WO2009122753A1 - フォトレジスト組成物 - Google Patents
フォトレジスト組成物 Download PDFInfo
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- WO2009122753A1 WO2009122753A1 PCT/JP2009/001559 JP2009001559W WO2009122753A1 WO 2009122753 A1 WO2009122753 A1 WO 2009122753A1 JP 2009001559 W JP2009001559 W JP 2009001559W WO 2009122753 A1 WO2009122753 A1 WO 2009122753A1
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- WIPO (PCT)
- Prior art keywords
- polyol
- compound
- photoresist composition
- group
- aromatic
- Prior art date
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Classifications
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- 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
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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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
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/45—Friedel-Crafts-type
Definitions
- the present invention uses a photoresist composition containing a novel polyol compound and a vinyl ether compound, a method for forming a resist coating using the photoresist composition, the resulting resist coating, and the resist coating.
- the present invention relates to a method for forming a resist pattern.
- a base material component that has film-forming ability and changes to alkali-solubility by the action of acid, and generates acid upon exposure
- a chemically amplified resist containing an acid generator component is known.
- Examples of reducing the LER by reducing the average particle size per molecule include, for example, a photo described in Patent Document 1 containing a polyhydric phenol compound and an acid generator component that generates an acid upon exposure. Examples include resist compositions.
- this photoresist composition is not satisfactory in terms of resolution, etching resistance, and pattern collapse. That is, the present situation is that no photoresist composition has been found that can reduce LER, has excellent resolution and etching resistance, and can suppress pattern collapse.
- an object of the present invention is to provide a novel photoresist composition that can reduce LER, is excellent in resolution and etching resistance, and can suppress pattern collapse.
- Another object of the present invention is to provide a method for forming a resist coating film using the above photoresist composition, a resist coating film formed by the method for forming a resist coating film, and a method for forming a resist pattern using the resist coating film. It is to provide.
- the present inventor has found that a photopolymer containing a polyol compound in which an aliphatic group and an aromatic group having a plurality of hydroxyl groups on an aromatic ring are alternately bonded, and a vinyl ether compound. It has been found that the resist composition can easily react the polyol compound and the vinyl ether compound by heating. And the high molecular compound obtained by reaction discovered that it was excellent in alkali developing solution insolubility, or alkali developing solution poor solubility, and etching resistance, and can suppress pattern collapse.
- the polymer compound obtained by reacting the polyol compound with the vinyl ether compound can be easily decomposed by the action of an acid, thereby reducing the LER and increasing the resolution. It has been found that image properties can be exhibited.
- the present invention has been completed based on these findings and further research.
- the present invention provides a photoresist composition containing a polyol compound in which an aliphatic group and an aromatic group having a plurality of hydroxyl groups on an aromatic ring are alternately bonded, and a vinyl ether compound.
- the polyol compound is preferably a polyol compound obtained by an acid-catalyzed reaction between an aliphatic polyol and an aromatic polyol, and the acid-catalyzed reaction is preferably a Friedel-Crafts reaction.
- the aliphatic polyol is preferably an alicyclic polyol, and more preferably an adamantane polyol in which two or more hydroxyl groups are bonded to the tertiary position of the adamantane ring.
- the aromatic polyol is preferably hydroquinone or naphthalene polyol.
- the weight average molecular weight of the polyol compound is preferably 500 to 5,000.
- vinyl ether compound a polyvalent vinyl ether compound is preferable.
- the present invention also provides a method for forming a resist coating film, which comprises applying the photoresist composition to a substrate and then heating to react a polyol compound and a vinyl ether compound.
- the present invention further provides a resist coating film formed by the method for forming a resist coating film.
- the present invention further provides a method for forming a resist pattern, characterized by exposing and developing the resist coating film.
- the photoresist composition according to the present invention contains a polyol compound in which an aliphatic group and an aromatic group having a plurality of hydroxyl groups in an aromatic ring are alternately bonded, and a vinyl ether compound, and thus can be easily heated. Can be reacted.
- the polymer compound for photoresist obtained by the reaction is insoluble in alkali developer or hardly soluble in alkali developer, has excellent etching resistance, and can suppress pattern collapse. Furthermore, the polymer compound for photoresist can be easily decomposed by the action of an acid, can reduce LER, and has excellent resolution.
- EUV Extreme Ultraviolet: wavelength of about 13.5 nm
- LER can be reduced to 2 nm or less even in photolithography with a line-and-space pattern of 22 nm or less, and a high-resolution resist.
- a pattern can be formed.
- the photoresist composition according to the present invention contains a polyol compound in which an aliphatic group and an aromatic group having a plurality of hydroxyl groups in an aromatic ring are alternately bonded, and a vinyl ether compound.
- the polyol compound has a structure in which an aliphatic group and an aromatic group having a plurality of hydroxyl groups on an aromatic ring are alternately bonded.
- a unit in which one aliphatic group and one aromatic group are bonded (repeatedly).
- a polyol compound (for example, a compound in which one or more aromatic groups are bonded to one aliphatic group, a compound in which two or more aliphatic groups are bonded to one aromatic group), and a repeating unit May be a polyol compound having 2 or more, or a mixture thereof.
- the polyol compound can be produced by various methods, for example, a method in which an aliphatic polyol and an aromatic polyol are acid-catalyzed, a method in which an aliphatic polyvalent halide and an aromatic polyol are acid-catalyzed, phenol And a method in which formaldehyde is reacted with an acid catalyst or an alkali catalyst.
