WO1998037458A1 - Composition d'un agent de reserve - Google Patents

Composition d'un agent de reserve Download PDF

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Publication number
WO1998037458A1
WO1998037458A1 PCT/JP1998/000705 JP9800705W WO9837458A1 WO 1998037458 A1 WO1998037458 A1 WO 1998037458A1 JP 9800705 W JP9800705 W JP 9800705W WO 9837458 A1 WO9837458 A1 WO 9837458A1
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WIPO (PCT)
Prior art keywords
acid
amines
resist composition
compound
group
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PCT/JP1998/000705
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English (en)
Japanese (ja)
Inventor
Atsushi Sone
Kimiaki Tanaka
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Nippon Zeon Co., Ltd.
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Publication of WO1998037458A1 publication Critical patent/WO1998037458A1/fr

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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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

  • the present invention relates to a resist composition useful for manufacturing an integrated circuit (IC), a large-scale integrated circuit (LSI), or the like using a lithography technique.
  • the present invention relates to a resist composition useful for manufacturing semiconductor devices by ultra-fine processing using activating radiation such as far-ultraviolet rays such as ArF excimer lasers, charged particles such as electron beams, and X-rays.
  • activating radiation such as far-ultraviolet rays such as ArF excimer lasers, charged particles such as electron beams, and X-rays.
  • a fine pattern is formed on the substrate using lithography technology.
  • lithography technology (1) a photosensitive polymer material called a resist is dissolved in an organic solvent on a substrate such as a silicon wafer on which a layer to be processed (for example, an oxide film) is formed. The resist solution is applied, and the excess organic solvent is evaporated by a pre-bake to form a resist film. (2) The resist film is partially exposed to light (ultraviolet rays, (Ultraviolet rays, electron beams, X-rays, etc.) to form a latent image. (3) Use a developer to remove unnecessary portions of the resist film to form a negative or positive resist pattern. 4 Dry etching of the exposed surface of the substrate etc. using this resist pattern as an etching resistant mask. 5 Finally, removing unnecessary resist. I have.
  • a technology capable of forming a fine pattern of 0.5 / m or less is required.
  • the yield has been significantly reduced.
  • far-ultraviolet light short-wave ultraviolet light
  • a KrF excimer laser with a wavelength of 248 nm
  • a wavelength of 193 A lithographic technique using a nm ArF excimer laser is being studied.
  • a novolak resin is used as a base polymer for a resist.
  • nopolak resin has good transparency to ultraviolet light with a wavelength of 350 to 450 nm, it has a shorter wavelength of far ultraviolet light and a KrF or ArF excimer laser.
  • the transmittance is extremely deteriorated. Therefore, if a resist using a novolak resin as a base polymer was used, there was a problem that sufficient sensitivity could not be obtained and the pattern shape was poor.
  • chemically amplified resists include, for example, (1) a base polymer, (2) a photoacid generator (a compound that generates an acid by light irradiation), and (3) an acid sensitive substance (light A three-component resist composition is known, which reacts with an acid generated from an acid generator by irradiation as a catalyst to change the solubility of a base polymer.
  • a two-component resist composition comprising a (blocked) polymer compound and a photoacid generator is known.
  • the acid (protonic acid) generated by the photoacid generator upon irradiation with light is transferred to the resist solid phase by heat treatment after exposure to light.
  • Acids are used to catalytically amplify chemical changes in the base polymer and other components.
  • the protecting group is removed by a chain reaction using an acid generated by light irradiation as a catalyst, so that the base polymer can be used in a developer. Restores solubility.
  • Japanese Patent Application Laid-Open No. 5-249673 discloses a photosensitive composition comprising a resin binder and a photoacid generator, wherein the resin binder comprises a phenolic unit and a non-aromatic cyclic compound.
  • a photosensitive composition comprising a polymer having an alcohol unit, wherein at least a part of the hydroxyl group of the polymer is protected by an acid labile (1 abi 1 e) group. Proposed.
  • a base polymer a polymer formed by partial hydrogenation of a novolak resin or a poly (vinyl alcohol) is used.
  • a partially hydrogenated polymer As the base polymer, the transmittance for short-wavelength activating radiation can be increased.
  • ArF excimer laser exposure In lithography using light having a shorter wavelength, it is not preferable that an aromatic ring absorbing the shorter wavelength be present in the base polymer.
