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CN-115981100-B - Hydrofluoric acid-resistant protective material for lithography and lithography process thereof

CN115981100BCN 115981100 BCN115981100 BCN 115981100BCN-115981100-B

Abstract

The application discloses a hydrofluoric acid-resistant protective material for photoetching and a photoetching process thereof, which are prepared by self-making high-performance phenolic resin with narrow molecular weight distribution, and the material obtained by mixing the high-performance phenolic resin with a ring-shaped structure compound, an additive and a solvent in a system has moderate viscosity, strong adhesive force with a substrate to be etched, good leveling property and excellent hydrofluoric acid etching resistance, and can protect glass. In addition, the obtained hydrofluoric acid-resistant protective material for lithography has good uniformity, and can effectively reduce the occurrence of collapse defects in the lithography process. The hydrofluoric acid-resistant protective material for lithography, which is obtained by the application, is used for positive photoresist, has excellent high heat resistance, can be used for a production flow with a high-temperature process, can form good pattern morphology in an exposure process, has good contrast, and has high sensitivity and resolution.

Inventors

  • Tang Bangwen
  • SU XIAOMING

Assignees

  • 武汉梵佳鑫科技有限公司

Dates

Publication Date
20260512
Application Date
20220811

Claims (9)

  1. 1. The hydrofluoric acid-resistant protective material for lithography is characterized by comprising, by weight, 10-40% of resin, 10-20% of a cyclic structure compound, 50-90% of a solvent and 1-3% of an auxiliary agent; The resin is modified phenolic resin; the preparation method of the modified phenolic resin specifically comprises the following steps: s1, adding 10 parts by weight of first monohydroxy cresol, 5-15 parts by weight of formaldehyde and 0.03-0.07 part by weight of catalyst into water for reaction, and adding a neutralizer for neutralization; S2, continuously adding 8 parts by weight of second monohydroxy cresol, 5-15 parts by weight of formaldehyde, 0.01-0.04 part by weight of catalyst and 3-10 parts by weight of 2-hydroxy-1-hydroxymethyl naphthalene into the product obtained in the S1, and heating to 70-85 ℃ for reaction for 1-2.5 hours; S3, continuously adding 2-7 parts by weight of polyhydroxy phenol and 2-8 parts by weight of 4,4' -dihydroxydiphenyl ether into the product obtained in the S2, and heating to 80-95 ℃ for reaction for 3-5 hours; S4, washing the product obtained in the step S3, separating out a water phase, and then drying at 40-70 ℃ to obtain the product.
  2. 2. The hydrofluoric acid resistant protective material for lithography according to claim 1, wherein the catalyst in S1, S2 is at least one selected from the group consisting of p-toluene sulfonic acid, oxalic acid, hydrochloric acid, sulfuric acid, succinic acid, dodecylbenzene sulfonic acid.
  3. 3. The hydrofluoric acid resistant protective material for lithography according to claim 1, wherein the catalysts in S1, S2 are oxalic acid and dodecylbenzene sulfonic acid; The volume ratio of oxalic acid to dodecylbenzene sulfonic acid is 1 (0.7-2).
  4. 4. The hydrofluoric acid resistant protective material for lithography of claim 1, wherein the polyhydric phenol in S3 is selected from at least one of 2-methyl resorcinol, 2, 5-dimethyl resorcinol, 1, 3-resorcinol, 1, 4-hydroquinone, 2, 6-dimethyl hydroquinone, 4-methyl resorcinol, 4, 5-dimethyl resorcinol.
  5. 5. The hydrofluoric acid resistant protective material for lithography according to claim 1, wherein the cyclic structure compound is selected from at least one of 2-diazonium-1-naphthoquinone-4-sulfonate, 2-diazonium-1-naphthoquinone-5-sulfonate, N-hydroxynaphthalimide triflate, 5- [ N- (t-butoxyformyl) amino ] -1, 3-trimethyl-6 ' -nitroindoline spiropyran, 1- (2-hydroxyethyl) -3, 3-dimethylindoline-6 ' -nitrobenzospiropyran, 1, 3-trimethyl-3H-indoline spironaphthoxazine, 1, 3-trimethyl-9 ' -benzoyloxy-indoline spironaphthoxazine, 2' -bipyridine, 4' -bipyridine, triphenylsulfonium perfluorobutylsulfonate, triphenylsulfonium triflate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate.
  6. 6. The hydrofluoric acid resistant protective material for lithography according to claim 5, wherein the cyclic structure compound is N-hydroxynaphthalimide triflate and di (4-t-butylphenyl) iodonium p-toluenesulfonate; The mass ratio of the N-hydroxynaphthalene dicarboximide trifluoro-methanesulfonate to the di (4-tert-butylphenyl) iodonium p-toluenesulfonate is 1 (1-2).
  7. 7. The hydrofluoric acid resistant protective material for lithography of claim 1, wherein the auxiliary agent comprises at least one of a cross-linking agent, an adhesion promoter, and a tackifier.
  8. 8. A hydrofluoric acid resistant protective material for use in lithography according to claim 1, wherein the auxiliary agent comprises a cross-linking agent, an adhesion promoter; The adhesion promoter is at least one selected from melamine resin, fluorine-containing surfactant, coupling agent and polymethyl vinyl ether.
  9. 9. A lithographic process comprising the steps of: (1) Coating the hydrofluoric acid-resistant protective material for lithography on the surface of a material to be subjected to lithography according to any one of claims 1-8, heating in a tunnel furnace, and drying; (2) Aligning the material obtained in the step (1), and performing exposure treatment; (3) Spraying or immersing the material obtained in the step (2) into a developing solution for developing treatment; (4) Heating the material obtained in the step (3) to carry out hardening treatment; (5) Spraying or immersing the material obtained in the step (4) into a photoresist stripping solution for photoresist stripping treatment.

