WO2005075446A1 - Ester d'hemiacetal et d'acide carboxylique insature, polymere et composition de resine pour agent photoresistant - Google Patents

Ester d'hemiacetal et d'acide carboxylique insature, polymere et composition de resine pour agent photoresistant Download PDF

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Publication number
WO2005075446A1
WO2005075446A1 PCT/JP2005/000794 JP2005000794W WO2005075446A1 WO 2005075446 A1 WO2005075446 A1 WO 2005075446A1 JP 2005000794 W JP2005000794 W JP 2005000794W WO 2005075446 A1 WO2005075446 A1 WO 2005075446A1
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Prior art keywords
group
ring
formula
acid
meth
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PCT/JP2005/000794
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English (en)
Japanese (ja)
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WO2005075446A9 (fr
Inventor
Hiroshi Koyama
Keizo Inoue
Takahiro Iwahama
Mari Sumida
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Daicel Chemical Industries, Ltd.
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Priority claimed from JP2004028595A external-priority patent/JP4651283B2/ja
Priority claimed from JP2004303478A external-priority patent/JP4780945B2/ja
Application filed by Daicel Chemical Industries, Ltd. filed Critical Daicel Chemical Industries, Ltd.
Priority to KR1020067017810A priority Critical patent/KR101115224B1/ko
Priority to US10/537,120 priority patent/US20060160247A1/en
Publication of WO2005075446A1 publication Critical patent/WO2005075446A1/fr
Publication of WO2005075446A9 publication Critical patent/WO2005075446A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
    • 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
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • Unsaturated carboxylic acid hemiacetal ester, polymer compound and resin composition for photoresist Unsaturated carboxylic acid hemiacetal ester, polymer compound and resin composition for photoresist
  • the present invention relates to an unsaturated carboxylic acid useful as a monomer component of a resin for photoresist used when performing fine processing of a semiconductor, etc.
  • the present invention relates to a polymer compound containing a repeating unit corresponding to a myacetal ester, a resin composition for a photoresist containing the polymer compound, and a method for producing a semiconductor.
  • Positive photoresists used in the semiconductor manufacturing process have properties such as the property that the irradiated area changes to alkali-soluble due to light irradiation, adhesion to silicon wafers, plasma etching resistance, and transparency to light used. Must be.
  • the positive type photoresist is generally used as a solution containing a polymer as a main agent, a photoacid generator, and several additives for adjusting the above properties. In order to prepare a polymer, it is extremely important that the polymer as the main agent has the above-mentioned properties in a well-balanced manner.
  • the lithography exposure light source used in semiconductor manufacturing is becoming shorter and shorter each year, and is shifting from a 248 nm wavelength KrF excimer laser to a 193 nm wavelength ArF excimer laser. .
  • the resist polymer used in these KrF or ArF excimer laser exposure machines is desorbed by the acid generated from the photoacid generator upon exposure to Al
  • a monomer unit having a function of being soluble in a re-developing solution a unit having a 2-methyladamantane_2-inole group ⁇ 1-adamantinole 1-methylethyl group is known. (Japanese Patent Laid-Open No. 9-73173, etc.).
  • conventional photoresist resins having these units have not always been satisfactory in terms of sensitivity and degree of development.
  • the balance between substrate adhesion, etching resistance and acid desorption was not sufficient. Disclosure of the invention
  • An object of the present invention is to provide a polymer compound having excellent acid-releasing property or excellent acid-releasing property and excellent substrate adhesion when used for a photoresist, and a monomer thereof, a method for producing the monomer, It is an object of the present invention to provide a resin composition for photoresist containing the polymer compound, and a method for manufacturing a semiconductor using the resin composition.
  • Another object of the present invention is to provide a polymer compound for photoresist having a good balance of substrate adhesion, etching resistance and acid desorption property, a resin composition for photoresist containing the polymer compound, and An object of the present invention is to provide a method for manufacturing a semiconductor using the resin composition.
  • Still another object of the present invention is to provide a polymer compound for photoresist, a resin composition for photoresist, and a method for producing a semiconductor, which can form a fine pattern with high accuracy.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, it has been found that an unsaturated carboxylic acid having a specific structure containing a polymer compound containing a repeating unit corresponding to a miacetal ester as a resin for photoresist is excellent.
  • the present inventors have found that acid desorption properties or excellent acid desorption properties and excellent substrate adhesion are exhibited, and fine patterns can be formed with high accuracy, and the present invention has been completed.
  • RR aa is a hydrogen atom atom, a hahalogenogen atom atom, an aralkyquill group having a carbon number of 11 to 66 or 5 or a carbon number of 5 to 11
  • RR bb represents a hydrogenated hydrocarbon group having a hydrogen atom atom at the 11-position.
  • RR indicates a hydrogen atom atom or a carbohydrocarbon group
  • RR dd includes a cyclic bone skeleton. Shows organic organic base
  • the aforementioned cyclic skeleton of RR dd may be laratata tonton skeleton or non-aromatic aromatic polycyclic polycyclic 10 skeleton. The case remains good. .
  • R represents a hydrogen atom or a hydrocarbon group
  • R d represents an organic group having a cyclic skeleton
  • R B and R f each represent a hydrogen atom or a hydrocarbon group.
  • the present invention also provides the following formula (I):
  • Ra represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms
  • Rb represents a hydrocarbon group having a hydrogen atom at the 1-position.
  • R. represents a hydrogen atom or a hydrocarbon group
  • R d represents an organic group containing a cyclic skeleton.
