A hydrofluoric acid resistant protective material for photolithography and a photolithography process thereof

Abstract

The application discloses a kind of for photoetching resistant hydrogen fluoride protective material and photoetching process thereof, by self-made synthesis molecular weight distribution narrow high-performance phenolic resin, with the material viscosity obtained after being mixed with cyclic structure compound, additive, solvent in system, between the adhesion of substrate to be etched is strong, leveling is good, and it has excellent resistant hydrogen fluoride etching performance, can protect glass.In addition, the obtained for photoetching resistant hydrogen fluoride protective material has good uniformity, can effectively reduce the occurrence of collapse in photoetching process Badly.The obtained for photoetching resistant hydrogen fluoride protective material in the application is used for positive photoresist, has excellent high heat resistance, can be used for the production process with high-temperature process, can form good pattern topography in exposure process, contrast is good, and it has high sensitivity and resolution.

Description

Technical Field

[0001] This invention relates to the field of photoresist preparation, G03F7 / 039, and particularly to a hydrofluoric acid resistant protective material for photolithography and its photolithography process. Background Technology

[0002] Glass is widely used as a substrate for photolithography due to its unique electroosmotic and optical properties, as well as its weak fluorescence background interference. By modifying its surface, it can be easily photolithographically and etched onto silicon wafers using hydrofluoric acid and its mixtures, forming tiny bumps and depressions on the glass surface to create chips with desired patterns. Coating the glass-silicon wafer surface with positive photoresist provides high resolution, good step coverage, and good contrast, and can also effectively protect the substrate surface; however, its heat resistance and hydrofluoric acid resistance are relatively poor.

[0003] Patent CN202111417715.3 discloses a positive photoresist composition, its preparation method, and its application. In this composition, an acidic catalyst and crosslinking agent are added to a phenolic resin with a molecular weight of 1000-10000. This results in good insolubility in the non-exposed area, while an anionic initiator in the exposed area deactivates the catalyst, increasing its solution concentration in the developer and achieving better development. However, this method cannot address the corrosive effect of the etching solution on the glass. Patent CN200910082368.6 provides a method for preparing a protective film during the etching of glass microfluidic chips. A metal sacrificial layer and positive photoresist are deposited on a glass substrate. After exposure, a formaldehyde monomer aqueous solution or glutaraldehyde aqueous solution of a certain concentration and pH value is used as a crosslinking agent to increase the tolerance of the protective film formed by the positive photoresist on the glass surface and reduce the etching depth on the glass substrate. However, this method does not improve the adhesion and resolution of the developed surface. Summary of the Invention

[0004] To address the aforementioned problems, the first aspect of this invention provides a hydrofluoric acid-resistant protective material for photolithography, wherein the raw materials for its preparation, by weight percentage, include: 10-40% resin, 10-20% cyclic compound, 50-90% solvent, and 1-3% additives.

[0005] In some preferred embodiments, the resin is selected from at least one of phenolic resin, polyhydroxystyrene resin, polyimide, polyvinylphenol resin, and polyacrylic acid resin; preferably, the resin is phenolic resin; more preferably, the phenolic resin is modified phenolic resin.

[0006] In some preferred embodiments, the preparation method of the modified phenolic resin specifically includes the following steps:

[0007] S1. Add 10 parts by weight of monohydroxycresol, 5-15 parts by weight of formaldehyde, and 0.03-0.07 parts by weight of catalyst to water to react, and add a neutralizing agent to neutralize to neutral;

[0008] S2. Add 8 parts by weight of second monohydroxycresol, 5-15 parts by weight of formaldehyde, 0.01-0.04 parts by weight of catalyst, and 3-10 parts by weight of 2-hydroxy-1-hydroxymethylnaphthalene to the product obtained in S1, and heat to 70-85°C for 1-2.5 h.

[0009] S3. Add 2-7 parts by weight of polyhydroxyphenol and 2-8 parts by weight of 4,4'-dihydroxydiphenyl ether to the product obtained in S2, and heat to 80-95℃ for 3-5 hours.

[0010] S4. Wash the product obtained in S3 with water to separate the aqueous phase, and then dry it at 40-70℃ to obtain the final product.

[0011] In some preferred embodiments, the first monohydroxycresol in S1 is selected from at least one of 2-methylphenol, 3-methylphenol, and 4-methylphenol; preferably, the first monohydroxycresol in S1 is 3-methylphenol.

