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CN-121995692-A - KrF photoresist composition and preparation method thereof

CN121995692ACN 121995692 ACN121995692 ACN 121995692ACN-121995692-A

Abstract

The invention relates to the technical field of photoresist, and particularly discloses a KrF photoresist composition and a preparation method thereof. The KrF photoresist composition comprises KrF resin, organic base, surfactant, photoacid generator and organic solvent, wherein the KrF resin is prepared by copolymerizing four monomers with a structural general formula of A-D, and the preparation method comprises the following steps of uniformly mixing the KrF resin, the organic base, the surfactant, the photoacid generator and the organic solvent in a nitrogen atmosphere according to a proportion to obtain the KrF photoresist composition. The KrF photoresist composition has the advantages of high photosensitivity and high resolution.

Inventors

  • Tian Rubo
  • WANG FEI
  • YANG JIE
  • HAN SHAOPENG
  • YANG WENGUANG
  • ZHU SHIYU

Assignees

  • 万华化学集团股份有限公司

Dates

Publication Date
20260508
Application Date
20241104

Claims (10)

  1. 1. A KrF photoresist composition, comprising the following components in mass percent: 5% -50%, preferably 10% -30% of KrF resin; 0.01-10%, preferably 0.05-5% of organic base; 0.01-10%, preferably 0.1-5% of surfactant; 0.1-15%, preferably 0.5-5% of photoacid generator; 15-90%, preferably 55-85% of organic solvent.
  2. 2. The KrF photoresist composition according to claim 1, wherein the KrF resin is obtained by copolymerizing monomers having the general formulas a to D: Wherein R 1 ～R 11 is independently selected from H or C1-C20 straight-chain or branched-chain alkyl or naphthene base, C1-C20 hydroxy-substituted alkyl, C1-C20 halogen-substituted alkyl, preferably R 1 ～R 11 is independently selected from H or C1-C8 straight-chain or branched-chain alkyl or naphthene base, C1-C8 hydroxy-substituted alkyl, C1-C8 halogen-substituted alkyl.
  3. 3. The KrF resin according to claim 2, wherein the molar ratio of the monomers A to D is 1 (4 to 8): 1 to 3): 0.5 to 1.
  4. 4. The KrF photoresist composition according to claim 2, wherein the KrF resin has a molecular weight of 5000 to 30000, preferably a molecular weight of 8000 to 15000.
  5. 5. The KrF photoresist composition according to claim 1, wherein the surfactant is selected from one or more of fluorine-based surfactant, silicon-based surfactant, nonionic surfactant, preferably selected from one or more of ammonium perfluorooctanoate, ammonium perfluorooctylsulfonate, ammonium perfluorohexanoate, cetyl trimethyl siloxane, methyltriethoxysilane, vinyltriethoxysilane, γ -aminopropyl triethoxysilane, phenyltriethoxysilane, polyethylene glycol octylphenyl ether, polyethylene glycol dodecyl ether, polyethylene glycol octyl ether, polyethylene glycol stearate, polyethylene glycol laurate, sorbitan monooleate, polyvinylpyrrolidone, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether.
  6. 6. The KrF photoresist composition according to claim 1, wherein the organic base is selected from one or more of tripropylamine, tributylamine, triisobutylamine, trioctylamine, triethanolamine, triethoxy ethanolamine, trimethoxymethoxy ethyl amine, tetramethyl ammonium hydroxide.
  7. 7. The KrF photoresist composition according to claim 1, wherein the photoacid generator is selected from one or more of onium salts, triazines, sulfonyldiazomethane, oxime esters, nitrobenzyl sulfonate esters, preferably perfluorobutyltriphenylsulfonium salt, trifluoromethyltriphenylsulfonium salt, o-trifluoromethyltriphenylsulfonium salt, p-trifluoromethyltriphenylsulfonium salt, perfluorobutyldiphenyliodonium salt, trifluoromethyldiphenyliodonium salt, o-trifluoromethyldiphenyliodonium salt, p-trifluoromethyldiphenyliodonium salt, bis (4-tert-butylphenyl) iodocamphorsulfonate, bis (4-tert-butylphenyl) iodotrimethylacetophenone, trichloroacetophenone, tribromomethylphenyl sulfone, 4-phenoxydichloroacetophenone, 4, 6-bis (trichloromethyl) -1,3,5 triazine, α -bis (arylsulfonyl) diazomethane, α -carbonyl- α -sulfonyldiazomethane, N-trifluoromethylsulfonyl-phthalimide, N-phthaloyl succinimide, α -phenylsulfinyl-8-phenylsulfinate, α -phenylsulfonium or more preferably from among α -trifluoromethylsulfonyl sulfonium salts, α -phenylsulfonium salts, and more preferably from among α -phenylsulfonium salts, p-trifluoromethylsulfonyl sulfonium salts, α -bis (tert-butylsulfonium salts, and α -phenylsulfonium salts.
  8. 8. The KrF photoresist composition according to claim 1, wherein the organic solvent is selected from one or more of ketone solvents, polyols, alkyl ethers, alkyl ester solvents, amide solvents, preferably one or more of acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monobutyl ether, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone, more preferably one or more of diethylene glycol methyl ether, propylene glycol monomethyl ether, ethyl lactate.
  9. 9. The method for preparing the KrF photoresist composition according to any of claims 1-8, comprising the steps of uniformly mixing KrF resin, organic base, surfactant, photoacid generator and organic solvent in proportion under nitrogen atmosphere, and filtering to obtain a photoresist mixture.
  10. 10. The method according to claim 9, wherein the filtration is performed with a filtration accuracy of 0.1-2 μm, preferably 0.1-0.5 μm.