  • a polymer compound comprising a repeating unit represented by the formula:
  • the polymer compound further comprises at least one selected from a ratatone skeleton-containing monomer, a cyclic ketone skeleton-containing monomer, an acid anhydride group-containing monomer, and an imido group-containing monomer. And a repeating unit [excluding the repeating unit represented by the formula (I)] corresponding to the monomer of the formula (I). Further, the polymer compound further includes a repeating unit corresponding to at least one monomer selected from a hydroxyl group-containing monomer, a mercapto group-containing monomer, and a carboxyl group-containing monomer. You may go out.
  • the present invention further provides a resin composition for photoresist containing at least the above polymer compound and a photoacid generator.
  • the present invention further provides the resin composition for a photoresist as a substrate or Provided is a method for manufacturing a semiconductor, which comprises a step of forming a resist coating film by coating on a substrate and forming a pattern through exposure and development.
  • the vinyl ether-based monomer and the vinyl ether compound in the present specification include a compound in which a hydrogen atom of a bullet group is substituted with a substituent.
  • a protecting group such as a hydroxyl group, a commonly used protecting group in the field of organic synthesis can be used.
  • the polymer compound and its monomer which show the outstanding acid desorption property or the excellent acid desorption property and substrate adhesiveness when used for photoresists are provided.
  • the resin composition for photoresists of the present invention is excellent in acid desorption properties, and exhibits well-balanced substrate adhesion, etching resistance and acid desorption properties. For this reason, a fine pattern can be accurately formed in the manufacture of a semiconductor.
  • the unsaturated carboxylic acid hemiacetal ester of the present invention is represented by the above formula (1).
  • Ra represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms
  • R b represents a hydrocarbon group having a hydrogen atom at the 1-position.
  • R d represents an organic group having a cyclic skeleton.
  • the halogen atom in Ra includes a fluorine atom, a chlorine atom, a bromine atom and the like.
  • alkyl group having 1 to 6 carbon atoms include methyl, ethynole, propynole, isopropynole, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl and the like. Of these, an alkyl group, particularly a methyl group, is preferred.
  • haloalkyl group having 1 to 6 carbon atoms examples include a chloroalkyl group such as a chloromethyl group; triphenylenomethylinole, 2,2,2-triphenylenoletinole, and pentafluoro.
  • a fluoroanolealkyl group such as an ethyl group (preferably, a d- 3 fluoroalkyl group).
  • hydrocarbon radical having 1-position a hydrogen atom in R b for example, methyl, Echinore, propyl, i Sopuro Pinore, Puchinore, Lee Sopuchiru, alkyl groups such as s one-butyl group (e.g.
  • C I 6 Alkyl groups especially —3 alkynole groups); cyclopropynole groups such as cyclopropynole, cyclopentynole, and cyclohexyl groups (for example, 3- to 6-membered cycloalkynole groups); cyclopentynolemethyl, cyclohexylmethyl groups Cycloalkyl groups such as mono- or di- (3- to 6-membered cycloalkyl) 1 C- 3 alkyl groups; aralkyl groups such as benzinole, 1-methylbenzyl, 1-phenylpentyl, etc. For example, mono- or diphenyl-1-d-3 alkyl group).
  • R b a C ⁇ 3 alkyl group such as a methyl, ethyl, propyl, and isopropyl group is preferable, and a methyl group is particularly preferable.
  • hydrocarbon group for R c examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and s-butyl groups (eg, C ⁇ 6 alkyl groups, especially C t - 3 alkyl groups); Cycloalkynole groups (eg, 3- to 6-membered cycloalkyl groups) such as cyclopropyl, cyclopentynole, and cyclohexyl groups; and aryl groups such as phenyl groups.
  • R. The by a hydrogen atom; methyl, Echiru, propyl, preferably C Bok 3 alkyl groups such as isopropyl, especially, a hydrogen atom, a methyl group good or arbitrary.
  • Examples of the cyclic skeleton in the organic group including the cyclic skeleton of Rd include a lactone skeleton and a cyclic skeleton other than the lactone skeleton.
  • the lactone skeleton includes a lactone ring (for example, a lactone ring such as a lipolactone ring, a ⁇ -valerolactone ring, and an ⁇ -force prolactone ring). Or aromatic carbocyclic or heterocyclic ring fused Skeleton included.
  • a skeleton composed of only a lactone ring, and a skeleton in which a non-aromatic carbon ring or a heterocyclic ring (particularly, a non-aromatic carbon ring) is fused to the lactone ring are preferable.
  • Ring constituting the lactone skeleton ⁇ alkyl group such as a methyl group (e.g., a d 4 alkyl group), Haroanorekiru groups such as preparative Rifuruoromechiru group (e.g., C I 4 haloalkyl group), a chlorine atom Ya off Tsu containing Halogen atom such as atom, hydroxy group optionally protected by a protecting group, hydroxyalkyl group optionally protected by a protecting group, mercapto group optionally protected by a protecting group, protecting group May have a substituent such as a ropoxyl group, an amino group which may be protected with a protecting group, and a sulfonic acid group which may be protected with a protecting group.
  • the protecting group include those commonly used in the field of organic synthesis.
  • lactone skeletons include skeletons (groups) represented by the following formulas (6a), (6b), (6c), (6d), (6e), (6f), and (6g). .
  • R 9 ⁇ R 3 6 are the same or different, a hydrogen atom, a halogen atom, Arukinore group, a haloalkyl group, an optionally protected human Dorokishiru group with a protecting group, is protected with a protecting group
  • a hydroxyalkyl group which may be protected by a protecting group X represents an alkylene group, an oxygen atom, a sulfur atom or no bond
  • Vi V 3 represents the same or different, Indicates CH 2 —, one CO— or one COO—. At least one of ⁇ ′ to ⁇ 3 is one COO—.
  • At least two of R 27 to R 31 may combine to form a ring together with a carbon atom or a carbon-carbon bond.
  • at least two groups out of R 32 to R 36 may be bonded to form a ring together with a carbon atom or a carbon-carbon bond.