[0012] In some preferred embodiments, the catalysts in S1 and S2 are selected from at least one of p-toluenesulfonic acid, oxalic acid, hydrochloric acid, sulfuric acid, succinic acid, and dodecylbenzenesulfonic acid; preferably, the catalysts in S1 and S2 are oxalic acid and dodecylbenzenesulfonic acid.

[0013] In some preferred embodiments, the volume ratio of oxalic acid to dodecylbenzenesulfonic acid is 1:(0.7-2); preferably, the volume ratio of oxalic acid to dodecylbenzenesulfonic acid is 1:1.1.

[0014] 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, and 2,3,5-trimethylphenol; preferably, the second monohydroxycresol in S2 is 3,5-dimethylphenol.

[0015] In some preferred embodiments, the polyhydroxyphenol in S3 is selected from at least one of 2-methylresorcinol, 2,5-dimethylresorcinol, 1,3-resorcinol, 1,4-hydroquinone, 2,6-dimethylhydroquinone, 4-methylresorcinol, and 4,5-dimethylresorcinol; preferably, the polyhydroxyphenol in S3 is 1,4-hydroquinone.

[0016] Phenolic resins possess excellent adhesion and high-temperature resistance, but their specific structure affects their solubility in the developer, thus impacting resolution. In this application, a phenolic resin prepared by reacting first monohydroxycresol, second monohydroxycresol, and formaldehyde is used as the film-forming material for positive photoresist. It exhibits good adhesion to the photolithographic material and strong chemical resistance after film formation. In particular, the addition of polyhydroxyphenol during preparation improves the heat resistance of the phenolic resin while simultaneously increasing its resolution. It is speculated that this is because 1,4-hydroquinone, in synergy with 2-hydroxy-1-hydroxymethylnaphthalene, 4,4'-dihydroxydiphenyl ether, and other components in the system, increases hydrogen bonding forces and reactive sites, promoting the cross-linking of 2-hydroxy-1-hydroxymethylnaphthalene and 4,4'-dihydroxydiphenyl ether, narrowing the molecular weight distribution range of the phenolic resin, and improving its performance, thereby increasing its thermal decomposition temperature and dissolution rate. The resulting phenolic resin, along with the cyclic compounds and additives in the system, works synergistically to maintain its heat resistance and high resolution, while also exhibiting good resistance to hydrofluoric acid corrosion, thus better protecting the glass material.

[0017] In some preferred embodiments, the cyclic compound is selected from 2-diazo-1-naphthoquinone-4-sulfonate, 2-diazo-1-naphthoquinone-5-sulfonate, N-hydroxynaphthalimide trifluoromethanesulfonate, 5-[N-(tert-butyloxyformyl)amino]-1,3,3-trimethyl-6'-nitroindolinespiropyran, 1-(2-hydroxyethyl)-3,3-dimethylindoline-6'-nitrobenzospiropyran, 1,3,3-trimethyl-3H At least one of the following: indolinespironaphthazine, 1,3,3-trimethyl-9'-benzoyloxy-indolinespironaphthazine, 2,2'-bipyridine, 4,4'-bipyridine, triphenylthionium perfluorobutylsulfonate, triphenylthionium trifluoromethanesulfonate, and di(4-tert-butylphenyl)iodoonium p-toluenesulfonate; preferably, the cyclic compound is N-hydroxynaphthalimide trifluoromethanesulfonate and di(4-tert-butylphenyl)iodoonium p-toluenesulfonate.

[0018] In some preferred embodiments, the mass ratio of N-hydroxynaphthalimide trifluoromethanesulfonate to p-toluenesulfonic acid di(4-tert-butylphenyl)iodonium salt is 1:(1-2); preferably, the mass ratio of N-hydroxynaphthalimide trifluoromethanesulfonate to p-toluenesulfonic acid di(4-tert-butylphenyl)iodonium salt is 1:1.5.

[0019] In some preferred embodiments, the solvent is selected from at least one of propylene glycol methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethyl acetate, propylene glycol methyl ether acetate, ethyl acetate, n-butyl acetate, N-methylpyrrolidone, and cyclohexanone; preferably, the solvent is diethylene glycol monomethyl ether and N-methylpyrrolidone.

[0020] In some preferred embodiments, the volume ratio of diethylene glycol monomethyl ether to N-methylpyrrolidone is 1:(1.2-2.5); preferably, the volume ratio of diethylene glycol monomethyl ether to N-methylpyrrolidone is 1:1.7.