Description

KrF photoresist composition and preparation method thereof Technical Field The invention belongs to the technical field of photoresist, and particularly relates to a KrF photoresist composition and a preparation method thereof. Background Photolithography and etching are one of the key process technologies for semiconductor chip fabrication, and photoresist is the core material in modern semiconductor chip photolithography processes. In the process of manufacturing the semiconductor chip, a mask pattern is projected onto photoresist by utilizing a light source with specific wavelength of an exposure machine, the photoresist undergoes photochemical reaction, and then the required photoetching pattern is finally obtained through a baking process and set developing conditions. In the semiconductor process, photoresist is used as a process mask layer, and the quality of the formed pattern and the quality of the physical and chemical properties of the film play a key role in the subsequent process and directly influence the device performance of the chip. However, the conventional photoresist material may have problems of limited resolution or insufficient photosensitive performance at high resolution. Therefore, based on the urgent need for higher resolution and higher performance microelectronic devices, it is important to find a photoresist resin and photoresist composition having high resolution and high sensitivity. Disclosure of Invention Aiming at the defect that the photoresist resin in the prior art has insufficient photosensitivity and resolution, the invention provides a KrF photoresist composition capable of improving photosensitivity and resolution and a preparation method thereof. In order to achieve the above object, the present invention has the following technical scheme: In a first aspect, the present invention provides a KrF photoresist composition comprising, by mass: 5% -50%, preferably 10% -30% of KrF resin; 0.01-10%, preferably 0.05-5% of organic base; 0.01-10%, preferably 0.1-5% of surfactant; 0.1-15%, preferably 0.5-5% of photoacid generator; 15-90%, preferably 55-85% of organic solvent. In the invention, the KrF resin is obtained by copolymerizing monomers with the general formulas A-D: Wherein R 1～R11 is independently selected from H, C1-C20 straight-chain or branched alkyl or naphthene base, C1-C20 hydroxy substituted alkyl, C1-C20 halogen substituted alkyl; preferably, R 1～R11 is independently selected from H or C1-C8 straight or branched chain alkyl or cycloalkyl, C1-C8 hydroxy substituted alkyl, C1-C8 halogen substituted alkyl. More preferably, R 1～R11 is independently selected from H, C1-C6 straight or branched chain alkyl or cycloalkyl, C1-C3 hydroxy substituted alkyl. In the invention, the molar ratio of the monomers A to D is 1 (4 to 8): (1 to 3): (0.5 to 1). In the present invention, the copolymerization method used for the KrF resin is radical polymerization, and is prepared by the method of patent US2008/0193878 A1. In the present invention, the molecular weight of the KrF resin is 5000 to 30000, preferably 8000 to 15000. In the invention, the surfactant is selected from one or more of fluorine-based surfactants, silicon-based surfactants and nonionic surfactants, preferably selected from one or more of ammonium perfluorooctanoate, ammonium perfluorooctylsulfonate, ammonium perfluorohexanoate, hexadecyltrimethyl siloxane, methyltriethoxysilane, vinyltriethoxysilane, gamma-aminopropyl triethoxysilane, phenyltriethoxysilane, polyethylene glycol octylphenyl ether, polyethylene glycol dodecyl ether, polyethylene glycol octyl ether, polyethylene glycol stearate, polyethylene glycol laurate, sorbitan monooleate, polyvinylpyrrolidone, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether and polyethylene glycol monopropyl ether. In the invention, the organic base is selected from one or more of tripropylamine, tributylamine, triisobutylamine, trioctylamine, triethanolamine, triethoxy ethanolamine, trimethoxymethoxy ethylamine and tetramethyl ammonium hydroxide. In the present invention, the photoacid generator is selected from one or more of onium salts, triazines, sulfonyldiazomethane, oxime esters, nitrobenzyl sulfonate esters, preferably selected from perfluorobutyl triphenylsulfonium salt, trifluoromethyl triphenylsulfonium salt, o-trifluoromethyltrimethylsulfonium salt, p-trifluoromethyltrimethylsulfonium salt, perfluorobutyl diphenyliodonium salt, trifluoromethyl diphenyliodonium salt, o-trifluoromethyldiphenyliodonium salt, p-trifluoromethyldiphenyliodonium salt, bis (4-t-butylphenyl) iodocamphorsulfonate, bis (4-t-butylphenyl) iodotrifluoromethanesulfonate, trichloroacetophenone, tribromomethylphenyl sulfone, 4-phenoxydichloroacetophenone, 4, 6-bis (trichloromethyl) -1,3,5 triazine, alpha, one or more of α -bis (arylsulfonyl) diazomethane, α -carbonyl- α -sulfonyldiazomethane, N-trifluoromethylsulfonyloxy phthalimide, N-trifluoromethylsulfonyloxy-1, 8-na