  • Equations (6a)-(6g) Examples of the halogen atom in ⁇ to 6 and R 9 to R 36 include a fluorine atom and a chlorine atom.
  • Examples of the alkyl group include straight- or branched-chain carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutynole, s-butyl, t-butyl, hexyl, octyl, decyl, and dodecyl groups. And the like. Among them, carbon number :! Alkyl groups of 4 are preferred.
  • Examples of the noroalkyl group include fluoroalkyl groups having 1 to 13 carbon atoms, such as trifluoromethyl and pentafluoroethyl groups.
  • Examples of the hydroxyl group which may be protected with a protecting group include a hydroxyl group and a substituted oxy group (for example, a C alkoxy group such as methoxy, ethoxy, propoxy group, etc.).
  • Examples of the hydroxyalkyl group which may be protected with a protecting group include a group in which a hydroxyl group which may be protected with the protecting group is bonded via an alkylene group having 1 to 6 carbon atoms. Is mentioned.
  • Examples of the mercapto group that may be protected with a protecting group include a mercapto group, a mercapto group protected with the same protecting group as the above-mentioned hydroxyl group, and the like.
  • the carboxyl group which may be protected by a protecting group, and the like one C_ ⁇ _ ⁇ _R y group.
  • R y represents a hydrogen atom or an alkyl group, and the alkyl group is a straight-chain such as methyl, ethyl, propyl, isopropyl, buty ⁇ , isobutyl, s-butyl, t-butyl, hexyl, etc.
  • the alkylene group for X includes a linear or branched alkylene group having about 1 to 3 carbon atoms (preferably 1 or 2) such as methylene, dimethylmethylene, ethylene, propylene, and trimethylene groups. And the
  • the ring formed together with the carbon bond includes an alicyclic carbocycle (including a bridged carbocycle) such as a cyclopentane ring, a cyclohexane ring, and a norbornane ring.
  • the rings constituting the skeleton represented by the formulas (6a) to (6g) may have the substituent as described above.
  • the “ring” constituting the cyclic skeleton other than the lactone skeleton includes a monocyclic or polycyclic non-aromatic or aromatic ring.
  • the monocyclic non-aromatic ring includes, for example, an alicyclic ring such as a cycloalkane ring of about 3 to 15 members such as a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, a cyclodecane ring; a tetrahydrofuran ring And a 3- to 15-membered non-aromatic heterocycle such as a pyrrolidine ring, a piperidine ring and a morpholine ring.
  • Is a polycyclic nonaromatic ring for example, Adamantan ring; norbornane ring, Bruno Ruborunen ring, bornane ring, isobornane ring, preparative Rishikuro [. 5.2.1 0 2 '6] decane ring, Te Torashikuro [4. 4. 0. I 2 ' 5.
  • Bridged carbon ring such as bicyclic, tricyclic, or tetracyclic ring such as a pentadecane ring (for example, having about 6 to 20 carbon atoms) A bridged carbon ring).
  • Monocyclic or polycyclic Examples of the aromatic ring include an aromatic carbon ring such as a benzene ring, a naphthalene ring, a pyridine ring and a quinoline ring, and an aromatic heterocyclic ring.
  • a non-aromatic ring is preferable, and a polycyclic non-aromatic ring is more preferable, from the viewpoints of light transmittance and etching resistance when polymerized and used as a photoresist resin.
  • a polycyclic non-aromatic carbocyclic ring bridged carbocyclic ring.
  • a ring containing a norbornane ring or a norbornene ring, or a ring obtained by hydrogenating a polycyclic aromatic condensed ring (particularly, a completely hydrogenated ring) is particularly preferable.
  • a non-aromatic cyclic skeleton is preferable, and a non-aromatic polycyclic skeleton, particularly, a polycyclic non-aromatic carbocyclic skeleton is preferable.
  • Al kill group such as a methyl group (e.g., alkyl group), triflate Ruo b Haroarukinore group such as a methyl group (e.g., C 4 haloalkyl group),
  • a halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, or a mercapto which may be protected by a protecting group May have a substituent such as a group, a carboxyl group which may be protected with a protecting group, an amino group which may be protected with a protecting group, and a sulfonic acid group which may be protected with a protecting group.
  • the protecting group include those commonly used in the field of organic synthesis.
  • the organic group containing a cyclic skeleton in R d includes the following formula (2)
  • A represents a linking group
  • Z 1 represents a ring constituting a cyclic skeleton
  • linking group in A examples include a single bond; methylene, Linear or branched alkylene groups such as methylene, dimethylmethylene, ethylene, propylene, and trimethylene groups; carbonyl groups; oxygen atoms (ether bonds; ___- 1); oxycarbonyl groups (ester bonds; —); An amino lponyl group (amide bond; one CONH—); and a group in which a plurality of these groups are bonded.
  • Preferred linking groups include a single bond, a linear or branched alkylene group (particularly, a d- 3 alkylene group) and the like.
  • the linking group includes, for example, a halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group optionally protected by a protecting group, a hydroxyalkyl group optionally protected by a protecting group, or a protecting group. Substitution of an optionally protected mercapto group, a carboxyl group optionally protected by a protecting group, an amino group optionally protected by a protecting group, a sulfonate group optionally protected by a protecting group It may have a group.
  • the Uchiraku tons backbone cyclic skeleton in the z 1 skeleton represented by the formula (6a) ⁇ (6g) are exemplified up. Also, as the ring constituting the cyclic skeletal non Lata tons skeleton of the cyclic skeleton in Z 1, include those exemplified above.
  • the group represented by the formula (2) Compounds having an organic group containing a cyclic skeleton other than the ratatone skeleton among the compounds contained therein include the following compounds, but are not limited thereto.