  • Japanese Patent Application Laid-Open Publication No. Hei 7-199467 describes a polymer having no aromatic ring as a “polymer compound containing a group that converts polarity by reacting with an acid”.
  • Lulic acid ester copolymers for example, tricyclodecanoinolemethacrylate, tetrahydrobiranylmethacrylate / It is proposed to use methacrylic acid copolymer].
  • methacrylic acid copolymer for chemically amplified resist compositions using a (meth) acrylic acid ester copolymer as a base polymer. Among them, there are many proposals.
  • the chemically amplified resist composition may cause an abnormality in the cross-sectional shape of the pattern due to the influence of the surroundings. For example, under the influence of the substrate material, a footing may occur at the interface between the pattern and the substrate.
  • the acid is neutralized by a trace amount of a basic substance present in the atmosphere and loses its catalytic activity, a poorly soluble layer is formed on the resist pattern film surface, and this poorly soluble layer is formed. It is known that it remains like an eave (T-Topping).
  • JP-A-6-26611 discloses that (a) an alkali-soluble polymer of an alkali-soluble polymer is modified by an acid-labile group.
  • a chemically amplified resist composition comprising a protected polymer and (b) a compound capable of generating an acid upon exposure to light, It has been proposed to add an amine compound selected from the group consisting of an imidazole compound, an alanine compound, an adenine compound, and an adenosine compound.
  • these amine compounds are strongly basic or sublimable compounds having no boiling point, there was a problem in the storage stability of the resist composition.
  • an alcohol-soluble polymer having a phenol skeleton is regarded as a polymer.
  • the phenolic hydroxyl group is etherified or esterified by treating it with an etherified ester IJ or an esterifying agent, the transmittance of short-wavelength activating radiation is reduced. Not enough.
  • Japanese Patent Application Laid-Open No. 7-129929 proposes to add a basic compound having a pKa of 6 or less to a chemically amplified resist composition.
  • the basic compound used in the examples is a low-boiling amide compound such as pyridine or N-methylaniline, and in a semiconductor manufacturing process including a step of baking at a high temperature, It does not always provide sufficient performance.
  • the base polymer is an aromatic ring-containing polymer such as polyvinyl phenol or partially hydrogenated polyvinyl phenol. , The transmittance of short-wavelength activating radiation is not sufficient. Disclosure of the invention
  • An object of the present invention is to form a pattern having a high sensitivity and a high resolution with respect to short-wavelength activating radiation, a good cross-sectional shape, a good mask linearity, and a light exposure.
  • An object of the present invention is to provide a chemically amplified resist composition having excellent post-baking resistance and excellent storage stability.
  • the present inventors have conducted intensive studies to overcome the above-mentioned problems of the prior art. (1) Protecting the functional group that controls the solubility of the base polymer with an acid-labile group
  • the chemically amplified resist composition containing the polymer compound obtained above and (2) a photoacid generator has, as the polymer compound, a functional group which is decomposed by an acid to impart solubility to the acid.
  • a polymer compound (A) having a functional group which is decomposed by an acid to impart solubility, and has no aromatic ring is obtained by irradiation with activating radiation.
  • a compound (B) which generates an acid and an amine (C) having a molecular weight of 100 to 240 and a boiling point of 200 to 350 ° C at 760 mmHg. ) is provided.
  • the polymer compound (A) used in the present invention is a polymer compound having a functional group that is decomposed by an acid to impart alkali solubility and does not have an aromatic ring such as a benzene nucleus.
  • the high molecular compound having a functional group that is decomposed by an acid to impart alkali solubility generally refers to an alkali-soluble group of an alkali-soluble polymer that is not stable to an acid. It is a polymer protected by a group.
  • Examples of the functional group that is decomposed by an acid to impart alkanol solubility include t-butyl ester group and t-butyl carbonate described in Japanese Patent Publication No. 2-27660; Japanese Patent Publication No. 5 — 6 9 4 2 0 Tertiary alkyloxy group, t-aminoloxy group, t-aminoloxycarbonyl group, tertiary alkyloxy group, tertiary alkyloxycarbonyl group, tertiary alkyloxycarbonyloxy group; -Acetal structure described in Japanese Patent Application Laid-Open No. 4-3451; Ketal structure described in Japanese Unexamined Patent Application Publication No.