- the aliphatic polyol is a compound in which a plurality of hydroxyl groups are bonded to an aliphatic hydrocarbon group, and the following formula (1) R- (OH) n1 (1) (In the formula, R represents an aliphatic hydrocarbon group, and n1 represents an integer of 2 or more) It is represented by
- R in the formula (1) includes, for example, a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and a group in which these are bonded.
- the chain aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, dodecyl group, etc.)
- an alkenyl group having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as vinyl, allyl and 1-butenyl groups
- Examples thereof include alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as ethynyl and propynyl groups.
- the cycloaliphatic hydrocarbon group includes a cycloalkyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl group; Cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as pentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl groups, norbornyl, adamantyl, tetracyclo [4 4.0.1, 2,5 . And a bridged cyclic hydrocarbon group such as 1 7,10 ] dodecan-3-yl group.
- the hydrocarbon group in which the chain aliphatic hydrocarbon group and the cyclic aliphatic hydrocarbon group are bonded to each other includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C 3-20 cyclohexane). Alkyl-C 1-4 alkyl group and the like).
- the hydrocarbon group includes various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxycarbonyls.
- the hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.
- an alicyclic polyol is preferable in that the etching resistance can be improved.
- the alicyclic polyol is a compound having an alicyclic skeleton, and the hydroxyl group may be directly bonded to the alicyclic skeleton or may be bonded via a linking group.
- the linking group is selected from an alkylene group (C 1-6 alkylene group, etc.), one or more of the alkylene groups, and —O—, —C ( ⁇ O) —, —NH—, —S—. And a group to which at least one group is bonded.
- Examples of the alicyclic polyol include cyclohexane diol, cyclohexane triol, cyclohexane dimethanol, isopropylidene dicyclohexanol, decalin diol, and tricyclodecane dimethanol;
- R in the formula (1) is represented by the following formula (2a ) To (2j), or a ring in which two or more of these are bonded, and a bridged alicyclic polyol in which two or more hydroxyl groups are bonded to R.
- aliphatic polyol a bridged alicyclic polyol is preferable, and an adamantane polyol in which two or more hydroxyl groups are bonded to the tertiary position of the adamantane ring (2a) is particularly preferable in terms of excellent etching resistance. .
- the aromatic polyol in the present invention is a compound having at least one aromatic ring and having a plurality of hydroxyl groups bonded to the aromatic ring.
- R '-(OH) n2 (3) (In the formula, R ′ represents an aromatic hydrocarbon group, and n2 represents an integer of 2 or more) It is represented by When R ′ has a plurality of aromatic rings, the plurality of hydroxyl groups may be bonded to the same aromatic ring, or may be bonded to different aromatic rings.
- R ′ in the formula (3) examples include an aromatic hydrocarbon group and a group in which a chain aliphatic hydrocarbon group and / or a cyclic aliphatic hydrocarbon group is bonded to the aromatic hydrocarbon group.
- the aromatic hydrocarbon group examples include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as phenyl and naphthyl groups.
- the chain aliphatic hydrocarbon group and the cyclic aliphatic hydrocarbon group include the same examples as the examples of the chain aliphatic hydrocarbon group and the cyclic aliphatic hydrocarbon group in R.
- Examples of the group in which the chain aliphatic hydrocarbon group is bonded to the aromatic hydrocarbon group include an alkyl-substituted aryl group (for example, a phenyl group or a naphthyl group substituted with about 1 to 4 C 1-4 alkyl groups), etc. Is included.
- the aromatic hydrocarbon group may be various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups), carboxyl groups, substituted Oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc. You may do it.
- the hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.
- an aromatic or non-aromatic heterocycle may be condensed with the ring of the aromatic hydrocarbon group.
- aromatic polyols examples include naphthalene polyols such as hydroquinone, resorcinol, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, biphenol, bis (4-hydroxyphenyl) methane, bisphenol A, 1,1,1- And (4-hydroxyphenyl) ethane.
- hydroquinone and naphthalene polyol can be preferably used because they are easily available.
- Examples of the acid catalyst used in the acid catalyst reaction include Lewis acids such as aluminum chloride, iron (III) chloride, tin (IV) chloride, and zinc (II) chloride; HF, sulfuric acid, p-toluenesulfonic acid, and phosphoric acid. And the like. These can be used alone or in admixture of two or more. When used for semiconductor production, it is preferable to use an organic acid such as sulfuric acid or p-toluenesulfonic acid, since the contamination of metal components is avoided.
- the amount of the acid catalyst to be used is, for example, about 0.01 to 10 mol, preferably about 0.1 to 5 mol, per 1 mol of the aliphatic polyol.
- the acid catalyzed reaction is performed in the presence or absence of a solvent inert to the reaction.
- a solvent include hydrocarbons such as hexane, cyclohexane, and toluene; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, and chlorobenzene; diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, and the like.
- Linear or cyclic ethers such as acetonitrile and benzonitrile; esters such as ethyl acetate and n-butyl acetate; carboxylic acids such as acetic acid; amides such as N, N-dimethylformamide; ketones such as acetone and methyl ethyl ketone; nitromethane, Nitro compounds such as nitrobenzene; and mixtures thereof.
- the reaction temperature in the acid-catalyzed reaction can be appropriately selected according to the type of reaction components.
- the reaction temperature is, for example, room temperature (25 ° C.) to 200 ° C., preferably 50 to 150 ° C. Degree.
- the reaction may be carried out by any system such as batch system, semi-batch system, and continuous system.
- the amount of the aromatic polyol used is generally about 1.0 to 100 mol, preferably about 3.0 to 50 mol, and more preferably about 5.0 to 20 mol with respect to 1 mol of the aliphatic polyol. A large excess of aromatic polyol may be used.