  • the unsaturated carboxylic acid hemiacetal ester represented by the formula (1) is, for example, as shown in the following reaction formula, the unsaturated carboxylic acid represented by the formula (3) and the unsaturated carboxylic acid represented by the formula (4).
  • the reaction can be carried out in a solvent or under a non-solvent with the butyl ether compound to be produced.
  • the product, the compound represented by the formula (5), corresponds to the compound represented by the formula (1).
  • R a , R. and R d are the same as above.
  • R e and R f each represent a hydrogen atom or a hydrocarbon group, and one CHR SR f corresponds to R b ).
  • the acid catalyst is not particularly limited, and any of an inorganic acid and an organic acid can be used.
  • the inorganic acid include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; and polyacids such as phosphomolybdic acid, chemolybdic acid, phosphorus tungstic acid, and silicotungstic acid; Body catalyst and the like.
  • organic acid examples include carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid; and sulfonic acids such as methanesnolefonic acid, trifluoromethanesulfonic acid, benzenesnolefonic acid, p-tonolenesnolefonic acid, and naphthalenesulfonic acid.
  • carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid
  • sulfonic acids such as methanesnolefonic acid, trifluoromethanesulfonic acid, benzenesnolefonic acid, p-tonolenesnolefonic acid, and naphthalenesulfonic acid.
  • An on-exchange resin may be used.
  • a Lewis acid can be used.
  • a pyridinium salt an ammonium salt, an alkali metal salt, an alkaline
  • the solvent is not particularly limited as long as it is a solvent inert to the reaction.
  • examples thereof include aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; Alicyclic hydrocarbons such as mouth hexane; halogenated hydrocarbons such as methylene chloride; ethers such as tetrahydrofuran and ethylene glycol—non-resin-methinoleate; non-acetones such as N, N-dimethylformamide Examples include protonic polar solvents.
  • the amount of the unsaturated carboxylic acid represented by the formula (3) is, for example, about 0.5 to 50 mol, preferably 0.9 to 100 mol per 1 mol of the butyl ether compound represented by the formula (4). It is about 10 mol.
  • the amount of the acid catalyst to be used is, for example, about 0.001 :! to about 1 mol, preferably about 0.001 to 0.3 mol, per 1 mol of the vinyl ether compound represented by the formula (4). It is.
  • a polymerization inhibitor such as 4-methoxyphenol
  • the amount of the polymerization inhibitor to be added is, for example, about 0.0001 to 0.05 mol, preferably 0.00001 to 1 mol of the vinyl ether compound represented by the formula (4).
  • O.0.1 is about 1 mole.
  • the reaction temperature varies depending on the type of the reaction raw material, the type of the catalyst used, and the like, but is usually about 10 to 100 ° C, preferably about 0 to 60 ° C.
  • R b and R in the formula (1) are all hydrogen atoms, and are also useful as monomers of polymer compounds for photoresist.
  • R b and R in the formula (1) Is a hydrogen atom [compound represented by the formula (:)], for example, as shown in the following reaction formula, an unsaturated carboxylic acid represented by the formula (3) and a compound represented by the formula (A) It can be produced by reacting the represented halomethyl ether compound in the presence of a base.
  • R a and R d are the same as above.
  • Y represents a halogen atom.
  • Examples of the halogen atom in Y include a chlorine, bromine, and iodine atom.
  • the reaction is performed in the presence or absence of a solvent.
  • the solvent described above can be used as the solvent.
  • As the base for example, an organic base such as triethylamine and pyridine, or an inorganic base such as sodium hydroxide, sodium carbonate and sodium hydrogen carbonate can be used.
  • the amount of the unsaturated carboxylic acid represented by the formula (3) is, for example, about 0.5 to 10 mol, preferably 0.8, per mol of the halomethyl ether compound represented by the formula (A). About 2 moles.
  • the amount of the base used is, for example, about 1 to 5 mol per mol of the unsaturated carboxylic acid represented by the formula (3). Yes.
  • a small amount of a polymerization inhibitor such as 4-methoxyphenol may be added to the system.
  • the reaction temperature is usually about ⁇ 10 ° C. to 100 ° C., preferably about 0 to 60 ° C.
  • the reaction product can be separated and purified by a separation means such as liquid property adjustment, extraction, concentration, distillation, crystallization, recrystallization, column chromatography and the like.
  • the halomethyl ether conjugate represented by the formula (A) is, for example, as shown in the following reaction formula, a hydroxy compound represented by the formula (C) added to formaldehyde or its equivalent (para). Formaldehyde, 1,3,5-trioxane, etc.) and a halogen hydride represented by the formula (D).
  • Examples of the hydrogen halide represented by the formula (D) include hydrogen chloride and hydrogen bromide.
  • the reaction is performed in the presence or absence of a solvent.
  • the solvents described above can be used as the solvent.
  • the amount of formaldehyde or an equivalent thereof used is, for example, about 0.8 to 10 mol, preferably 1 to 1 mol, per mol of the hydroxy compound represented by the formula (C), in terms of formaldehyde. It is about 5 moles.
  • the amount of the hydrogen halide represented by the formula (D) is, for example, about 1 to 5 mol per mol of the hydroxy compound represented by the formula (C), and a large excess may be used.
  • the reaction temperature is usually about ⁇ 10 ° C.
  • reaction product can be separated and purified by a separation means such as adjustment of liquid properties, extraction, concentration, distillation, crystallization, recrystallization, and column chromatography.
  • the polymer compound of the present invention contains a repeating unit (monomer unit) corresponding to the above-mentioned unsaturated carboxylic acid mesacetal ester, that is, a unit represented by the formula (I).
  • the repeating unit may be one kind or two or more kinds.