  • Substitutable 1-viranyl group; 3-oxocyclohexyl group Or 5—Me 3 Substitutable such as oxocyclohexyl group, etc.
  • Substitutable such as 3-oxocyclohexyl group; 3- (5-pentanoid) group, 3-methyl-5- (5-pentanoide) group 3 — (5 — pentanoide) group; 2 — methyl-1 2 — adamantyl group etc.
  • Substitutable 2 adamantyl group; cyclic ester-containing groups such as mevalonic crackon group Is exemplified. These groups may be directly bonded to the base polymer, or may be bonded via a divalent or higher valent organic group.
  • Such a polymer compound (A) include 2-substituted 2-norbornane-2-substituted methacrylate esters described in JP-A-5-80515.
  • a copolymer of an acrylate ester compound having a norpolnanone skeleton in the ester moiety and an adamantan skeleton in the ester moiety described in JP-A-5-257284 (Co) polymers of acrylate esters based on acrylates and acrylates having an adamantanone skeleton in the ester moiety described in JP-A-5-265212 Copolymers of lylic acids with tetrahydroviranyl ester, (meta) acrylic acid 3 —isolated as described in JP-A-5-346666 Copolymers having repeating units derived from hexyl hexyl, (1) a (meth) acrylate having a functional group decomposed by an acid, and (2) an alicyclic alkyl (met
  • a copolymer containing a structural unit derived from an alicyclic alkyl (meth) acrylate is preferable because it has excellent register properties.
  • the polymer compound (A) has a (meth) acrylate (a ⁇ ) having a functional group decomposed by an acid and an alicyclic alkyl (meth) acrylate (a The copolymer (A) with 2 ) is more preferable in order to achieve a high balance of resist properties.
  • the polymer (A) is a functional group that is decomposed by an acid.
  • the copolymer is a copolymer of methacrylate having a methacrylate and an alicyclic alkyl methacrylate.
  • a copolymer of a (meth) acrylate compound having a cyclic ester such as an amino acid structure and a (meta) acrylate compound having an adamantane skeleton in an ester portion is exemplified.
  • a (meth) acrylate having a functional group that can be decomposed by an acid where a ⁇ is (soil) is a nickel lactone (Meta) acrylates are preferred, (c) nick lactones are preferred, and alicyclic alkyl (meta) acrylates are preferred.
  • a ⁇ is (soil) is a nickel lactone (Meta) acrylates
  • nick lactones are preferred
  • alicyclic alkyl (meta) acrylates are preferred.
  • 2-methinolate 2-adamantyl (meta) acrylate is preferable, and 2-methylone 2-adamantyl methacrylate Is more preferred.
  • the polymer compound (A) is formed by co-polymerization of (Sat) -mevalonic crack methacrylate and 2—methyl-1-2—adamantyl methacrylate. Most preferably, they are united.
  • Such a copolymer is represented by the formula (1)
  • R 1 and R 2 each independently represent an alkyl group having 1 to 3 carbon atoms, m and n each represent a ratio of each repeating unit, and m: n is a molar ratio, usually 30: 70 to 70: 30; preferably 40: 60 to 60: 40, more preferably 45: 55 to 55: 45. ]
  • examples of the alkyl group having 1 to 3 carbon atoms include a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • Particularly preferred examples of the copolymer represented by the formula (1) include 2-methyl-2 -adamantyl methacrylate in which R 1 is a methyl group, and R 2 in a methyl group.
  • Certain (Sat) is a copolymer with nickel lactone methacrylate.
  • Such a copolymer is prepared, for example, by dissolving a monomer component in an organic solvent, adding a polymerization initiator such as azosobutyronitrile, and reacting at a reaction temperature of 40 to 150 ° C. It can be obtained by reacting for 1 to 24 hours. After the polymerization reaction, it can be optionally purified by a conventional method.
  • a polymerization initiator such as azosobutyronitrile
  • the weight average molecular weight (Mw) of the polymer compound (A) used in the present invention is not particularly limited, but is usually from 1,000 to 100,000, preferably More preferably, it is 2, 000 to 50,000, 0000, more preferably, 3, 000 to 20, 0, 000. If the weight average molecular weight of the high molecular compound (A) is too low, the resist film tends to be brittle and the heat resistance of the resist film tends to decrease. Conversely, if the weight average molecular weight is too high, There is a problem that the resist film becomes cloudy during coating.
