol monomethyl ether and 12.12 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
〔比較例３〕
　上記合成例４で得られたポリマー０．８ｇを含有する溶液１．６ｇにテトラメトキシメチルグリコールウリル（日本サイテックインダストリーズ（株）製、商品名：ＰＯＷＤＥＲＬＩＮＫ〔登録商標〕１１７４）０．２ｇ及び５－スルホサリチル酸０．０２ｇを混合し、プロピレングリコールモノメチルエーテル２５．０２ｇ及びプロピレングリコールモノメチルエーテルアセテート１２．１２ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、レジスト下層膜形成用組成物（溶液）を調製した。 [Comparative Example 3]
To 1.6 g of a solution containing 0.8 g of the polymer obtained in Synthesis Example 4, 0.2 g of tetramethoxymethylglycoluril (manufactured by Nippon Cytec Industries, Ltd., trade name: POWDERLINK [registered trademark] 1174) and 5- 0.02 g of sulfosalicylic acid was mixed and dissolved in 25.02 g of propylene glycol monomethyl ether and 12.12 g of propylene glycol monomethyl ether acetate to obtain a solution. Then, it filtered using the polyethylene micro filter with a hole diameter of 0.10 micrometer, and also filtered using the polyethylene micro filter with the hole diameter of 0.05 micrometer, and prepared the composition (solution) for resist underlayer film formation.
〔レジストパターンの形成及び評価〕
　シリコンウエハー上に、本明細書の実施例１乃至実施例５、比較例１乃至比較例３で調製された各レジスト下層膜形成用組成物をスピンコートし、２０５℃で１分間加熱することにより、レジスト下層膜を形成した。そのレジスト下層膜上に、ＡｒＦエキシマレーザー用レジスト溶液（住友化学（株）製、商品名：ＰＡＲ８５５）をスピンコートし、１１５℃で９０秒間加熱を行い、ＡｒＦエキシマレーザー用露光装置（（株）ニコン製、ＮＳＲ　Ｓ３０７Ｅ）を用い、所定の条件で露光する。露光後、１０５℃で９０秒間加熱（ＰＥＢ）を行い、クーリングプレート上で室温まで冷却し、現像及びリンス処理をし、レジストパターン（第１のパターン）を形成した。 [Formation and evaluation of resist pattern]
By spin-coating each of the resist underlayer film forming compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 of this specification on a silicon wafer and heating at 205 ° C. for 1 minute. A resist underlayer film was formed. An ArF excimer laser resist solution (manufactured by Sumitomo Chemical Co., Ltd., trade name: PAR855) is spin-coated on the resist underlayer film, heated at 115 ° C. for 90 seconds, and exposed to an ArF excimer laser (Corporation) Using Nikon NSR S307E), exposure is performed under predetermined conditions. After exposure, heating (PEB) was performed at 105 ° C. for 90 seconds, cooling to room temperature on a cooling plate, development and rinsing treatment were performed, and a resist pattern (first pattern) was formed.
　目的の線幅を６５ｎｍ或いは８０ｎｍのラインアンドスペースとし、最適露光量、最適フォーカス時のレジストパターン寸法を測長ＳＥＭにて計測し、レジストパターンの、基板（シリコンウエハー）と垂直方向の断面形状を断面ＳＥＭにて観察して、目的のレジストパターンが形成されているか否かを確認することができる。 The target line width is set to 65 nm or 80 nm line and space, and the resist pattern dimensions at the optimum exposure and focus are measured with a length measuring SEM, and the sectional shape of the resist pattern in the direction perpendicular to the substrate (silicon wafer) is measured. By observing with a cross-sectional SEM, it can be confirmed whether or not a target resist pattern is formed.