[0021] In some preferred embodiments, the additive includes at least one of a crosslinking agent, an adhesion promoter, and a tackifier; preferably, the additive includes a crosslinking agent and an adhesion promoter.

[0022] In some preferred embodiments, the mass ratio of the crosslinking agent to the adhesion promoter is 1:(0.7-1.8); preferably, the mass ratio of the crosslinking agent to the adhesion promoter is 1:0.9.

[0023] In some preferred embodiments, the crosslinking agent is selected from at least one of formaldehyde, glutaraldehyde, amino resin, melamine phosphate, benzomelamine, and melamine-modified polyurethane; preferably, the crosslinking agent is glutaraldehyde and amino resin; more preferably, the crosslinking agent is glutaraldehyde and highly methylated amino resin.

[0024] In some preferred embodiments, the mass ratio of glutaraldehyde to amino resin is 1:(0.5-1.2); preferably, the mass ratio of glutaraldehyde to amino resin is 1:0.7.

[0025] In some preferred embodiments, the glutaraldehyde is a glutaraldehyde aqueous solution with a volume fraction of 2-5%; preferably, the glutaraldehyde is a glutaraldehyde aqueous solution with a volume fraction of 4%.

[0026] In some preferred embodiments, the monomer content of the highly methylated amino resin is 50-78%, and the viscosity at 23°C is 2000-5500 mPa·s; preferably, the monomer content of the highly methylated amino resin is 59%, and the viscosity at 23°C is 2600-5000 mPa·s.

[0027] In some preferred embodiments, the adhesion promoter is selected from at least one of melamine resin, fluorinated surfactant, coupling agent, and polymethyl vinyl ether; preferably, the adhesion promoter is a coupling agent; more preferably, the adhesion promoter is vinyltris(β-methoxyethoxy)silane or organotitanate.

[0028] In some preferred embodiments, the mass ratio of vinyltris(β-methoxyethoxy)silane to organotitanate is 1:(1.5-2.5); preferably, the mass ratio of vinyltris(β-methoxyethoxy)silane to organotitanate is 1:1.8.

[0029] In some preferred embodiments, the preparation method of the hydrofluoric acid resistant protective material for photolithography is as follows: the raw materials are mixed in a certain proportion.

[0030] A second aspect of the present invention provides a photolithography process, comprising the following steps:

[0031] (1) Coat the surface of the material to be photolithographically with a hydrofluoric acid resistant protective material for photolithography, and heat and dry it in a tunnel furnace;

[0032] (2) Align the material obtained in (1) and expose it;

[0033] (3) Spray or immerse the material obtained in (2) in developing solution for developing treatment;

[0034] (4) Heat the material obtained in (3) to perform a hard film treatment;

[0035] (5) Spray or immerse the material obtained in (4) in a degumming solution for degumming treatment.

[0036] In some preferred embodiments, the heating temperature in (1) is 90-130°C and the drying time is 5-20 min; preferably, the heating temperature in (1) is 100-120°C and the drying time is 8-15 min; more preferably, the heating temperature in (1) is 110°C and the drying time is 10 min.

[0037] In some preferred embodiments, the energy value of the exposure process in S2 is 150–500 mJ / cm. 2 The half-width is 1.5–4.5 μm; preferably, the energy value of the exposure process in S2 is 300 mJ / cm. 2 The half-width is 3μm.

[0038] In some preferred embodiments, the exposure wavelength in S2 is a broadband ultraviolet (g+h+i), and the exposure method is either contact exposure or near exposure.

[0039] In some preferred embodiments, the heating temperature in step S4 is 120–160°C and the heating time is 10–40 min; preferably, the heating temperature in step S4 is 130–150°C and the heating time is 15–30 min; more preferably, the heating temperature in step S4 is 140°C and the heating time is 25 min.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] (1) In this application, a high-performance phenolic resin with a narrow molecular weight distribution is synthesized in-house. After mixing with cyclic compounds, additives, and solvents in the system, the resulting material has moderate viscosity, strong adhesion to the substrate to be etched, good leveling properties, and excellent resistance to hydrofluoric acid etching, thus protecting the glass. In addition, the resulting hydrofluoric acid-resistant protective material for photolithography has good uniformity, which can effectively reduce the occurrence of chipping defects in the photolithography process.