  • the weight-average molecular weight / number-average molecular weight (MwZMn) of the polymer compound (A) used in the present invention is usually from 1.0 to 3.0, preferably from 1.0 to 2.5. Preferably it is between 1.0 and 2.0.
  • both the weight average molecular weight (M w) and the number average molecular weight (M n) were measured using a refractive index meter (RI) in gel solvent in tetrahydrofuran solvent. It is measured as a polystyrene equivalent value measured by chromatography.
  • the resist composition of the present invention contains the polymer compound (A) and a compound (B) that generates an acid upon irradiation with activating radiation (that is, a photoacid generator; PAG). It is a chemically amplified resist.
  • An acid is generated from the photoacid generator by the irradiation of the activating radiation, and the acid is used as a catalyst to remove the protecting group of the polymer compound (A) in a chain reaction, thereby improving the alkali solubility. I do.
  • the photoacid generator (B) used in the present invention is not particularly limited as long as it is a substance that generates brenstead acid or Louis acid when exposed to activating radiation.
  • Known compounds such as organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.
  • sodium salts include sodium salts such as diazonium salts, ammonium salts, diphenyl-donium triflate; sulfonates such as triphenylsulfonium triflate; Dimethyl salt; examples include phosphonium salt, arsonium salt, and oxonium salt.
  • halogenated organic compounds include halogen-containing oxazine-based compounds, halogen-containing triazine-based compounds, halogen-containing acetate-non-compounds, and halogen-containing benzophenone-containing compounds.
  • Compounds, halogen-containing sulfoxide compounds, halogen-containing sulfon compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, and halogen-containing triazoles Compounds, halogen-containing 2-pyrone compounds, other halogen-containing heterocyclic compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, sulfenylhalai Compounds.
  • examples of the halogenated organic compound include tris (2,3—dibromopropinole) phosphate and tris (2,3—jib-mouth).
  • B Propinolate) Phosphate, Tetrabromochlorobutane, Hexaclo benzene, Hexabromobenzene, Hexabuta Cyclododecane, Heki Micrododesen for sub mouth, Mobifenil for hex sub mouth, bisect phenyl alcohol, Tetraclo bis bisphenol A, Tetrablo bisphenol Bis (chloroethyl) ether of bisphenol A, bis (chloroethyl) ether of tetrachloro, bis (bromoethyl) ether of tetrabromobisphenol A, bisphenol -Nore A's screw (2,3 Pill) Ether, bisphenol A bis (2,3—dipropyl propyl) Ether, tetrachloride
  • quinone diazide compounds include 1,2—benzoquinone diazide 4—snolefonic acid ester and 1,2—naphthoquinone diazide.
  • 4-Sulfonate ester 1, 2-Naphthoquinone diazide 1-5-Sulfonate ester, 2, 1-Naphthoquinone diazide 4-Sulfonate Acid ester, 2,1—benzoquinonediazide-15-sulfonate of quinonediazide derivative such as sulfonate ester; 1,2-benzoquinodia 1-2-diazido 4-snorrephonic acid chloride, 1, 2-naphthoquinone 1-2-diazide 1-4-sulphonic acid chloride, 1, 2-naph Tokinon-1 2 — Diazide 5 — Sulfonic acid chloride, 1, 2 —Naphthoquinone 1 —Diazido 6 —
  • a, a' Examples of bis (sulfonyl) diazomethane compounds include unsubstituted, symmetrically or asymmetrically substituted alkyl, alkenyl, aralkyl, aromatic, and the like. And a, a'-bis (sulfonyl) diazomethane having a heterocyclic group.
  • Examples of a-carbonyl-unsulfonyldiazomethane compounds include unsubstituted, symmetrically or asymmetrically substituted alkyl, alkenyl, aralkyl, aromatic, And carbonyl- ⁇ -sulfoninoresizomethane having a heterocyclic group.
  • sulfone compound examples include a sulfone compound having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, or heterocyclic group. And disulfone compounds.
  • Examples of the organic acid ester include a carboxylic acid ester, a sulfonate, a phosphate and the like.