  • Such a high molecular compound can be obtained by subjecting the above unsaturated carboxylic acid to a miacetal ester to polymerization. Since the repeating unit represented by the formula (I) has a hemiacetal ester structure, it has an acid-eliminating function (alkali-soluble function).
  • the acid generated from the photoacid generator upon exposure removes the alcohol portion (hemiacetal portion) of the ester to form a free carboxyl group, which makes the ester more soluble in the alkaline developer.
  • the hemiacetal ester structure contains three oxygen atoms, it has higher hydrophilicity than the conventional acid-eliminable unit having a simple ester structure (containing two oxygen atoms), and has a resist solvent.
  • the solubility and the wettability with respect to an alkaline developer are improved.
  • the repeating unit represented by the formula (I) has a lactone skeleton, the adhesion to the substrate is excellent.
  • Such a polymer compound having a repeating unit having both an acid-eliminating function and a substrate adhesion function has a higher acid-elimination property than a conventional polymer compound having a repeating unit having only an acid-eliminating function.
  • Substrate adhesion can be significantly increased while maintaining the number of leaving groups, so that high substrate adhesion can be achieved, and the number of acid-labile groups and the number of substrate adhesion groups are maintained
  • R d in the formula (I) is a group containing a polycyclic non-aromatic carbocyclic ring (bridged carbocyclic ring), it exhibits high light transmittance and dry etching resistance.
  • the polymer compound of the present invention can sufficiently perform various functions required as a resist.
  • other repeating units may be provided in addition to the repeating unit represented by the above formula (I).
  • Such another repeating unit can be formed by copolymerizing a polymerizable unsaturated monomer corresponding to the repeating unit with the unsaturated rubonic acid and a miacetal ester.
  • the other repeating unit for example, a repeating unit having a substrate adhesion and a Z or hydrophilic function, a repeating unit improving an acid desorption property, a repeating unit improving an etching resistance function, and improving transparency And repeating units.
  • the hydrophilic function includes a function of increasing solubility in a resist solvent or an alkaline developer.
  • a monomer used to promote copolymerization smoothly or to make the copolymer composition uniform may be used as a comonomer.
  • a repeating unit having substrate adhesion and Z or hydrophilic function can be introduced into a polymer by using a polymerizable unsaturated monomer having a polar group as a comonomer.
  • the polar group include (1) a lactone ring-containing group, a carbonyl group, an acid anhydride group, and an imido group; and (2) a hydroxyl group optionally having a protective group.
  • the polymerizable unsaturated monomer having a polar group include: (a) a monomer containing a ratatone skeleton, a monomer containing a cyclic ketone skeleton, a monomer containing an acid anhydride group, and a monomer containing an imido group.
  • a monomer such as a monomer such as a monomer, (b) a monomer containing a hydroxy group (including a compound in which a hydroxy group is protected), a monomer containing a mercapto group (a compound in which a mercapto group is protected) ), A carboxy group-containing monomer (including a compound having a protected carboxyl group), an amino group-containing monomer (including a compound having a protected amino group), and sulfonate Group-containing monomers (including conjugates in which the sulfonic acid group is protected) And a compound known in the resist field can be used.
  • These monomers can be used alone or in combination of two or more. For example, by combining the monomer belonging to the above (a) and the monomer belonging to the above (b), it is possible to develop a balanced resist property S.
  • the repeating unit that enhances the acid elimination function includes, for example, (c) a hydrocarbon group having a tertiary carbon, a 2-tetrahydrofuranyl group, or a 2-tetrahydro group at a position adjacent to the oxygen atom constituting the ester.
  • the hydrocarbon group is a COOR x group (R x represents a tertiary hydrocarbon group, 2-tetrahydrofuranyl group or 2-tetrahydrovinylyl group).
  • a (meth) acrylate ester derivative or the like bonded directly or via a linking group can be introduced into a polymer by using as a comonomer.
  • a (meth) atalinoleic acid ester derivative a compound known in the field of resist can be used.
  • an unsaturated carboxylic acid used to impart various functions as a resist to the polymer compound of the present invention is represented by the following formula (8a) To (8g). These correspond to the lactone skeleton-containing monomer and the cyclic ketone skeleton-containing monomer.
  • R represents a hydrogen atom or a methyl group. 1 ⁇ to 16 , R 9 to R 36 , X, to V 3 are the same as described above.
  • Representative examples of the compound represented by the formula (8a) include, but are not limited to, the following compounds.
  • Representative examples of the compound represented by the formula (8b) include, but are not limited to, the following compounds.
  • Representative examples of the compound represented by the formula (8c) include the following compounds, but are not limited thereto.
  • Representative examples of the compound represented by the formula (8d) include the following compounds, but are not limited thereto.
  • Representative examples of the compound represented by the formula (8g) include the following compounds, but are not limited thereto.
  • polymerizable unsaturated monomers other than myacetal esters include unsaturated carboxylic acids used to impart various functions as a resist to the polymer compound of the present invention, such as maleic anhydride, Maleimide. These correspond to the acid anhydride group-containing monomer and the imide group-containing monomer.
  • the following are typical examples of polymerizable unsaturated monomers other than myacetal esters used for imparting various functions as a resist to the polymer compound of the present invention.
  • a compound represented by the formula (9). These compounds are the same as those described above for the hydroxyl group-containing monomer, mercapto. It corresponds to a group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a sulfonic acid group-containing monomer and a cyclic ketone skeleton-containing monomer.
  • ring Z 2 represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms.
  • R represents a hydrogen atom or a methyl group.
  • R 37 represents a substituent bonded to ring Z 2 , Same or different, may be protected by an oxo group, an alkyl group, a hydroxyl group optionally protected by a protecting group, a hydroxyalkyl group optionally protected by a protecting group, or a protecting group A carboxyl group, an amino group which may be protected by a protecting group, or a sulfonic acid group which may be protected by a protecting group, provided that at least one of n R 37s is an oxo group or a protecting group A hydroxyl group which may be protected with a group, a hydroxyalkyl group which may be protected with a protecting group, a carboxyl group which may be protected with a protecting group, an amino which may be protected with a protecting group Group or protected by a protecting group.