- the above reaction produces the corresponding polyol compound.
- the reaction product can be separated and purified by a general separation and purification means such as liquid property adjustment, filtration, concentration, crystallization, washing, recrystallization, column chromatography and the like.
- the crystallization solvent may be any solvent that does not dissolve the produced polyol compound, and examples thereof include hydrocarbons such as hexane, heptane, and cyclohexane.
- the raw material aliphatic polyol and aromatic polyol can be easily removed and the purification efficiency is improved, so that the produced polyol compound does not dissolve, and the raw material aliphatic polyol.
- a solvent in which the aromatic polyol is dissolved for example, ether such as tetrahydrofuran; ketone such as acetone and 2-butanone; ester such as ethyl acetate; alcohol such as methanol and ethanol.
- ether such as tetrahydrofuran
- ketone such as acetone and 2-butanone
- ester such as ethyl acetate
- alcohol such as methanol and ethanol
- crystallization is used to include precipitation.
- the reaction product often contains a component insoluble in an alkali developer.
- Such components include (i) a relatively high molecular weight component having a molecular weight exceeding 2000, and (ii) even if the molecular weight is 1000 to 2000, the phenolic hydroxyl group in the polyol compound is in contact with a solvent or the like during the reaction. There are compounds sealed by transesterification and the like.
- a polyol compound containing a component insoluble in an alkali developer is used for resist applications, there is a possibility that the roughness during pattern formation will be adversely affected, or particles may be generated during development, which may remain as foreign matter in the pattern.
- the solution in which the polyol compound is dissolved in a solvent is mixed with a poor solvent for the compound having a phenolic hydroxyl group, and the hydrophobic impurities are removed by precipitation or layer separation (separated as a liquid material). It is preferable to provide a process. Since this component can be efficiently removed, LER can be reduced, and a polyol compound useful for preparing a resist composition excellent in resolution and etching resistance is efficiently produced with high purity. be able to.
- the solvent used for the polyol compound solution examples include ethers such as tetrahydrofuran; ketones such as acetone and 2-butanone; esters such as ethyl acetate and n-butyl acetate; alcohols such as methanol and ethanol. These solvents can be used alone or in admixture of two or more.
- the polyol compound solution used for the removal of hydrophobic impurities may be a reaction solution obtained by an acid-catalyzed reaction. The reaction solution is diluted, concentrated, filtered, adjusted for liquidity, solvent exchange, etc. Any of the solutions obtained by performing the above operations may be used.
- the content of the polyol compound in the solution containing the polyol compound used for the operation of removing hydrophobic impurities is, for example, 1 to 40% by weight, preferably 3 to 30% by weight.
- the poor solvent for the compound having a phenolic hydroxyl group examples include a solvent having a phenol solubility (25 ° C.) of 1 g / 100 g or less.
- Specific examples of the poor solvent for the compound having a phenolic hydroxyl group include, for example, aliphatic hydrocarbons such as hexane and heptane, hydrocarbons such as alicyclic hydrocarbons such as cyclohexane; water and water-soluble organic solvents (for example, methanol And alcohols such as ethanol; ketones such as acetone; nitriles such as acetonitrile; cyclic ethers such as tetrahydrofuran] and the like; water and the like.
- These solvents can be used alone or in admixture of two or more.
- the amount of the poor solvent used is, for example, 1 to 55 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the solution containing the polyol compound
- the poor solvent may be added to the polyol compound solution, or the polyol compound solution may be added to the poor solvent, but the poor solvent is added to the polyol compound solution. More preferably, is added in small portions.
- Precipitation or separated hydrophobic impurities can be removed by methods such as filtration, centrifugation, and decantation. Thereafter, the polyol compound can be deposited or separated into layers by further mixing the solution after removing the hydrophobic impurities with a poor solvent for the compound having a phenolic hydroxyl group.
- the poor solvent may be added to the solution after removing the hydrophobic impurities, or the solution after removing the hydrophobic impurities may be added to the poor solvent, but the hydrophobic impurities are removed to the poor solvent. It is more preferable to add the later solution.
- the amount of the poor solvent in this step is, for example, 60 to 1000 parts by weight, preferably 65 to 800 parts by weight with respect to 100 parts by weight of the solution (solution containing the polyol compound) after removing the hydrophobic impurities. .
- the precipitated or layer-separated polyol compound can be recovered by filtration, centrifugation, decantation, or the like.
- the poor solvent used when depositing or separating layers of hydrophobic impurities and the poor solvent used when depositing or separating layers of the target polyol compound may be the same or different.
- the obtained polyol compound is subjected to drying as necessary.
- the weight average molecular weight (Mw) of the polyol compound in the present invention is about 500 to 5000, preferably about 1000 to 3000, and more preferably about 1000 to 2000.
- the weight average molecular weight of the polyol compound exceeds 5,000, the particle size of the polyol compound becomes too large, so that it tends to be difficult to reduce LER.
- the weight average molecular weight of the polyol compound is less than 500, the heat resistance tends to decrease.
- the molecular weight distribution (Mw / Mn) is, for example, about 1.0 to 2.5.
- said Mn shows a number average molecular weight
- both Mn and Mw are values of standard polystyrene conversion.
- polyol compound in the present invention examples include polyol compounds described in the following formulas (4a), (4b), and (4c).
- s, t and u are the same or different and represent an integer of 0 or more. “...” Indicates that the repeating unit of “adamantane ring-hydroquinone” may be further repeated, and may be terminated here.