  • Examples of the organic acid amide include carboxylic acid amide, sulfonate amide, and phosphoric acid amide.
  • Examples of the organic acid imide include a carboxylic acid imide, a sulfonate imide, and a phosphoric acid imide.
  • the above-mentioned photoacid generator is also used for a KrF excimer laser resist, and among these, the wavelength near the ArF excimer laser (18) (5.5 to 220 nm), for example, the formula (2) disclosed in Japanese Patent Application Laid-Open No. R,
  • R. is a linear, branched or cyclic alkyl
  • R 3 is a linear, branched or cyclic alkyl group, a 2-oxo cyclic alkyl group, or a 2-oxo linear chain Joma other branched alkyl group
  • Y one is, BF, A s -, S b F 6 -, PF 6 -, CF 3 C 0 0 one, C 1 0 4 - or the CF 3 S 0 3 — And so on.
  • Y one is, BF, A s -, S b F 6 -, PF 6 -, CF 3 C 0 0 one, C 1 0 4 - or the CF 3 S 0 3 — And so on.
  • R 2 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group; Is a hydrogen atom, a straight-chain, branched or cyclic alkyl group, or a haloalkyl group represented by a benzoalkyl group such as trifluorophenol. ]
  • the compound represented by is preferred.
  • these compounds include, for example, cyclohexylmethyl (2-year-old cyclohexyl) sulfonium trifluorene snorrehonate, dicytamine Chromohexyl (2-oxocyclohexyl) sulfonium trifluorene snorehonate, 2-oxocyclohexyl (2-nonorebornyl) ) Sulfonium trifluorene methanol snorehonate, 2-cyclohexenoresinolenorhinolene cyclohexanone, dimethyl (2-year old ciscyclohexyl) Tri-Fol-Lo-Norme, Tri-Fenol Sulfonium, Tri-Fr-No-Sl Tri-no-re-no-me, sn-re-ho-na-to, N-Hydroxy-succin
  • photoacid generators (B) can be used alone or in combination of two or more.
  • the mixing ratio of the photoacid generator (B) is usually from 0.01 to 50 parts by weight, preferably from 0.2 to 30 parts by weight, per 100 parts by weight of the polymer compound (A). Parts by weight. If the proportion of the photoacid generator is too small, it is difficult to form a resist pattern. On the other hand, if the proportion is too large, development residue tends to be generated during development, and Problems such as the deterioration of the cross-sectional shape of the car.
  • the molecular weight is 100 to 240, preferably 120 to 220, more preferably 1 to 220. 40-200, boiling point at 720 mm Hg is 200-350. C, preferably using amines at 210-330 ° C.
  • the melting point of the amines is too large, the melting point generally tends to be high, so that when the resist composition (especially a solution of the resist composition) is stored, or when the resist film is developed with an alkaline developer.
  • amines tend to precipitate, and conversely, if they are too small, the boiling point will be low. If the boiling point of amines is too high, the molecular weight usually increases and the molecular structure becomes a bulky compound, so that diffusion in the resist film becomes insufficient and the surface becomes a hardly soluble layer. Pattern shape is reduced due to the influence of If the boiling point of the amines is too low, they will volatilize at the baking temperature at the time of pattern formation, and there is a tendency that a sufficient reforming effect cannot be obtained by the addition.
  • amines (C) include, for example, fats such as nonylamine, desilamine, tridecinoleamine, tetradecylamine, pentadecylamine, etc.
  • Aliphatic N-amimins such as Jamilamin
  • Aliphatic N-amimins such as Triptylamin and Triamilamin
  • 4-Aminobenzene Benzomin Aromatic amines such as amin, diphenylamine, tribenzylamine, and cycloaliphatic amines such as hexamethylentramine And the like.
  • aromatic amines such as diphenylamine and cycloaliphatic amines such as hexamethylenetetramine are preferred.
  • the mixing ratio of A Mi emissions such (C) is Soo Doo composition (A + B) with respect to 2 0 g, typically, 0. 0 0 IX 1 0 one 4 ⁇ 1 0 0 x 1 0 one 4 mol
  • Preferred Ku is 0. 0 1 x 1 0- 4 ⁇ 1 0 X 1 0 _ 4 mol.