Description

Hydrofluoric acid-resistant protective material for lithography and lithography process thereof Technical Field The invention relates to the field of photoresist preparation, and in particular relates to a hydrofluoric acid-resistant protective material for photoetching and a photoetching process thereof. Background Glass is widely used in photolithographic substrates for its particular electroosmotic and optical properties and its weak fluorescent background interference. The surface modification is carried out, and the etching is carried out by utilizing hydrofluoric acid and mixtures thereof, so that photoetching and etching can be easily carried out on a silicon wafer, and micro concave-convex is formed on the surface of glass, thus forming chips with required patterns and the like. The glass silicon wafer surface is coated with positive photoresist, so that the resolution is high, the step coverage is good, the contrast is good, the substrate surface can be effectively protected, but the heat resistance and the hydrofluoric acid resistance are poor. Patent CN202111417715.3 discloses a positive photoresist composition, a preparation method and application thereof, wherein an acid catalyst and a cross-linking agent are added into phenolic resin with the molecular weight of 1000-10000, the phenolic resin has good insolubility in a non-exposure area, and an anion initiator in the exposure area can inactivate the catalyst, increase the solution of the catalyst in a developing solution, and realize better developing effect. But it cannot satisfy the corrosive action of the etching liquid on the glass. The patent CN200910082368.6 provides a preparation method of a protective film for protecting a glass microfluidic chip during etching, wherein a metal sacrificial layer, positive photoresist and formaldehyde monomer aqueous solution or glutaraldehyde aqueous solution with a certain concentration and pH value are used as a cross-linking agent after exposure are plated on a glass substrate, so that the tolerance of the protective film formed by the positive photoresist on a glass surface is increased, and the etching depth of a glass basal plane is reduced. But does not improve the adhesion and resolution of the development. Disclosure of Invention In order to solve the problems, the first aspect of the invention provides a hydrofluoric acid-resistant protective material for lithography, which comprises, by weight, 10-40% of resin, 10-20% of a cyclic structure compound, 50-90% of a solvent, and 1-3% of an auxiliary agent. In some preferred embodiments, the resin is selected from at least one of phenolic resin, polyhydroxystyrene resin, polyimide, polyvinylphenol resin, polyacrylic resin, preferably the resin is phenolic resin, further preferably the phenolic resin is a modified phenolic resin. In some preferred embodiments, the preparation method of the modified phenolic resin specifically comprises the following steps: s1, adding 10 parts by weight of first monohydroxy cresol, 5-15 parts by weight of formaldehyde and 0.03-0.07 part by weight of catalyst into water for reaction, and adding a neutralizer for neutralization; S2, continuously adding 8 parts by weight of second monohydroxy cresol, 5-15 parts by weight of formaldehyde, 0.01-0.04 part by weight of catalyst and 3-10 parts by weight of 2-hydroxy-1-hydroxymethyl naphthalene into the product obtained in the S1, and heating to 70-85 ℃ for reaction for 1-2.5 hours; S3, continuously adding 2-7 parts by weight of polyhydroxy phenol and 2-8 parts by weight of 4,4' -dihydroxydiphenyl ether into the product obtained in the S2, and heating to 80-95 ℃ for reaction for 3-5 hours; S4, washing the product obtained in the step S3, separating out a water phase, and then drying at 40-70 ℃ to obtain the product. In some preferred embodiments, the first monohydroxycresol in S1 is selected from at least one of 2-methylphenol, 3-methylphenol, and 4-methylphenol, and preferably the first monohydroxycresol in S1 is 3-methylphenol. In some preferred embodiments, the catalyst in S1 and S2 is at least one selected from p-toluenesulfonic acid, oxalic acid, hydrochloric acid, sulfuric acid, succinic acid and dodecylbenzenesulfonic acid, and preferably, the catalyst in S1 and S2 is oxalic acid and dodecylbenzenesulfonic acid. In some preferred embodiments, the volume ratio of oxalic acid to dodecylbenzene sulfonic acid is 1 (0.7-2), preferably the volume ratio of oxalic acid to dodecylbenzene sulfonic acid is 1:1.1. In some preferred embodiments, the second monohydroxycresol in S2 is selected from at least one of 2, 3-dimethylphenol, 2, 4-dimethylphenol, 2, 5-dimethylphenol, 2, 6-dimethylphenol, 3, 5-dimethylphenol, 2,3, 5-trimethylphenol, and preferably the second monohydroxycresol in S2 is 3, 5-dimethylphenol. In some preferred embodiments, the polyhydric phenol in S3 is selected from at least one of 2-methyl resorcinol, 2, 5-dimethyl resorcinol, 1, 3-resorcinol, 1, 4-hydroquinon