[0042] (2) The hydrofluoric acid resistant protective material for photolithography obtained in this application is used as a positive photoresist. It has excellent high heat resistance and can be used in production processes with high temperature. It can form good pattern morphology in the exposure process, with good contrast, and has high sensitivity and resolution. Detailed Implementation

[0043] Example 1

[0044] 1. A hydrofluoric acid resistant protective material for photolithography, wherein the raw materials for its preparation include, by weight percentage: 35% resin, 15% cyclic compound, 1.5% additives, and the balance being solvent.

[0045] The resin is a phenolic resin. The phenolic resin is a modified phenolic resin.

[0046] The preparation method of the modified phenolic resin specifically includes the following steps:

[0047] S1. Add 10 parts by weight of monohydroxycresol, 8 parts by weight of formaldehyde, and 0.04 parts by weight of catalyst to water to react, and add a neutralizing agent to neutralize to neutral;

[0048] S2. Add 8 parts by weight of second monohydroxycresol, 7 parts by weight of formaldehyde, 0.02 parts by weight of catalyst, and 8 parts by weight of 2-hydroxy-1-hydroxymethylnaphthalene to the product obtained in S1, and heat to 80°C and react for 2 hours.

[0049] S3. Add 6 parts by weight of polyhydroxyphenol and 5 parts by weight of 4,4'-dihydroxydiphenyl ether to the product obtained in S2, and heat to 90°C for 4 hours.

[0050] S4. Wash the product obtained in S3 with water to separate the aqueous phase, and then dry it at 60°C to obtain the final product.

[0051] The first monohydroxycresol in S1 is 3-methylphenol.

[0052] The catalysts in S1 and S2 are oxalic acid and dodecylbenzenesulfonic acid.

[0053] The volume ratio of oxalic acid to dodecylbenzenesulfonic acid is 1:1.1.

[0054] The second monohydroxycresol in S2 is 3,5-dimethylphenol.

[0055] The polyhydroxyphenol in S3 is 1,4-hydroquinone.

[0056] The cyclic compound is N-hydroxynaphthalimide trifluoromethanesulfonate and p-toluenesulfonate di(4-tert-butylphenyl)iodonium salt.

[0057] The mass ratio of the hydroxynaphthalimide trifluoromethanesulfonate to p-toluenesulfonic acid di(4-tert-butylphenyl)iodonium salt is 1:1.5.

[0058] The solvent is diethylene glycol monomethyl ether and N-methylpyrrolidone.

[0059] The volume ratio of diethylene glycol monomethyl ether to N-methylpyrrolidone is 1:1.7.

[0060] The additives include crosslinking agents and adhesion promoters.

[0061] The mass ratio of the crosslinking agent to the adhesion promoter is 1:0.9.

[0062] The crosslinking agent is glutaraldehyde and a highly methylated amino resin.

[0063] The mass ratio of glutaraldehyde to amino resin is 1:0.7.

[0064] The glutaraldehyde is a 4% (v / v) aqueous solution of glutaraldehyde.

[0065] The highly methylated amino resin has a monomer content of 59% and a viscosity of 2600–5000 mPa·s at 23°C (Cymel-303 LF).

[0066] The adhesion promoter is a coupling agent; the adhesion promoter is vinyltris(β-methoxyethoxy)silane or organotitanate (CAS No.: 109768-37-8).

[0067] The mass ratio of vinyltris(β-methoxyethoxy)silane to organotitanate is 1:1.8.

[0068] The preparation method of the hydrofluoric acid resistant protective material used for photolithography is as follows: the raw materials are mixed in a certain proportion.

[0069] 2. A photolithography process, comprising the following steps:

[0070] (1) Coat the surface of the material to be photolithographically with a hydrofluoric acid resistant protective material for photolithography, and heat and dry it in a tunnel furnace;

[0071] (2) Align the material obtained in (1) and expose it;

[0072] (3) Spray or immerse the material obtained in (2) in developing solution for developing treatment;

[0073] (4) Heat the material obtained in (3) to perform a hard film treatment;

[0074] (5) Spray or immerse the material obtained in (4) in a degumming solution for degumming treatment.

[0075] The heating temperature in (1) is 110°C and the drying time is 10 min.

[0076] The energy value of the exposure treatment in (2) is 300 mJ / cm. 2 The half-width is 3μm.