- the vinyl ether compound is used to form a protective group for inhibiting the polyol compound from dissolving in an alkaline developer, and includes, for example, a monovinyl ether compound, a polyvalent vinyl ether compound (for example, a divinyl ether compound, Trivinyl ether compound, tetravinyl ether compound, hexavinyl ether compound) and the like. These can be used alone or in admixture of two or more. In the present invention, even if the weight average molecular weight of the polyol compound is small, the polymer compound for photoresist obtained by heating the polyol compound and the vinyl ether compound becomes liquid and it is difficult to form a resist coating film.
- a vinyl ether compound having a molecular weight of a certain level or more for example, a molecular weight of about 100 to 500. If the molecular weight of the vinyl ether compound is too small, the risk of contamination of the optical system due to outgas generated by EUV exposure tends to increase. On the other hand, if the molecular weight of the vinyl ether compound is too large, the viscosity becomes too high and it tends to be difficult to apply to the base material, and the vinyl ether compound remains as a residue on the base material or substrate after development, causing development defects. There is a fear.
- the vinyl ether compound can be synthesized, for example, by reacting vinyl acetate with alcohol in the presence of an iridium catalyst.
- Examples of the vinyl ether compound used in the present invention include compounds represented by the following formulas (5a) to (5m) and (6a) to (6n).
- the photoresist composition according to the present invention contains the polyol compound and the vinyl ether compound.
- the content of the polyol compound and the vinyl ether compound can be appropriately adjusted according to the number of phenolic hydroxyl groups and vinyl ether groups. For example, about 100 to 100 vinyl ether groups with respect to 100 phenolic hydroxyl groups, preferably Is about 50 to 80. If the number of vinyl ether groups is less than 30, the protection of phenolic hydroxyl groups becomes insufficient, making it difficult to sufficiently impart insolubility or poor solubility in an alkaline developer, and at the time of forming a resist pattern The unexposed portion is dissolved or swollen in the alkaline developer, and it tends to be difficult to accurately reproduce the target pattern.
- the photoresist composition according to the present invention preferably contains a photoacid generator and a resist solvent.
- photoacid generator examples include conventional or known compounds that efficiently generate acid upon exposure, such as diazonium salts, iodonium salts (for example, diphenyliodohexafluorophosphate), sulfonium salts (for example, triphenylsulfonium hexafluoroantimony).
- diazonium salts for example, diphenyliodohexafluorophosphate
- sulfonium salts for example, triphenylsulfonium hexafluoroantimony
- sulfonate esters [eg 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane 1,2,3-trisulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenyl) Nylsulfonyloxymethyl) -1-hydroxy-1-benzoylmethane etc.], oxathiazole derivatives, s-triazine derivatives, disulfone derivatives (diphenyldisulfone etc.), imide compounds, oxime sulfonates, diazonaphthoquinones, benzo
- the amount of the photoacid generator used can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of the polyol compound, and the like. It can be selected from the range of about 1 to 25 parts by weight, more preferably about 2 to 20 parts by weight.
- the resist solvent examples include glycol solvents, ester solvents, ketone solvents, and mixed solvents thereof.
- propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl isobutyl ketone, methyl amyl ketone, and a mixed solution thereof are preferable, and in particular, propylene glycol monomethyl ether acetate alone solvent, propylene glycol monomethyl ether acetate and A solvent containing at least propylene glycol monomethyl ether acetate such as a mixed solvent of propylene glycol monomethyl ether and a mixed solvent of propylene glycol monomethyl ether acetate and ethyl lactate is preferably used.
- the concentration of the polyol compound in the photoresist composition can be appropriately set according to the coating thickness as long as it is within a range that can be applied to the substrate, and is, for example, about 2 to 20% by weight, preferably It is about 5 to 15% by weight. If the polyol compound concentration is too high, the viscosity becomes too high and it tends to be difficult to apply on the substrate. On the other hand, when the polyol compound concentration is too thin, it tends to be difficult to form a resist coating film.
- the photoresist composition according to the present invention contains alkali-soluble components such as alkali-soluble resins (for example, novolak resins, phenol resins, imide resins, carboxyl group-containing resins, etc.), colorants (for example, dyes), and the like. May be included.
- alkali-soluble resins for example, novolak resins, phenol resins, imide resins, carboxyl group-containing resins, etc.
- colorants for example, dyes
- the method for forming a resist coating film according to the present invention is characterized in that the above photoresist composition is applied to a substrate and then heated to react the polyol compound and the vinyl ether compound.
- the polyol compound in the present invention has a phenolic hydroxyl group that imparts solubility to an alkaline developer, and is hardly soluble in an alkaline developer by protecting the phenolic hydroxyl group with a protecting group that is easily released by the action of an acid.
- alkali developer insolubility can be imparted.
- the phenolic hydroxyl group of the polyol compound reacts with the vinyl ether group of the vinyl ether compound, and the acetal that is easily eliminated by the action of an acid.
- a structure can be formed.
- a polyvalent vinyl ether compound when used as the vinyl ether compound, two or more polyol compounds can be bonded via a protective group, so that the function of suppressing pattern collapse can be further improved and etching resistance can be further improved. Can demonstrate its sexuality.
- the base material examples include silicon wafer, metal, plastic, glass, ceramic and the like.
- the photoresist composition can be applied using a conventional application means such as a spin coater, a dip coater, or a roller coater.
- the thickness of the resist coating film is, for example, about 0.01 to 10 ⁇ m, preferably about 0.03 to 1 ⁇ m.
- Heating can be performed using a heating device such as a hot plate or an oven.
- the heating conditions are, for example, a temperature of 150 to 250 ° C. (preferably 150 to 200 ° C.) and about 1 minute to 1 hour (preferably 1 to 5 minutes).