  • Each component constituting the resist composition of the present invention is usually used by dissolving it in an organic solvent to form a resist film.
  • the proportion of the organic solvent used is such that the components constituting the resist composition are dissolved in a uniform amount.
  • the organic solvent is not particularly limited, and any of those generally used as a solvent for a resist composition can be used.
  • organic solvents e.g., acetone tons, main Chiruechiruke tons, which keto emissions such as shea click Ropen evening Bruno emissions, Kisano down to shea click b; n - flop 0 Bruno Lumpur, i -loop 0 Bruno Lumpur, n - butanoate Lumpur, i - butanoate Lumpur, t - butanoate one Honoré, shea click b to hexa Roh one Norre of any Anoreko one Honoré acids; E Ji les ring Li Koruji main Ethers such as ethyl alcohol, ethylene glycol, and dioxane; ethyl alcohol, methyl alcohol, ethylene glycol, ethyl alcohol, etc.
  • Alcohol ethers such as propylene monomethyl ether and propylene glycol monoether; propyl formate, butyrate, propyl acetate, butyl acetate, propionic acid Esters such as methyl, ethyl propionate, methyl butyrate, ethyl butyrate; methyl 2-oxypropionate, methyl 2-oxypropionate, methyl 2-methoxypropionate, 2 — Oxycarbonates such as methyl ethoxypropionate; cello sonolecetate, methyl cellosol acetate, solvent ethyl acetate, solvent sorbate acetate, solvent sorbase acetate, butyl cellulose, etc.
  • Cerro Solves Ternes: propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether Propylene glycols; ethylene glycol, methyl ether, diethyl alcohol methyl ether, diethyl alcohol methyl ether, diethyl glycol 1-Diethylenic alcohols such as rutile ether; Halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene N, N-dimethylformamide, N, N-dimethylinolacetamide, N-methylacetamide, N-methylpyro Polar solvents such as redox; and the like. These organic solvents can be used alone or in combination of two or more.
  • additives generally added to the resist composition can be added to the resist composition of the present invention, if necessary.
  • additives include, for example, silicone-based or fluorine-based surfactants, storage stabilizers, sensitizers, and striation inhibitor.
  • Compatible additives can be mentioned.
  • an acid generated from the photoacid generator (B) by the irradiation of the activating radiation acts on the developer of the high molecular compound (A) in the irradiated portion.
  • the solubility changes. That is, the protecting group in the functional group of the polymer compound (A) is removed by the catalytic action of the acid, and the polymer compound is converted into an alkali-soluble group. Therefore, the resist composition of the present invention acts as a post-type resist by using an alkaline developer.
  • the resolution can be improved by adding amines (C). Improves register characteristics such as properties, pattern shape, and maskability.
  • an alkali developer is usually used as a developer.
  • the alkali developer include, for example, aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium gayate, and ammonia; Aqueous solutions of primary amines such as pyramin; Aqueous solutions of secondary amines such as getylamine and dipropylamine; Tertiary amines such as trimethylammine and triethylamine Aqueous solutions of alcohols; aqueous solutions of alcohol amines such as getyl ethanolamine, triethanolamine, etc .; Labylammonium Hydroxide, Trimethyl Hydroxymethylide Ammonium Hydroxide, Triethyl Hydroxymethide A Nmoniu shuttleless Dorokishi de, such as an aqueous solution of Application Benefits main Chinorehi Doroki Shechirua Nmoniu shuttleless Doroki shea de of any quaternary A Nmoniu arm
  • a water-soluble organic solvent such as isopropanol, a surfactant, a resin dissolution inhibitor or the like can be preferably added, such as ethanol or ethylene glycol.
  • a resist composition solution is applied to a substrate by a method such as spin coating and dried, and dried to a desired film thickness (dry film thickness).
  • a resist film of about 0.01 / m to 2 ⁇ m) is formed.
  • This resist film is subjected to butter exposure using activating radiation.
  • activating radiation a short wavelength of 190 to 250 nm, such as a deep ultraviolet ray, a KrF excimer laser, an ArF excimer laser, etc. Light sources can be used.
  • a temperature within a range where the resist film is not deteriorated by heat usually 80 to 190 ° C, preferably 100 to 170 ° C
  • Prebaking at ° C is preferred. If the pre-bake temperature is lower than this range, a hardly soluble layer is likely to be generated on the surface, and if the pre-bake temperature is higher, thermosetting or thermal decomposition may occur. I don't like it.