　ダブルパターニング工程における２回目のリソグラフィー性能を確認する実験として、まず１回目のリソグラフィー工程のモデルとして模擬的にフォトマスクを介さずに露光を行い、更に現像処理を行った。露光、現像エリアは通常ラインアンドスペースのスペースを模倣したものである。その結果、第１のパターンは形成されない。現像後のレジスト下層膜表面上にレジストパターン（第２のパターン）を、前述の第１のパターン形成と同様の方法で形成することで、２回目の露光での性能を検証することが可能である。 As an experiment for confirming the lithography performance of the second time in the double patterning process, first, as a model of the first lithography process, exposure was performed without using a photomask in a simulated manner, and further development processing was performed. The exposure and development areas are usually imitated lines and spaces. As a result, the first pattern is not formed. It is possible to verify the performance in the second exposure by forming a resist pattern (second pattern) on the resist underlayer film surface after development by the same method as the first pattern formation described above. is there.
　第１のパターンと第２のパターンの裾形状を断面ＳＥＭにて比較し、裾引き形状、パターン倒れ、ストレート形状の３段階で評価を行った。その結果を表１に示す。図１及び図２に断面ＳＥＭ像を示す。
Figure JPOXMLDOC01-appb-T000011
 The skirt shape of the first pattern and the second pattern was compared with a cross-sectional SEM, and evaluation was performed in three stages: skirt shape, pattern collapse, and straight shape. The results are shown in Table 1. 1 and 2 show cross-sectional SEM images.
Figure JPOXMLDOC01-appb-T000011
実施例１乃至実施例５のレジスト下層膜形成用組成物を用いてレジスト下層膜を形成し、その上に形成したフォトレジストパターンの裾形状を示す断面ＳＥＭ像である。It is a cross-sectional SEM image which shows the skirt shape of the photoresist pattern which formed the resist underlayer film using the composition for resist underlayer film formation of Example 1 thru | or Example 5, and formed on it. 比較例１乃至比較例３のレジスト下層膜形成用組成物を用いてレジスト下層膜を形成し、その上に形成したフォトレジストパターンの裾形状を示す断面ＳＥＭ像である。It is a cross-sectional SEM image which shows the bottom shape of the photoresist pattern which formed the resist underlayer film using the composition for resist underlayer film formation of the comparative example 1 thru | or the comparative example 3, and formed on it.

Claims (11)

  1. 　下記式（１）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｌはポリマーの主鎖の一部を構成する結合基を表し、Ｍは直接結合又は－Ｃ（＝Ｏ）－、－ＣＨ2－及び－Ｏ－から選ばれる少なくとも１種を含む連結基を表し、Ｑは少なくとも１つの水素原子がフッ素原子で置換されていてもよいアルキル基を表し、前記Ｌ、Ｍ及びＱのうち少なくとも１つはフッ素原子を含み、Ｒ1はアセチル基、アルコキシアルキル基、３級アルキル基又は水素原子を表す。）
    で表される構造単位Ｖ及びＷを少なくとも有する共重合体を含有するレジスト下層膜形成組成物用添加剤。     Following formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, L represents a linking group constituting a part of the main chain of the polymer, and M includes a direct bond or at least one selected from —C (═O) —, —CH 2 —, and —O—). Represents a linking group, Q represents an alkyl group in which at least one hydrogen atom may be substituted with a fluorine atom, at least one of L, M and Q includes a fluorine atom, R 1 represents an acetyl group, Represents an alkoxyalkyl group, a tertiary alkyl group or a hydrogen atom.)
    An additive for a resist underlayer film forming composition containing a copolymer having at least structural units V and W represented by the formula:
  2. 　前記式（１）において前記構造単位Ｖは、下記式（２）：
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ2は水素原子又はメチル基を表し、Ｍ及びＱは請求項１における定義と同義である。）
    で表される、請求項１に記載のレジスト下層膜形成組成物用添加剤。     In the formula (1), the structural unit V is represented by the following formula (2):
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 2 represents a hydrogen atom or a methyl group, and M and Q are as defined in claim 1).
    The additive for resist underlayer film forming composition of Claim 1 represented by these.