  • alicyclic hydrocarbon ring monocyclic having 6 to 20 carbon atoms in the ring Z 2, or may be a polycyclic ring, over fused ring and bridges.
  • Typical alicyclic hydrocarbon rings include, for example, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring, norbornene ring, bornane ring, isobornane ring, perhydroindene ring, decalin ring, 'Pahi mud fluorene ring (1, Rishikuro [7.4.3 0.0 3' 8] tridecane ring), Pahi Doroantora Sen ring, tricyclo [5.2.2 1.0 2 '6] decane ring, tricyclo [4.
  • the alicyclic hydrocarbon ring has a methyl group Alkyl group such (e.g., C, etc.
  • haloalkyl group such as group, a fluorine atom or a halogen atom, an optionally protected coercive Mamorumoto human Dorokishiru group such as a chlorine atom, a protecting group Or protected with a hydroxyalkyl group, a mercapto group which may be protected with a protecting group, an oxo group, a carboxyl group which may be protected with a protecting group, or a protecting group. It may have a substituent such as a good amino group or a sulfonate group which may be protected with a protecting group. ⁇
  • ano group for R 37 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group And linear or branched alkyl groups having about 1 to 20 carbon atoms.
  • a protected or unprotected amino group the amino group, substituted amino group (e.g., methylcarbamoyl Ruamino, Echiruamino, etc.
  • R z represents a hydrogen atom or an alkyl group, and the alkyl group is a linear or branched chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butynole, t-butynole, and hexyl. And an alkyl group having 1 to 6 carbon atoms.
  • Possible carboxyl groups are the same as described above.
  • Representative examples of the compound represented by the formula (9) include, but are not limited to, the following compounds.
  • carboxyl group-containing monomer for example, acrylic acid, methacrylic acid and the like can be used.
  • polymerizable unsaturated monomer used to enhance the acid-eliminating function of the polymer compound include, for example, 1-1 [(1-1) (meth) atalyloyloxy-1- 1-methylethyl] ridamantane, 2- (Meth) acryloyloxy 2-Methyladamantane, 2- (Meth) acryloyloxy
  • the proportion of the repeating unit represented by formula (I) is limited, and with respect to the total monomer units constituting the polymer, typically. 1 to: 1 0 ⁇ mole 0/0, preferably 1 0-9 0 mole 0/0, more preferably 3 0-8 about 0 mol%.
  • the ratio of [excluding the repeating unit represented by the formula (I)] is 0 to 95 mol%, preferably 0 to 60 mol%, and more preferably about 10 to 40 mol%. .
  • the proportion of the repeating unit corresponding to at least one monomer selected from a monomer containing a hydroxyl group, a monomer containing a mercapto group and a monomer containing a carboxyl group is 0 to 95 mol. %, preferably 5-9 0 mole 0/0, preferably in the al about 1 0-5 0 mol%.
  • the polymerization of the monomer mixture is performed by a conventional method used for producing an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, and the like.
  • solution polymerization can be performed.
  • drop polymerization is preferable among solution polymerizations.
  • a monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in an organic solvent are respectively prepared, and the organic solvent kept at a constant temperature is prepared.
  • ethers chain ethers such as glycol ethers such as methyl alcohol, propylene glycol monomethyl ether and the like, cyclic ethers such as tetrahydrofuran and dioxane), and esters (esters).
  • the polymer obtained by polymerization can be purified by precipitation or reprecipitation.
  • the precipitation or reprecipitation solvent may be either an organic solvent or water, or may be a mixed solvent.
  • the organic solvent used as the precipitation or reprecipitation solvent include: hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene, toluene, Aromatic hydrocarbons such as xylene), halogenated hydrocarbons (aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride); hydrogenated aromatics such as benzene and dichlorobenzene Group hydrocarbons), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), Monoethers (
  • a solvent containing at least a hydrocarbon is preferable as the organic solvent used as the precipitation or reprecipitation solvent.
  • the resin composition for photoresist of the present invention contains the polymer compound of the present invention and a photoacid generator.
  • the photoacid generator examples include conventional or known compounds which efficiently generate an acid upon exposure to light, such as diazonium salts, odonium salts (e.g., diphenyl hexafluorophosphate), and snorephonium salts (e.g., For example, triphenylenolesnorrefoname hexafluoroantimonate, trifenenoles / levonihexene hexanoleophthalate phosphate, triphenylenolesnorrefonium methanesulfonate, etc.), sulfonic acid ester [ For example, 1-feninole 1-(4-methinolefenole) snorehoninoleoxy 1 1 benzoylmethane, 1,2,3-trisinolephonyloxymethylbenzene, 1, 3-dinitro-1- (4-phenylenolesulfonyloxymethyl) benzene, 1-phenyl
  • Oxathiazole derivatives s-triazine derivatives, disulfone derivatives (such as diphenyldisulfone), imid compounds, oxime sulfonates, diazonaphthoquinone, and benzoin tosylate.
  • These photoacid generators can be used alone or in combination of two or more.
  • the amount of the photoacid generator to be used can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each monomer unit (repeat unit) in the polymer compound, and the like. 0. ⁇ ⁇
  • It can be selected from a range of about 30 parts by weight, preferably about 1 to 25 parts by weight, and more preferably about 2 to 20 parts by weight.
  • the resin composition for photoresist includes an alkali-soluble component such as an alkali-soluble resin (for example, a novolak resin, a phenol resin, an imido resin, and a carboxyl group-containing resin), a coloring agent (for example, a dye), and an organic compound.