- the resist coating film according to the present invention formed by the above-described method for forming a resist coating film is obtained by a reaction between a polyol compound and a vinyl ether compound, and is made of a polymer compound for photoresist that can be easily decomposed by an acid. Etching resistance is excellent, LER can be reduced, and pattern collapse can be suppressed. Therefore, it can be suitably used for various applications such as the production of semiconductor elements and liquid crystal display elements as a high-resolution resist coating film capable of reproducing a pattern with a fine dimension.
- the resist pattern forming method according to the present invention is characterized in that the resist coating film is exposed and developed, and the resist coating film is exposed through a predetermined mask to form a latent image pattern and then developed. Thus, a resist pattern is formed.
- light of various wavelengths such as ultraviolet rays and X-rays can be used.
- semiconductor resists g-rays, i-rays, and excimer lasers (eg, XeCl, KrF, KrCl, ArF, ArCl, etc.) are usually used.
- EUV Extreme Ultraviolet
- the exposure energy is, for example, about 1 to 1000 mJ / cm 2 , preferably about 10 to 500 mJ / cm 2 .
- An acid is generated from the photoacid generator by exposure, followed by a post-exposure baking process (hereinafter sometimes referred to as “PEB process”), whereby the generated acid acts on the protective group, and the photoresist
- PEB process a post-exposure baking process
- the protecting group in the polymer compound for use is quickly eliminated, and a phenolic hydroxyl group that contributes to solubilization of the alkaline developer is generated. Therefore, a predetermined pattern can be formed with high accuracy by developing with an alkali developer.
- the conditions for the PEB treatment are, for example, a temperature of 50 to 180 ° C., about 0.1 to 10 minutes, preferably about 1 to 3 minutes.
- the resist coating film that has been subjected to PEB treatment can be developed using a developer to remove the exposed portion. Thereby, patterning of a resist coating film is performed.
- Examples of the developing method include a liquid piling method, a dipping method, and a rocking dipping method.
- an alkaline aqueous solution for example, a 0.1 to 10% by weight tetramethylammonium hydroxide aqueous solution
- tetramethylammonium hydroxide aqueous solution can be used as the developer.
- Developed substrate is preferably washed with running water and air-dried using compressed air or compressed nitrogen. Thus, a resist pattern is formed on the substrate.
- LER can be reduced, pattern collapse can be suppressed,
- a high-resolution resist pattern having an and space pattern of 0.05 ⁇ m or less (for example, 0.01 to 0.05 ⁇ m) can be formed.
- the reaction liquid after washing was 15.6 g.
- the washed reaction solution was poured into 100 g of n-heptane, an orange powder was precipitated. This was recovered by filtration and dried at 60 ° C. for 12 hours.
- 2.2 g of polyol compound 2 was obtained.
- the weight average molecular weight in terms of standard polystyrene was 800, and the molecular weight distribution was 1.26.
- Example 1 100 parts by weight of the polyol compound 1 obtained in Production Example 1, 50 parts by weight of 1,4-di (vinyloxymethyl) cyclohexane, 5 parts by weight of triphenylsulfonium trifluoromethanesulfonate, and propylene glycol monomethyl ether acetate were mixed. A photoresist composition 1 having a polyol compound concentration of 15% by weight was obtained. The obtained photoresist composition 1 was applied onto a silicon wafer by spin coating so as to have a thickness of 500 nm, and heated with a hot plate at a temperature of 150 ° C. for 180 seconds to form a resist coating film 1.
- the resist coating film 1 was exposed using a KrF excimer laser through a mask at an irradiation amount of 30 mJ / cm 2 , and then subjected to PEB treatment at a temperature of 100 ° C. for 60 seconds. Subsequently, the film was developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water. As a result, a 0.20 ⁇ m line and space pattern was obtained.
- Example 2 instead of the polyol compound 1 obtained in Production Example 1, the polyol compound 2 obtained in Production Example 2 was used in Example 2, and the polyol compound 3 obtained in Production Example 3 was used in Example 3.
- Example 3 When the same operation as in Example 1 was performed, a 0.20 ⁇ m line and space pattern was obtained in any case.
- Example 4 100 parts by weight of the polyol compound 1 obtained in Production Example 1, 50 parts by weight of 1,3-divinyloxyadamantane, 5 parts by weight of triphenylsulfonium trifluoromethanesulfonate, and propylene glycol monomethyl ether acetate were mixed to obtain a polyol compound concentration. A 15% by weight photoresist composition 4 was obtained. The obtained photoresist composition 4 was applied on a silicon wafer by spin coating so as to have a thickness of 500 nm, and heated with a hot plate at a temperature of 150 ° C. for 180 seconds to form a resist coating film 4.
- the resist coating film 4 was exposed through a mask at a dose of 30 mJ / cm 2 using a KrF excimer laser, and then subjected to PEB treatment at a temperature of 100 ° C. for 60 seconds. Subsequently, the film was developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water. As a result, a 0.20 ⁇ m line and space pattern was obtained.
- Example 5 instead of the polyol compound 1 obtained in Production Example 1, the polyol compound 2 obtained in Production Example 2 was used in Example 5, and the polyol compound 3 obtained in Production Example 3 was used in Example 6. As in Example 4, a 0.20 ⁇ m line and space pattern was obtained in all cases.
- Example 7 100 parts by weight of the polyol compound 1 obtained in Production Example 1, 50 parts by weight of 2,6-dioxa-4,8-divinyloxybicyclo [3.3.0] octane, 5 parts by weight of triphenylsulfonium trifluoromethanesulfonate And propylene glycol monomethyl ether acetate were mixed to obtain a photoresist composition 7 having a polyol compound concentration of 15% by weight.