  • a post-exposure bake is usually performed.
  • the post-exposure bake temperature is usually 70 to 18 ° C. In order to develop the resist film after the exposure, the above-described developer may be used.
  • the methods for evaluating the physical properties and register characteristics of the polymer compound are as follows.
  • Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) in tetrahydrofuran solvent using a refractometer (RI). ) Is the Polystyrene conversion value measured by).
  • the measurement conditions are as follows.
  • composition ratio of the copolymer is a value measured by an ifi-NMR spectrum.
  • the minimum line size (unit: ⁇ m) where the line width of the line and space (hereinafter abbreviated as L & S) and the space width pass equally And
  • the exposure amount (unit: mJ / cm 2 ) when the above-mentioned resolution was obtained was defined as the sensitivity.
  • the resist film is exposed at an exposure amount such that the L & S line width and space width of 0.2 ⁇ m pass through at the same length, and then the exposure starts from the 0.1 m L & S.
  • the actual dimensions of the 25 ⁇ m L & S were measured with a length-measuring SEM, and how much the dimensions differed from the mask dimensions was measured. If the difference is less than 10% of the mask dimension, it is judged that there is mask linearity ("Yes" in the table), and if it is more than 10%, there is no mask linearity. ("None" in the table).
  • the resist composition solution is stored at room temperature for 6 months from the date of manufacture, and after 6 months, the resist composition solution is applied on a silicon wafer substrate, and a dust inspection device (silicon wafer surface) is applied.
  • a dust inspection device silicon wafer surface
  • Those with less than 50 particles were evaluated as having good storage stability ("good” in the table), and those with 50 or more particles were evaluated as having poor storage stability ("bad” in the table). .
  • MLMA mevalonic lactone methacrylate
  • 2MAdMA 2-methyl-12-adamantyl methacrylate copo
  • the chemically amplified resist composition to which the amine having a molecular weight of 100 to 240 and a boiling point of 200 to 350 ° C is added is an ArF ferrite.
  • Exposure with a single laser beam (193 nm wavelength) provides excellent resolution and It showed a pattern shape and maskability, and was found to be excellent in sensitivity, PED resistance, storage stability, etc.
  • a mask having high sensitivity, high resolution, and a good cross-sectional shape can be formed with respect to short-wavelength activating radiation such as an ArF excimer laser beam, and a mask can be formed.
  • a chemically amplified resist composition having good linearity, excellent PED resistance, and excellent storage stability is provided.
  • the resist composition of the present invention is useful when manufacturing semiconductor elements such as ICs and LSIs, liquid crystal display substrates, print substrates, and the like by lithography technology, It is suitable for a semiconductor element manufacturing process that requires pattern formation.

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention porte sur une composition d'agent de réserve comprenant: (A) un composé de poids moléculaire élevé présentant au moins un groupe fonctionnel décomposé par un acide pour lui donner une solubilité alcaline et exempt de cycles aromatiques; (B) un composé produisant un acide lorsqu'on le soumet à un rayonnement actinique; et (C) une amine d'un poids moléculaire compris entre 100 et 240, et dont le point d'ébullition sous 760 mmHg est compris entre 200 et 350 °C.
