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CN-121978865-A - Negative development photoresist composition containing hydrophobic resin, preparation method and application thereof

CN121978865ACN 121978865 ACN121978865 ACN 121978865ACN-121978865-A

Abstract

The invention relates to a negative development photoresist containing hydrophobic resin, a preparation method and application thereof. The photoresist composition containing the hydrophobic resin can form a protective layer from the hydrophobic resin to the surface of a film during film formation. The photoresist film formed by the photoresist composition has low surface energy, high receding contact angle (such as more than or equal to 85 degrees), low sliding angle (such as less than 15 degrees) and advancing contact angle of not more than 100 degrees, and is beneficial to reducing exposure defects and improving exposure efficiency.

Inventors

  • XU JIAN
  • GAO JIAXING
  • Zhuang Guanming
  • DONG WENJUN
  • WANG KUNMING
  • GU PENG

Assignees

  • 国科天骥(山东)新材料有限责任公司

Dates

Publication Date
20260505
Application Date
20251226

Claims (10)

  1. 1. A photoresist composition comprising a hydrophobic resin comprising a repeating unit represented by the following formula (a) and formula (B); ; wherein m and n are the same or different and are each independently 1 or 2; R 1 is unsubstituted, optionally substituted by one or two R 2 , C 1-12 alkylene, oxaC 1-12 alkylene or thiaC 1-12 alkylene; R 3 is unsubstituted, optionally substituted by one or two R 4 , C 1-12 alkylene, oxaC 1-12 alkylene or thiaC 1-12 alkylene; R 2 is C 1-12 perfluoro substituted alkyl; R 4 is C 1-12 alkyl; a is the mole fraction of repeating units (A) to total repeating units, B is the mole fraction of repeating units (B) to total repeating units, a is 0.01-0.3, and B is 0.7-0.99.
  2. 2. The photoresist composition of claim 1, wherein m is 1; Preferably, n is 1.
  3. 3. The photoresist composition of claim 1 or 2, wherein R 1 ,R 3 , the same or different, are independently of each other C 1-6 alkylene, oxac 1-6 alkylene, or thiac 1-6 alkylene; Preferably, R 1 ,R 3 , identical or different, are, independently of one another, C 1-3 alkylene, oxaC 1-5 alkylene or thiaC 1-5 alkylene; also preferably, R 1 ,R 3 are the same or different and are independently methylene, ethylene, propylene 、-CH 2 -O-、-CH 2 -O-CH 2 -、-O-CH 2 CH 2 -、-CH 2 CH 2 -O-CH 2 -、-C 3 H 6 -O-、-C 3 H 6 -O-CH 2 -、-CH 2 -S-、-CH 2 -S-CH 2 -、-S-CH 2 CH 2 -、-CH 2 CH 2 -S-CH 2 -、-C 3 H 6 -S-、-C 3 H 6 -S-CH 2 -.
  4. 4. The photoresist composition of any of claims 1-3, wherein R 2 is perfluoro substituted C 1-10 alkyl; Preferably, R 2 is perfluoro substituted C 3-8 alkyl; preferably, R 2 is perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl or perfluorooctyl.
  5. 5. The photoresist composition of any of claims 1-4, wherein R 4 is C 3-10 alkyl; Preferably, R 4 is propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl or 1, 2-dimethylbutyl; Preferably, a is 0.03-0.25 or 0.05-0.20, or 0.08-0.15; Preferably, b is 0.75-0.97 or 0.8-0.95, or 0.85-0.93; Preferably, the weight average molecular weight Mw of the hydrophobic resin is 3000-10000; Preferably, the hydrophobic resin has a molecular weight distribution index PDI of 1.5 to 3.0.
  6. 6. The photoresist composition of any one of claims 1-5, wherein the hydrophobic resin is prepared by an epoxy ring-opening copolymerization reaction comprising a monomer represented by formula (I) below and a monomer represented by formula (II); Wherein R 1 、R 2 、R 3 、R 4 , m and n have the definition as defined in any one of claims 1 to 5.
  7. 7. The photoresist composition of any one of claims 1-6, wherein the photoresist composition further comprises a film forming resin; preferably, the film-forming resin is selected from at least one of the following polymers P-1, P-2, P-3, P-4 or P-5; preferably, the polymer P-1 comprises 4 repeating units: Preferably, the polymer P-2 comprises 3 repeating units: preferably, the polymer P-3 comprises 3 repeating units: Preferably, the polymer P-4 comprises 4 repeating units: ; preferably, the polymer P-5 comprises 5 repeating units: ; Wherein the subscript of each repeating unit indicates the mole fraction of that repeating unit relative to the total repeating units of the polymer; preferably, the photoresist composition further comprises a solvent; Preferably, the solvent is at least one selected from propylene glycol methyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether, cyclohexanone, butyl acetate, gamma-butyrolactone and methyl isobutyl ketone; preferably, the photoresist composition further comprises a photoacid generator; Preferably, the photoacid generator is selected from sulfonium salt ion acid generators, such as one or two selected from PAG-1 to PAG-13: ; ; ; Preferably, the photoresist composition further comprises a photo-decomposable base; Preferably, the photo-decomposable base is selected from one or two of PDB-1 to PDB-8: 。
  8. 8. a hydrophobic resin, wherein the hydrophobic resin comprises a repeating unit represented by the formula (a) and the formula (B) as set forth in claim 1.
  9. 9. A patterned film formed using the photoresist composition of any one of claims 1-7.
  10. 10. A patterned substrate, wherein a pattern on the patterned substrate is formed by the photoresist composition of any one of claims 1-7.