- the obtained photoresist composition 7 was applied onto a silicon wafer by spin coating so as to have a thickness of 500 nm, and heated by a hot plate at 150 ° C. for 180 seconds to form a resist coating film 7.
- the resist coating film 7 was exposed at a dose of 30 mJ / cm 2 through a mask using a KrF excimer laser, and then subjected to PEB treatment at a temperature of 100 ° C. for 60 seconds. Subsequently, the film was developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water. As a result, a 0.20 ⁇ m line and space pattern was obtained.
- Example 8 instead of the polyol compound 1 obtained in Production Example 1, the polyol compound 2 obtained in Production Example 2 was used in Example 8, and the polyol compound 3 obtained in Production Example 3 was used in Example 9 except that When the same operation as in Example 7 was performed, a line and space pattern of 0.20 ⁇ m was obtained in any case.
- Example 10 In place of the polyol compound 1 obtained in Production Example 1, Example 10 was carried out in the same manner as in Example 1 except that the polyol compound 4 obtained in Production Example 4 was used. An and space pattern was obtained.
- the photoresist composition of the present invention can be easily reacted by heating.
- the polymer compound for photoresist obtained by the reaction is insoluble in alkali developer or hardly soluble in alkali developer, and has etching resistance. And can suppress pattern collapse. Furthermore, the polymer compound for photoresist can be easily decomposed by the action of an acid, can reduce LER, and has excellent resolution.
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Abstract
Description
本発明の他の目的は、上記フォトレジスト組成物使用したレジスト塗膜の形成方法、該レジスト塗膜の形成方法により形成されたレジスト塗膜、該レジスト塗膜を使用したレジストパターンの形成方法を提供することにある。
本発明に係るフォトレジスト組成物は、脂肪族基と芳香環に水酸基を複数個有する芳香族基とが交互に結合しているポリオール化合物と、ビニルエーテル化合物とを含有する。
前記脂肪族ポリオールは、脂肪族炭化水素基に複数個の水酸基が結合している化合物であり、下記式(1)
R-(OH)n1 (1)
(式中、Rは脂肪族炭化水素基を示し、n1は2以上の整数を示す)
で表される。
本発明における芳香族ポリオールは、芳香環を少なくとも1つ有しており、複数個の水酸基が芳香環に結合している化合物であり、下記式(3)
R’-(OH)n2 (3)
(式中、R’は芳香族炭化水素基を示し、n2は2以上の整数を示す)
で表される。R’に芳香環を複数個有する場合は、複数個の水酸基は同一の芳香環に結合していてもよく、異なる芳香環に結合していてもよい。
ビニルエーテル化合物は、ポリオール化合物がアルカリ現像液へ溶解することを抑止するための保護基を形成するために使用されるものであり、例えば、モノビニルエーテル化合物、多価ビニルエーテル化合物(例えば、ジビニルエーテル化合物、トリビニルエーテル化合物、テトラビニルエーテル化合物、ヘキサビニルエーテル化合物)などが挙げられる。これらは、単独で、又は2種以上を混合して使用することができる。本発明においては、ポリオール化合物の重量平均分子量が小さくとも、ポリオール化合物とビニルエーテル化合物とを加熱して得られたフォトレジスト用高分子化合物が液体となりレジスト塗膜を形成することが困難となることを防ぐことができ、作業性に優れる点、及び、耐エッチング性を向上することができ、パターン形成後のパターン倒れを防止することができる点で、ジビニルエーテル化合物、又はジビニルエーテル化合物とモノビニルエーテル化合物の混合物を好適に使用することができる。
本発明に係るレジスト塗膜の形成方法は、上記フォトレジスト組成物を基材に塗布し、その後、加熱してポリオール化合物とビニルエーテル化合物とを反応させることを特徴とする。
本発明に係るレジストパターンの形成方法は、上記レジスト塗膜を露光、現像することを特徴とし、該レジスト塗膜に、所定のマスクを介して露光して潜像パターンを形成し、次いで現像することにより、レジストパターンを形成する。
カラム:TSKgel SuperHZM-Mを3本
カラム温度:40℃
溶離液:テトラヒドロフラン
溶離液流速:0.6mL/min
試料濃度:20mg/mL
注入量:10μL
ジムロート冷却管、温度計、撹拌子を装備した200mLの3つ口フラスコに、1,3,5-アダマンタントリオール2.18g、ヒドロキノン7.82g、p-トルエンスルホン酸13.51g、及び酢酸n-ブチル56.67gを仕込み、よく撹拌した。次に、フラスコ内を窒素置換した後、140℃に加温したオイルバスにフラスコを漬けて、撹拌しながら加熱を開始した。還流状態で2時間加熱し続けた後、冷却した。