  • an alkali-soluble component such as an alkali-soluble resin (for example, a novolak resin, a phenol resin, an imido resin, and a carboxyl group-containing resin), a coloring agent (for example, a dye), and an organic compound.
  • Solvents eg, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents of these, etc.
  • Etc. may be included.
  • the coating film (resist film) is exposed to a light beam through a predetermined mask (or, after the exposure, the beta film is exposed).
  • a fine pattern can be formed with high precision by forming a latent image pattern and then developing.
  • Examples of the base material or the substrate include a silicon wafer, metal, plastic, glass, and ceramic.
  • Application of the resin composition for photoresist is performed using a conventional coating method such as a spin coater, dip coater, or roller coater. This can be done using steps.
  • the thickness of the coating film is, for example, about 0.01 to 20 zm, and preferably about 0.05 to 2 m.
  • wavelengths of light such as ultraviolet rays and X-rays
  • Various wavelengths of light can be used for the exposure.
  • semiconductor resists g-rays, i-rays, excimer lasers (eg, XeC1, KrF) are usually used.
  • a r 2 and the like are used.
  • the exposure energy is, for example, about 0.1 to 100 mj / cm 2 .
  • an acid Upon irradiation with light, an acid is generated from the photoacid generator, and the acid generates a protective group (for example, a carboxyl group of a monomer unit having an acid-labile group of the polymer compound (alkaline soluble unit)).
  • a protective group for example, a carboxyl group of a monomer unit having an acid-labile group of the polymer compound (alkaline soluble unit)
  • (Eliminable group) is rapidly eliminated, and a carboxyl group or the like contributing to solubilization is generated. Therefore, a predetermined pattern can be accurately formed by development with water or an alkaline developer.
  • the concentrate is purified by silica gel column chromatography, and the 2- (1-methacryloyl) represented by the following formula (12) is obtained. Ruokishietokishi) to give an 4-O hexa tricyclo [4.2.3 1.0 3 '7] non Hmm 5-one 2 5. 5 g (9 6 mm o 1, 8 1% yield). This substance was a mixture of two isomers, and the abundance was about 1: 1.
  • 3-hydroxy-11-spiroxaspiro [4.5] decane-2-one represented by the formula (13) can be obtained from cyc hexanol and methyl acrylate by the literature [Chem. Commun. 7, 613-614 (2000)], and used after purification by silica gel ram chromatography.
  • reaction solution was washed successively with 170 ml of water, 170 ml (twice) of a 10% by weight aqueous sodium carbonate solution and 170 ml of water, and the organic layer was concentrated under reduced pressure.
  • the concentrate is purified by silica gel column chromatography, and the [1- (adamantan-1-yl) ethoxy] ethyl (meta) acrylate represented by the following formula (17) is obtained. [1-[2-(Adamantane 1-1) ethoxy]] Ethyl (meta) acrylate spectrum data]
  • the concentrate was purified by silica gel column chromatography to obtain 11- (bornyloxy) ethyl methacrylate 22.8 g (85 mmo1, yield 85%) represented by the following formula (19).
  • Bornyl vinyl ether was synthesized from (-)-borneol and propionate bull using the method described in JP-A-2003-73332 and purified by distillation. .
  • PGM Propylene glycol monomethyl ether acetate
  • the obtained reaction solution was added dropwise to a mixed solution of 733 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was recovered with Nutsuchi.
  • the obtained polymer was dried under reduced pressure to obtain 13.5 g of the desired product.
  • the weight average molecular weight (M w ) of the obtained polymer was 110,000, and the molecular weight distribution (M w / M n ) was 1.90 (GPC measurement value, converted to polystyrene).
  • PGM Propylene glycol monomethyl ether acetate
  • the obtained polymer was dried under reduced pressure to obtain 12.6 g of the desired product.
  • the weight average molecular weight (M w ) of the obtained polymer was 990, and the molecular weight distribution (M w / M n ) was 1.91 (measured GPC value, in terms of polystyrene).
  • the obtained reaction solution was dropped into a mixed solution of 733 g of hexane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutsche.
  • the obtained polymer is dried under reduced pressure, 12.8 g were obtained.
  • the weight average molecular weight (M w ) of the obtained polymer was 90, and the molecular weight distribution (M W ZMJ was 1.89 (GPC measurement value,-′ in terms of styrene)).
  • PGM EA propylene glycol monomethyl enoate ethereal acetate
  • PGME propylene glycol monomethyl ether
  • the obtained reaction solution was dropped into a mixed solution of 733 g of hexane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutsche.
  • the obtained polymer was dried under reduced pressure to obtain 12.5 g of the desired product.
  • the obtained polymer had a weight average molecular weight (M w ) of 110,000 and a molecular weight distribution (M w / M n ) of 1.88. (GPC measurement value, converted to polystyrene).
  • the obtained reaction solution was added dropwise to a mixed solution of 733 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutsche.
  • the obtained polymer was dried under reduced pressure to obtain 13.5 g of the desired product.
  • the weight average molecular weight (M w ) of the obtained polymer was 930, and the molecular weight distribution (M W / MJ was 1.92 (GP C measurement value, converted to polystyrene).
  • the obtained reaction solution was added dropwise to a mixed solution of 7333 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was recovered with a nut.
  • the obtained polymer was dried under reduced pressure to obtain 13.5 g of the desired product.
  • the obtained polymer had a weight average molecular weight (M w ) of 980 and a molecular weight distribution (M w ZM n ) of 1.88 (GPC measurement value, converted to polystyrene).