[0077] In (2), the exposure wavelength is ultraviolet broadband (g+h+i), and the exposure method is contact exposure.

[0078] The heating temperature in (4) is 140°C and the heating time is 25 min.

[0079] The developing solution in (3) and the adhesive remover in (5) were both purchased from Hunan Fanxin Technology Co., Ltd.

[0080] Example 2:

[0081] 1. A hydrofluoric acid-resistant protective material for photolithography, which differs from Example 1 in that:

[0082] A hydrofluoric acid resistant protective material for photolithography, wherein the raw materials for preparation by weight percentage include: 30% resin, 18% cyclic compound, 1% additives, and the balance being solvent.

[0083] 2. A photolithography process, the same as in Example 1.

[0084] Comparative Example 1:

[0085] 1. A hydrofluoric acid-resistant protective material for photolithography, which differs from Example 1 in that:

[0086] The preparation method of the modified phenolic resin specifically includes the following steps:

[0087] S1. Add 10 parts by weight of monohydroxycresol, 8 parts by weight of formaldehyde, and 0.04 parts by weight of catalyst to water to react, and add a neutralizing agent to neutralize to neutral;

[0088] S2. Add 7 parts by weight of formaldehyde, 0.02 parts by weight of catalyst, and 8 parts by weight of 2-hydroxy-1-hydroxymethylnaphthalene to the product obtained in S1, and heat to 80°C for 2 hours.

[0089] S3. Add 6 parts by weight of polyhydroxyphenol and 5 parts by weight of 4,4'-dihydroxydiphenyl ether to the product obtained in S2, and heat to 90°C for 4 hours.

[0090] S4. Wash the product obtained in S3 with water to separate the aqueous phase, and then dry it at 60°C to obtain the final product.

[0091] 2. A photolithography process, the same as in Example 1.

[0092] Comparative Example 2:

[0093] 1. A hydrofluoric acid-resistant protective material for photolithography, which differs from Example 1 in that:

[0094] The highly methylated amino resin has a monomer content of 45% and a viscosity of 3600–6300 mPa·s at 23°C (Cymel-XW 3106).

[0095] 2. A photolithography process, the same as in Example 1.

[0096] Comparative Example 3:

[0097] 1. A hydrofluoric acid-resistant protective material for photolithography, which differs from Example 1 in that:

[0098] The adhesion promoter is vinyltris(β-methoxyethoxy)silane.

[0099] 2. A photolithography process, the same as in Example 1.

[0100] Performance testing

[0101] Sample preparation: The hydrofluoric acid resistant protective material for photolithography obtained in the examples and comparative examples is adhered to a glass surface of the same size, and then processed by the photolithography process in Example 1 to obtain the final product.

[0102] 1. Resolution: The processed samples obtained from the examples and comparative examples were tested with a laser microscope to confirm the resolution of the patterns. The cases that could be clearly distinguished with a line width of 5μm and L / S = 1 / 1 were recorded as A, and the cases that could not be clearly distinguished were recorded as B.

[0103] 2. Heat resistance: The temperature at which the processed samples obtained in the examples and comparative examples are recorded according to the resolution test method described above, with the resolution level ranging from A to B, is the heat resistance temperature.

[0104] 3. Adhesion: The coatings obtained in the examples and comparative examples were washed with water for 4 minutes and then peeled off. If the coating could not be peeled off, it was rated as Grade 1; if the degree of peeling was less than 30% of the total coating area, it was rated as Grade 2; and if the degree of peeling was greater than 30% of the total coating area, it was rated as Grade 3.

[0105] 4. Hydrofluoric acid resistance: The treated samples obtained in the examples and comparative examples were immersed in a 15% (v / v) aqueous solution of hydrofluoric acid for 12 hours, and the changes on the sample surface were observed. A complete coating was designated as A; a damaged area of ​​<30% was designated as B; a damaged area of ​​30-60% was designated as C; and a damaged area of ​​>60% was designated as D.

[0106] The specific test results are shown in Table 1.

[0107] Table 1. Performance test results of the examples and comparative examples.