冷却した反応液を分液ロートに移し、80gの蒸留水で洗浄した。さらに、65gの蒸留水で5回洗浄した。洗浄後の反応液は55.4gであった。洗浄後の反応液を500gのn-ヘプタンに注ぐと、橙色の粉体が析出した。これを濾過回収して60℃で12時間乾燥した結果、5.8gのポリオール化合物1を得た。得られたポリオール化合物1をGPC測定した結果、標準ポリスチレン換算の重量平均分子量は1100、分子量分布は1.69であった。
ジムロート冷却管、温度計、撹拌子を装備した200mLの3つ口フラスコに、1,3,5-アダマンタントリオール0.739g、ヒドロキノン3.98g、p-トルエンスルホン酸18.01g、及び酢酸n-ブチル18.01gを仕込み、よく撹拌した。次に、フラスコ内を窒素置換した後、140℃に加温したオイルバスにフラスコを漬けて、撹拌しながら加熱を開始した。還流状態で2時間加熱し続けた後、冷却した。
冷却した反応液を分液ロートに移し、20gの蒸留水で6回洗浄した。洗浄後の反応液は15.6gであった。洗浄後の反応液を100gのn-ヘプタンに注ぐと、橙色の粉体が析出した。これを濾過回収して60℃で12時間乾燥した結果、2.2gのポリオール化合物2を得た。得られたポリオール化合物2をGPC測定した結果、標準ポリスチレン換算の重量平均分子量は800、分子量分布は1.26であった。
ジムロート冷却管、温度計、撹拌子を装備した200mLの3つ口フラスコに、1,3,5-アダマンタントリオール2.18g、ヒドロキノン7.82g、p-トルエンスルホン酸13.51g、及び酢酸n-ブチル56.67gを仕込み、よく撹拌した。次に、フラスコ内を窒素置換した後、100℃に加温したオイルバスにフラスコを漬けて、撹拌しながら加熱を開始した。還流状態で2時間加熱し続けた後、冷却した。
冷却した反応液を分液ロートに移し、80gの蒸留水で洗浄した。さらに、65gの蒸留水で5回洗浄した。洗浄後の反応液は55.4gであった。洗浄後の反応液を500gのn-ヘプタンに注ぐと、橙色の粉体が析出した。これを濾過回収して60℃で12時間乾燥した結果、5.2gのポリオール化合物3を得た。得られたポリオール化合物3をGPC測定した結果、標準ポリスチレン換算の重量平均分子量は1310、分子量分布は2.08であった。
ジムロート冷却管、温度計、撹拌子を装備した200mLの3つ口フラスコに、1,3,5-アダマンタントリオール5.85g、ヒドロキノン24.18g、p-トルエンスルホン酸15.04g、及び酢酸n-ブチル170.02gを仕込み、よく撹拌した。次に、フラスコ内を窒素置換した後、140℃に加温したオイルバスにフラスコを漬けて、撹拌しながら加熱を開始した。還流状態で1時間加熱し続けた後、冷却した。
冷却した反応液を分液ロートに移し、100gの蒸留水で洗浄した。さらに、100gの蒸留水で5回洗浄した。洗浄後の反応液は181.4gであった。洗浄後の反応液に116.6gのn-ヘプタンを注ぐと、橙色の液状物が層分離して沈降した。沈降物を分液ロートで除去して、得られた上層をさらに207.9gのヘプタンに添加すると微黄色の液状物が沈降した。これを分液して45℃で8時間乾燥した結果、16.5gのポリオール化合物4を得た。得られたポリオール化合物4をGPC測定した結果、標準ポリスチレン換算の重量平均分子量は1000、分子量分布は1.13であった。
製造例1で得られたポリオール化合物1を100重量部、1,4-ジ(ビニルオキシメチル)シクロヘキサン50重量部、トリフェニルスルホニウムトリフルオロメタンスルホナート5重量部、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を混合し、ポリオール化合物濃度15重量%のフォトレジスト組成物1を得た。
得られたフォトレジスト組成物1をシリコンウェハ上にスピンコーティング法により厚み500nmとなるように塗布し、ホットプレートにより温度150℃で180秒間加熱して、レジスト塗膜1を形成した。レジスト塗膜1をKrFエキシマレーザーを使用して、マスクを介して、照射量30mJ/cm2で露光した後、温度100℃で60秒間PEB処理を行った。次いで、2.38%テトラメチルアンモニウムヒドロキシド水溶液により60秒間現像し、純水で洗い流したところ、0.20μmのライン・アンド・スペースパターンが得られた。
製造例1で得られたポリオール化合物1の代わりに、実施例2においては製造例2で得られたポリオール化合物2、実施例3においては製造例3で得られたポリオール化合物3を使用した以外は実施例1と同様に行ったところ、何れの場合も0.20μmのライン・アンド・スペースパターンが得られた。
製造例1で得られたポリオール化合物1を100重量部、1,3-ジビニルオキシアダマンタン50重量部、トリフェニルスルホニウムトリフルオロメタンスルホナート5重量部、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を混合し、ポリオール化合物濃度15重量%のフォトレジスト組成物4を得た。
得られたフォトレジスト組成物4をシリコンウェハ上にスピンコーティング法により厚み500nmとなるように塗布し、ホットプレートにより温度150℃で180秒間加熱して、レジスト塗膜4を形成した。レジスト塗膜4をKrFエキシマレーザーを使用して、マスクを介して、照射量30mJ/cm2で露光した後、温度100℃で60秒間PEB処理を行った。次いで、2.38%テトラメチルアンモニウムヒドロキシド水溶液により60秒間現像し、純水で洗い流したところ、0.20μmのライン・アンド・スペースパターンが得られた。
製造例1で得られたポリオール化合物1の代わりに、実施例5においては製造例2で得られたポリオール化合物2、実施例6においては製造例3で得られたポリオール化合物3を使用した以外は実施例4と同様に行ったところ、何れの場合も0.20μmのライン・アンド・スペースパターンが得られた。
製造例1で得られたポリオール化合物1を100重量部、2,6-ジオキサ-4,8-ジビニルオキシビシクロ[3.3.0]オクタン50重量部、トリフェニルスルホニウムトリフルオロメタンスルホナート5重量部、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を混合し、ポリオール化合物濃度15重量%のフォトレジスト組成物7を得た。
得られたフォトレジスト組成物7をシリコンウェハ上にスピンコーティング法により厚み500nmとなるように塗布し、ホットプレートにより温度150℃で180秒間加熱して、レジスト塗膜7を形成した。レジスト塗膜7をKrFエキシマレーザーを使用して、マスクを介して、照射量30mJ/cm2で露光した後、温度100℃で60秒間PEB処理を行った。次いで、2.38%テトラメチルアンモニウムヒドロキシド水溶液により60秒間現像し、純水で洗い流したところ、0.20μmのライン・アンド・スペースパターンが得られた。