  3. 　前記式（２）中、Ｑは、少なくとも１つの水素原子がフッ素原子で置換された炭素原子数１乃至３のアルキル基を表す、請求項２に記載のレジスト下層膜形成組成物用添加剤。 The additive for a resist underlayer film forming composition according to claim 2, wherein in the formula (2), Q represents an alkyl group having 1 to 3 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.
  4. 　前記共重合体は更に下記式（３）：
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ2は水素原子又はメチル基を表し、Ｍは請求項１における定義と同義であり、Ａはアダマンタン環又はラクトン環を含む置換基を表す。）
    で表される構造単位Ｘを有する、請求項１乃至請求項３のいずれか一項に記載のレジスト下層膜形成組成物用添加剤。     The copolymer further has the following formula (3):
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, R 2 represents a hydrogen atom or a methyl group, M has the same definition as in claim 1, and A represents a substituent containing an adamantane ring or a lactone ring.)
    The additive for resist underlayer film forming compositions as described in any one of Claims 1 thru | or 3 which have the structural unit X represented by these.
  5. 　樹脂バインダー、架橋性化合物、溶剤及び請求項１乃至請求項４のいずれか一項に記載のレジスト下層膜形成組成物用添加剤を含むリソグラフィー用レジスト下層膜形成組成物。 A resist underlayer film forming composition for lithography comprising a resin binder, a crosslinkable compound, a solvent, and the additive for a resist underlayer film forming composition according to any one of claims 1 to 4.
  6. 　架橋反応を促進させる化合物を更に含む請求項５に記載のリソグラフィー用レジスト下層膜形成組成物。 The resist underlayer film forming composition for lithography according to claim 5, further comprising a compound that promotes a crosslinking reaction.
  7. 　前記架橋性化合物はメチロール基又はアルコキシメチル基が結合した窒素原子を２つ乃至４つ有する含窒素化合物である請求項５又は請求項６に記載のリソグラフィー用レジスト下層膜形成組成物。 7. The resist underlayer film forming composition for lithography according to claim 5, wherein the crosslinkable compound is a nitrogen-containing compound having 2 to 4 nitrogen atoms bonded to a methylol group or an alkoxymethyl group.
  8. 　前記架橋反応を促進させる化合物はスルホン酸化合物である請求項６に記載のリソグラフィー用レジスト下層膜形成組成物。 The resist underlayer film forming composition for lithography according to claim 6, wherein the compound that promotes the crosslinking reaction is a sulfonic acid compound.
  9. 　前記架橋反応を促進させる化合物は酸発生剤とスルホン酸化合物との組み合わせである請求項６に記載のリソグラフィー用レジスト下層膜形成組成物。 The resist underlayer film forming composition for lithography according to claim 6, wherein the compound that promotes the crosslinking reaction is a combination of an acid generator and a sulfonic acid compound.
  10. 　請求項５乃至請求項９のいずれか一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ベークしてレジスト下層膜を形成する工程、前記レジスト下層膜上にレジスト膜を形成する工程、前記レジスト下層膜上に層形成された前記レジスト膜を露光する工程、露光後に現像液を用いて前記レジスト膜を現像することによって第１のパターンを前記レジスト下層膜上に形成する工程、及び前記第１のパターンと重ならないように、前記現像により露出した前記レジスト下層膜上に第２のパターンを形成する工程を含む、半導体装置の製造に用いるレジストパターンの形成方法。 A step of applying the resist underlayer film forming composition according to any one of claims 5 to 9 on a semiconductor substrate and baking the composition to form a resist underlayer film, and forming a resist film on the resist underlayer film A step, a step of exposing the resist film layered on the resist underlayer film, a step of forming a first pattern on the resist underlayer film by developing the resist film using a developer after exposure, And a method of forming a resist pattern used for manufacturing a semiconductor device, including a step of forming a second pattern on the resist underlayer film exposed by the development so as not to overlap the first pattern.
  11. 　前記露光は、ＡｒＦエキシマレーザーを用いて行われる、請求項１０に記載のレジストパターンの形成方法。 The resist pattern forming method according to claim 10, wherein the exposure is performed using an ArF excimer laser.
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