PCT/JP1998/000705 1997-02-20 1998-02-20 Composition d'un agent de reserve WO1998037458A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/52251 1997-02-20
JP5225197 1997-02-20

Publications (1)

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WO1998037458A1 true WO1998037458A1 (fr) 1998-08-27

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PCT/JP1998/000705 WO1998037458A1 (fr) 1997-02-20 1998-02-20 Composition d'un agent de reserve

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WO (1) WO1998037458A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6699635B1 (en) * 1998-12-24 2004-03-02 Fuji Photo Film Co., Ltd. Positive photosensitive composition
US6743564B2 (en) 2000-12-07 2004-06-01 Shin-Etsu Chemical Co., Ltd. Amine compounds, resist compositions and patterning process
US6749988B2 (en) 2000-11-29 2004-06-15 Shin-Etsu Chemical Co., Ltd. Amine compounds, resist compositions and patterning process
US7084303B2 (en) 2001-04-23 2006-08-01 Shin-Etsu Chemical Co., Ltd. Tertiary amine compounds having an ester structure and processes for preparing same
JP5220253B2 (ja) * 1999-10-27 2013-06-26 株式会社ダイセル アダマンチル（メタ）アクリレート類の製造法
EP2615176A1 (fr) 2012-01-11 2013-07-17 Paul-Ehrlich-Institut Bundesamt für Sera und Impfstoffe Nouvelles particules de lentivirus pseudotypées et leur utilisation dans la transduction ciblée in vitro de cellules souches embryonnaires humaines pluripotentes indifférenciées et cellules souches pluripotentes induites

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JPH0580515A (ja) * 1991-09-19 1993-04-02 Fujitsu Ltd レジスト組成物とレジストパターンの形成方法
JPH05127369A (ja) * 1991-10-31 1993-05-25 Nec Corp レジスト材料
JPH05249662A (ja) * 1991-10-17 1993-09-28 Shipley Co Inc 放射感受性の組成物及び方法
JPH05346668A (ja) * 1992-06-16 1993-12-27 Fujitsu Ltd レジスト組成物及びそれを用いたパターン形成方法
JPH07191463A (ja) * 1993-12-27 1995-07-28 Fujitsu Ltd レジストおよびこれを使った半導体装置の製造方法
JPH07252324A (ja) * 1994-01-31 1995-10-03 Nec Corp ビニル基を含有する単量体及びその重合体及びそれを用いた感光性樹脂組成物
JPH08305023A (ja) * 1995-04-28 1996-11-22 Fujitsu Ltd レジスト材料及びレジストパターンの形成方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0580515A (ja) * 1991-09-19 1993-04-02 Fujitsu Ltd レジスト組成物とレジストパターンの形成方法
JPH05249662A (ja) * 1991-10-17 1993-09-28 Shipley Co Inc 放射感受性の組成物及び方法
JPH05127369A (ja) * 1991-10-31 1993-05-25 Nec Corp レジスト材料
JPH05346668A (ja) * 1992-06-16 1993-12-27 Fujitsu Ltd レジスト組成物及びそれを用いたパターン形成方法
JPH07191463A (ja) * 1993-12-27 1995-07-28 Fujitsu Ltd レジストおよびこれを使った半導体装置の製造方法
JPH07252324A (ja) * 1994-01-31 1995-10-03 Nec Corp ビニル基を含有する単量体及びその重合体及びそれを用いた感光性樹脂組成物
JPH08305023A (ja) * 1995-04-28 1996-11-22 Fujitsu Ltd レジスト材料及びレジストパターンの形成方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6699635B1 (en) * 1998-12-24 2004-03-02 Fuji Photo Film Co., Ltd. Positive photosensitive composition
JP5220253B2 (ja) * 1999-10-27 2013-06-26 株式会社ダイセル アダマンチル（メタ）アクリレート類の製造法
US6749988B2 (en) 2000-11-29 2004-06-15 Shin-Etsu Chemical Co., Ltd. Amine compounds, resist compositions and patterning process
US6743564B2 (en) 2000-12-07 2004-06-01 Shin-Etsu Chemical Co., Ltd. Amine compounds, resist compositions and patterning process
US7084303B2 (en) 2001-04-23 2006-08-01 Shin-Etsu Chemical Co., Ltd. Tertiary amine compounds having an ester structure and processes for preparing same
US7378548B2 (en) 2001-04-23 2008-05-27 Shin-Etsu Chemical Co., Ltd. Tertiary amine compounds having an ester structure and processes for preparing the same
EP2615176A1 (fr) 2012-01-11 2013-07-17 Paul-Ehrlich-Institut Bundesamt für Sera und Impfstoffe Nouvelles particules de lentivirus pseudotypées et leur utilisation dans la transduction ciblée in vitro de cellules souches embryonnaires humaines pluripotentes indifférenciées et cellules souches pluripotentes induites
WO2013104728A1 (fr) 2012-01-11 2013-07-18 Paul-Ehrlich-Institut Bundesamt Für Sera Und Impfstoffe Nouvelles particules lentivirales pseudotypées et application associée dans la transduction ciblée in vitro de cellules souches embryonnaires humaines pluripotentes et de cellules souches pluripotentes induites indifférenciées

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