製造例1で得られたポリオール化合物1の代わりに、実施例8においては製造例2で得られたポリオール化合物2、実施例9においては製造例3で得られたポリオール化合物3を使用した以外は実施例7と同様に行ったところ、何れの場合も0.20μmのライン・アンド・スペースパターンが得られた。
製造例1で得られたポリオール化合物1の代わりに、実施例10においては製造例4で得られたポリオール化合物4を使用した以外は実施例1と同様に行ったところ、0.20μmのライン・アンド・スペースパターンが得られた。
Claims (12)
- 脂肪族基と芳香環に水酸基を複数個有する芳香族基とが交互に結合しているポリオール化合物と、ビニルエーテル化合物とを含有するフォトレジスト組成物。
- ポリオール化合物が、脂肪族ポリオールと芳香族ポリオールとの酸触媒反応により得られることを特徴とする請求項1に記載のフォトレジスト組成物。
- 酸触媒反応がFriedel-Crafts反応である請求項2に記載のフォトレジスト組成物。
- 脂肪族ポリオールが脂環式ポリオールである請求項2又は3に記載のフォトレジスト組成物。
- 脂肪族ポリオールがアダマンタン環の3級位に2個以上の水酸基が結合したアダマンタンポリオールである請求項2~4の何れかの項に記載のフォトレジスト組成物。
- 芳香族ポリオールがヒドロキノンである請求項2~5の何れかの項に記載のフォトレジスト組成物。
- 芳香族ポリオールがナフタレンポリオールである請求項2~5の何れかの項に記載のフォトレジスト組成物。
- ポリオール化合物の重量平均分子量が500~5000である請求項1~7の何れかの項に記載のフォトレジスト組成物。
- ビニルエーテル化合物が、多価ビニルエーテル化合物である請求項1~8の何れかの項に記載のフォトレジスト組成物。
- 請求項1~9に記載のフォトレジスト組成物を基材に塗布し、その後、加熱してポリオール化合物とビニルエーテル化合物とを反応させることを特徴とするレジスト塗膜の形成方法。
- 請求項10に記載のレジスト塗膜の形成方法により形成されたレジスト塗膜。
- 請求項11に記載のレジスト塗膜を露光、現像することを特徴とするレジストパターンの形成方法。
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WO2016203938A1 (ja) * | 2015-06-17 | 2016-12-22 | 三菱瓦斯化学株式会社 | アダマンタン構造含有重合体 |
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JPH07306532A (ja) * | 1994-05-12 | 1995-11-21 | Fuji Photo Film Co Ltd | ポジ型感放射線性樹脂組成物 |
JPH11338153A (ja) * | 1998-05-28 | 1999-12-10 | Nippon Petrochem Co Ltd | 遠紫外線用ポジ型レジスト組成物 |
JP2006285075A (ja) * | 2005-04-04 | 2006-10-19 | Shin Etsu Chem Co Ltd | レジスト材料並びにこれを用いたパターン形成方法 |
WO2006123700A1 (ja) * | 2005-05-17 | 2006-11-23 | Kyowa Hakko Chemical Co., Ltd. | フォトレジスト組成物 |
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JP4499471B2 (ja) * | 2004-04-28 | 2010-07-07 | 関西ペイント株式会社 | 感光性樹脂組成物 |
JP2007297317A (ja) * | 2006-04-28 | 2007-11-15 | Sumitomo Bakelite Co Ltd | ジアミノジヒドロキシベンゼン化合物 |
US20110027726A1 (en) * | 2008-04-04 | 2011-02-03 | Kiyoharu Tsutsumi | Polymer compound for photoresist |
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2009
- 2009-04-02 WO PCT/JP2009/001559 patent/WO2009122753A1/ja active Application Filing
- 2009-04-02 US US12/935,969 patent/US20110027717A1/en not_active Abandoned
- 2009-04-02 KR KR1020107022099A patent/KR20100133405A/ko not_active Application Discontinuation
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Patent Citations (4)
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JPH07306532A (ja) * | 1994-05-12 | 1995-11-21 | Fuji Photo Film Co Ltd | ポジ型感放射線性樹脂組成物 |
JPH11338153A (ja) * | 1998-05-28 | 1999-12-10 | Nippon Petrochem Co Ltd | 遠紫外線用ポジ型レジスト組成物 |
JP2006285075A (ja) * | 2005-04-04 | 2006-10-19 | Shin Etsu Chem Co Ltd | レジスト材料並びにこれを用いたパターン形成方法 |
WO2006123700A1 (ja) * | 2005-05-17 | 2006-11-23 | Kyowa Hakko Chemical Co., Ltd. | フォトレジスト組成物 |
Cited By (1)
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WO2016203938A1 (ja) * | 2015-06-17 | 2016-12-22 | 三菱瓦斯化学株式会社 | アダマンタン構造含有重合体 |
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JPWO2009122753A1 (ja) | 2011-07-28 |
KR20100133405A (ko) | 2010-12-21 |
US20110027717A1 (en) | 2011-02-03 |
JP5547059B2 (ja) | 2014-07-09 |
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