[0108] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 resolution A A B B A Heat resistance 165 160 130 140 145 Adhesion 1 1 2 1 3 Hydrofluoric acid resistant A A C B D

Claims

1. A hydrofluoric acid-resistant protective material for photolithography, characterized in that, By weight percentage, its preparation raw materials include: 10-40% resin, 10-20% cyclic compound, 50-90% solvent, and 1-3% additives. The resin is a modified phenolic resin; The preparation method of the modified phenolic resin specifically includes the following steps: S1. Add 10 parts by weight of monohydroxycresol, 5-15 parts by weight of formaldehyde, and 0.03-0.07 parts by weight of catalyst to water to react, and add a neutralizing agent to neutralize to neutral; S2. Add 8 parts by weight of second monohydroxycresol, 5-15 parts by weight of formaldehyde, 0.01-0.04 parts by weight of catalyst, and 3-10 parts by weight of 2-hydroxy-1-hydroxymethylnaphthalene to the product obtained in S1, and heat to 70-85℃ for 1-2.5 h. S3. Add 2-7 parts by weight of polyhydroxyphenol and 2-8 parts by weight of 4,4'-dihydroxydiphenyl ether to the product obtained in S2, and heat to 80-95℃ for 3-5 hours. S4. Wash the product obtained in S3 with water to separate the aqueous phase, and then dry it at 40~70℃ to obtain the final product.

2. The hydrofluoric acid-resistant protective material for photolithography according to claim 1, characterized in that, The catalysts in S1 and S2 are selected from at least one of p-toluenesulfonic acid, oxalic acid, hydrochloric acid, sulfuric acid, succinic acid, and dodecylbenzenesulfonic acid.

3. The hydrofluoric acid-resistant protective material for photolithography according to claim 1, characterized in that, The catalysts in S1 and S2 are oxalic acid and dodecylbenzenesulfonic acid; The volume ratio of oxalic acid to dodecylbenzenesulfonic acid is 1:(0.7~2).

4. The hydrofluoric acid-resistant protective material for photolithography according to claim 1, characterized in that, The polyhydroxyphenol in S3 is selected from at least one of 2-methylresorcinol, 2,5-dimethylresorcinol, 1,3-resorcinol, 1,4-hydroquinone, 2,6-dimethylhydroquinone, 4-methylresorcinol, and 4,5-dimethylresorcinol.

5. The hydrofluoric acid-resistant protective material for photolithography according to claim 1, characterized in that, The cyclic compound is selected from at least one of the following: 2-diazo-1-naphthoquinone-4-sulfonate, 2-diazo-1-naphthoquinone-5-sulfonate, N-hydroxynaphthalimide trifluoromethanesulfonate, 5-[N-(tert-butoxycarboxyl)amino]-1,3,3-trimethyl-6'-nitroindolinespiropyran, 1-(2-hydroxyethyl)-3,3-dimethylindoline-6'-nitrobenzospiropyran, 1,3,3-trimethyl-3H-indolinespironaphrazine, 1,3,3-trimethyl-9'-benzoyloxy-indolinespironaphrazine, 2,2'-bipyridine, 4,4'-bipyridine, triphenylthionium perfluorobutylsulfonate, triphenylthionium trifluoromethanesulfonate, and di(4-tert-butylphenyl)iodoonium p-toluenesulfonate.

6. The hydrofluoric acid-resistant protective material for photolithography according to claim 5, characterized in that, The cyclic compound is N-hydroxynaphthalimide trifluoromethanesulfonate and p-toluenesulfonate di(4-tert-butylphenyl)iodonium salt; The mass ratio of the N-hydroxynaphthalimide trifluoromethanesulfonate to p-toluenesulfonic acid di(4-tert-butylphenyl)iodonium salt is 1:(1~2).

7. The hydrofluoric acid-resistant protective material for photolithography according to claim 1, characterized in that, The additives include at least one of crosslinking agents, adhesion promoters, and tackifiers.

8. The hydrofluoric acid-resistant protective material for photolithography according to claim 1, characterized in that, The additives include crosslinking agents and adhesion promoters; The adhesion promoter is selected from at least one of melamine resin, fluorinated surfactant, coupling agent, and polymethyl vinyl ether.

9. A photolithography process, characterized in that, Includes the following steps: (1) Coating the hydrofluoric acid resistant protective material for photolithography as described in any one of claims 1 to 8 onto the surface of the material to be photolithographically processed, and heating and drying it in a tunnel furnace; (2) Align the material obtained in (1) and expose it; (3) Spray or immerse the material obtained in (2) in developing solution for developing treatment; (4) Heat the material obtained in (3) to perform a hardening treatment; (5) Spray or immerse the material obtained in (4) in a degumming solution to remove the glue.