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Abstract

Polymère comprenant des motifs de répétition correspondant à un ester d'hémiacétal et d'acide carboxylique insaturé représenté par la formule (1) suivante : (1) (dans laquelle Ra représente un hydrogène, un halogéno, un alkyle en C1-6 ou un halogénoalkyle en C1-6 ; Rb représente un groupe dérivé d'un hydrocarbure ayant un atome d'hydrogène en position 1- ; Rc représente un hydrogène ou un groupe dérivé d'un hydrocarbure ; et Rd représente un groupe organique contenant un squelette cyclique). Le polymère peut en plus contenir des motifs de répétition correspondant à au moins un monomère choisi parmi des monomères ayant un squelette lactone, des monomères ayant un squelette cétone cyclique, des monomères ayant un groupe anhydride d'acide et des monomères ayant un groupe imide [à part les motifs de répétition correspondant à l'ester d'hémiacétal et d'acide carboxylique insaturé] et/ou des motifs correspondant à au moins un monomère choisi parmi des monomères ayant un groupe hydroxy, etc. Lorsqu'il est utilisé dans un agent photorésistant, ce polymère a l'excellente propriété de libérer un acide.
PCT/JP2005/000794 2004-02-04 2005-01-17 Ester d'hemiacetal et d'acide carboxylique insature, polymere et composition de resine pour agent photoresistant WO2005075446A1 (fr)

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WO2006087865A1 (fr) * 2005-02-16 2006-08-24 Tokyo Ohka Kogyo Co., Ltd. Composition de resine positive et procede pour former un modele de resine
WO2006123496A1 (fr) * 2005-05-17 2006-11-23 Tokyo Ohka Kogyo Co., Ltd. Composition de reserve positive et procede pour la formation d'un dessin de reserve
WO2006126329A1 (fr) * 2005-05-24 2006-11-30 Tokyo Ohka Kogyo Co., Ltd. Composition de photorésistant positif, photorésistant à couche épaisse, procédé de production d'une matrice résistante épaisse, et procédé de production d’une borne de connexion
WO2007083458A1 (fr) * 2006-01-17 2007-07-26 Tokyo Ohka Kogyo Co., Ltd. Composition de réserve positive pour exposition par immersion et procédé de formation d'un motif de réserve
WO2008032522A1 (fr) * 2006-09-11 2008-03-20 Tokyo Ohka Kogyo Co., Ltd. Composition de réserve de type réserve positive et procédé pour la formation d'une impression de réserve
EP1947510A1 (fr) * 2005-11-11 2008-07-23 Tokyo Ohka Kogyo Co., Ltd. Composition de resist positif et procede de formation de motif de resist
JP2014142424A (ja) * 2013-01-22 2014-08-07 Tokyo Ohka Kogyo Co Ltd レジストパターン形成方法
CN111198479A (zh) * 2018-11-20 2020-05-26 东京应化工业株式会社 抗蚀剂组合物以及抗蚀剂图案形成方法

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KR101706869B1 (ko) * 2014-12-26 2017-02-15 주식회사 엘지화학 헤미아세탈 에스테르계 커플링제, 이를 이용한 스티렌-부타디엔계 단량체의 블록 공중합체 및 이를 포함하는 핫멜트 접착제 조성물
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JP2000187327A (ja) * 1998-10-15 2000-07-04 Fuji Photo Film Co Ltd 遠紫外線露光用ポジ型フォトレジスト組成物
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WO2006087865A1 (fr) * 2005-02-16 2006-08-24 Tokyo Ohka Kogyo Co., Ltd. Composition de resine positive et procede pour former un modele de resine
US7803512B2 (en) 2005-02-16 2010-09-28 Tokyo Ohka Kogyo Co., Ltd. Positive resist composition and method of forming resist pattern
US7781144B2 (en) 2005-05-17 2010-08-24 Tokyo Ohka Kogyo Co., Ltd. Positive resist composition and resist pattern forming method
WO2006123496A1 (fr) * 2005-05-17 2006-11-23 Tokyo Ohka Kogyo Co., Ltd. Composition de reserve positive et procede pour la formation d'un dessin de reserve
WO2006126329A1 (fr) * 2005-05-24 2006-11-30 Tokyo Ohka Kogyo Co., Ltd. Composition de photorésistant positif, photorésistant à couche épaisse, procédé de production d'une matrice résistante épaisse, et procédé de production d’une borne de connexion
US7871753B2 (en) 2005-11-11 2011-01-18 Tokyo Ohka Kogyo Co., Ltd. Positive resist composition and method of forming resist pattern
EP1947510A1 (fr) * 2005-11-11 2008-07-23 Tokyo Ohka Kogyo Co., Ltd. Composition de resist positif et procede de formation de motif de resist
EP1947510A4 (fr) * 2005-11-11 2010-10-06 Tokyo Ohka Kogyo Co Ltd Composition de resist positif et procede de formation de motif de resist
WO2007083458A1 (fr) * 2006-01-17 2007-07-26 Tokyo Ohka Kogyo Co., Ltd. Composition de réserve positive pour exposition par immersion et procédé de formation d'un motif de réserve
US7968269B2 (en) 2006-01-17 2011-06-28 Tokyo Ohka Kogyo Co., Ltd. Positive resist composition for immersion exposure and method of forming resist pattern
WO2008032522A1 (fr) * 2006-09-11 2008-03-20 Tokyo Ohka Kogyo Co., Ltd. Composition de réserve de type réserve positive et procédé pour la formation d'une impression de réserve
JP2014142424A (ja) * 2013-01-22 2014-08-07 Tokyo Ohka Kogyo Co Ltd レジストパターン形成方法
CN111198479A (zh) * 2018-11-20 2020-05-26 东京应化工业株式会社 抗蚀剂组合物以及抗蚀剂图案形成方法
CN111198479B (zh) * 2018-11-20 2024-05-28 东京应化工业株式会社 抗蚀剂组合物以及抗蚀剂图案形成方法

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