Description

Negative development photoresist composition containing hydrophobic resin, preparation method and application thereof Technical Field The invention relates to the technical field of photoresist materials, in particular to an NTD photoresist containing hydrophobic resin, a preparation method and application thereof. Background With the continuous development of semiconductor technology, the lithography technology is advancing to a higher resolution and smaller line width. NTD (Negative Tone Development, negative tone) photoresists are gaining wide attention for their advantages in micro-nano patterning. In the immersion lithography process, the protective coating of the photoresist needs to be self-separated to the surface layer of the photoresist, and meanwhile, the protective coating has excellent hydrophobicity and film forming property, so that moisture invasion and photoresist component dissolution during liquid immersion exposure are avoided, and the quality of developed patterns is ensured. The fluorine-containing polymer has excellent hydrophobicity due to strong electronegativity and low surface energy of fluorine atoms, and is an ideal material for preparing photoresist protective coatings. In the prior art, hydrophobic resins are mostly based on acrylate or olefin backbones, and hydrophobicity is realized by introducing fluorinated side chains, but the structure is highly similar to the components of photoresist film-forming resins, and is not beneficial to self-separation. The epoxy polymer is widely used for a surfactant, has good film forming property and chemical stability, and can be used for preparing resin with hydrophobicity and film forming property by introducing fluorinated side chains through epoxy ring opening polymerization, but the research on fluorine-containing epoxy copolymer resin special for NTD photoresist is less at present, and the structural design of the existing fluorine-containing epoxy resin is difficult to simultaneously meet the requirements of high hydrophobicity, good film forming property and photoetching pattern precision. Therefore, the hydrophobic resin based on epoxy ring-opening copolymerization, controllable structure and excellent performance is developed, and has important significance for improving the performance of the NTD photoresist. Disclosure of Invention The invention aims to provide an NTD photoresist composition containing hydrophobic resin, and a preparation method and application thereof. The hydrophobic resin has excellent hydrophobicity, film forming property and chemical stability, and can realize a receding contact angle of more than 85 degrees and a sliding angle of less than 15 degrees, thereby reducing the defects of photoresist and improving the exposure efficiency during photoetching. In order to achieve the above purpose, the invention adopts the following technical scheme: A photoresist composition comprising a hydrophobic resin comprising a repeating unit represented by the following formula (a) and formula (B); wherein m and n are the same or different and are each independently 1 or 2; R 1 is unsubstituted, optionally substituted by one or two R 2, C 1-12 alkylene, oxaC 1-12 alkylene or thiaC 1-12 alkylene; R 3 is unsubstituted, optionally substituted by one or two R 4, C 1-12 alkylene, oxaC 1-12 alkylene or thiaC 1-12 alkylene; R 2 is C 1-12 perfluoro substituted alkyl; R 4 is C 1-12 alkyl; a is the mole fraction of repeating units (A) to total repeating units, B is the mole fraction of repeating units (B) to total repeating units, a is 0.01-0.3, and B is 0.7-0.99. According to an embodiment of the invention, m is 1. According to an embodiment of the invention, n is 1. According to an embodiment of the invention, R 1,R3, identical or different, are, independently of one another, C 1-6 alkylene, oxaC 1-6 alkylene or thiaC 1-6 alkylene. According to an embodiment of the invention, R 1,R3, identical or different, are, independently of one another, C 1-3 alkylene, oxaC 1-5 alkylene or thiaC 1-5 alkylene. For example, R 1,R3 are identical or different and are each independently methylene, ethylene, propylene 、-CH2-O-、-CH2-O-CH2-、-O-CH2CH2-、-CH2CH2-O-CH2-、-C3H6-O-、-C3H6-O-CH2-、-CH2-S-、-CH2-S-CH2-、-S-CH2CH2-、-CH2CH2-S-CH2-、-C3H6-S-、-C3H6-S-CH2-; In some embodiments of the invention, R 1 is selected from methylene, ethylene, propylene, -CH 2-O-CH2 -, or-CH 2CH2-O-CH2 -. In some embodiments of the invention, R 3 is selected from the group consisting of methyleneoxy, ethyleneoxy, -CH 2-O-CH2 -, or-CH 2CH2-O-CH2 -. According to an embodiment of the invention, R 2 is a perfluoro substituted C 1-10 alkyl, for example perfluoro substituted C 3-8 alkyl, for example perfluoropropyl [ e.g. CF 3CF2CF2-、(CF3)2 FC- ], perfluorobutyl [ e.g. CF3CF2CF2CF2-、(CF3CF2)(CF3)FC-、(CF3)3C-)]、 perfluoropentyl, perfluorohexyl or perfluorooctyl. According to an embodiment of the invention, R 4 is C 3-10 alkyl, for example propyl, butyl, pentyl, hexyl, isopropyl, i