Preparation method of photoacid generator for semiconductor photoresist

Abstract

The invention discloses a preparation method of a photoacid generator for a semiconductor photoresist, which comprises the following specific steps: firstly, treating raw materials by using anion exchange resin to obtain triphenyl sulfur tetrafluorobutanol sulfonic acid onium salt; organic acid and organic acid anhydride are adopted as esterification reagents, esterification reaction is carried out on the esterification reagents and adamantanecarboxylic acid under mild conditions, and ((triphenylsulfonium, adamantane-1-carbonyl) oxy)-tetrafluorobutyl sulfonate and the derivative thereof are synthesized. The invention provides the efficient, economic and environment-friendly preparation method of the photoacid generator, the product has efficient acid production efficiency, the raw materials are wide in source and low in price, and the production cost is reduced; reaction conditions are mild, extreme conditions such as high temperature and high pressure are avoided, and production safety is improved; the esterification process is stable and controllable, and high quality and yield of the product are ensured; meanwhile, the selected esterification reagent has good solubility with water, removal in the subsequent treatment process is facilitated, and the production process is simplified.

Description

Technical Field

[0001] The invention relates to the field of semiconductor photoresists, and in particular to a method for preparing a photoacid generator for semiconductor photoresists. Background Art

[0002] Photoacid generators are key components of semiconductor photoresists and have a significant impact on the quality and precision of photolithography products. There are still some problems with the domestic synthesis technology of photoacid generators: First, the synthesis route of some photoacid generators is relatively long, resulting in low production efficiency and difficulty in meeting the needs of large-scale production. Second, the yield of some photoacid generators is low, which not only increases production costs but also limits their wide application.

[0003] Patent CN115536557B proposes a method for preparing a photoacid generator by preparing adamantane chloride and then synthesizing adamantane sulfonate. However, this method has obvious deficiencies and defects. Adamantane chloride is very easy to hydrolyze, and the harmful substances produced during the hydrolysis process can cause great damage to human eyes and respiratory mucosa, which not only increases the safety risk in the production process, but also limits the storage and transportation of adamantane sulfonate. In addition, the raw material price of adamantane chloride is high, resulting in excessively high manufacturing costs, which further limits the wide application of this method.

[0004] In view of the above shortcomings and defects, the present invention aims to propose a method for preparing a photoacid generator with low raw material price, controllable cost and mild reaction, so as to solve the problems of high synthesis cost, difficulty in mass production and unstable product quality of photoacid generators in the prior art. By optimizing the synthesis route and reaction conditions, the synthesis efficiency and yield of the photoacid generator are improved, the production cost and environmental pollution risk are reduced, and the product quality is ensured to be stable and reliable. Summary of the invention

[0005] Technical problem to be solved: The technical problem to be solved by the present invention is to provide a method for preparing a photoacid generator for semiconductor photoresist, with mild reaction conditions, controllable costs and less environmental pollution.

[0006] Technical solution: A method for preparing a photoacid generator for semiconductor photoresist, comprising the following steps: Add raw material A and anionic resin into a reaction kettle, add solvent, stir for 5 to 7 hours and filter, add raw material E into the filtrate and continue stirring for 3 to 5 hours, decompress the reaction solution and spin dry, add precipitation solvent, recrystallize, filter and vacuum dry to obtain intermediate product B; S2. The reactor was purged with nitrogen, the intermediate product B, the raw material D and the organic acid were added and stirred to dissolve, the reaction temperature was lowered to -20 ~ 0 °C, the organic anhydride solution was added dropwise, and after the addition was completed, the temperature was raised to 25 ~ 45 °C and the reaction was carried out for 10 ~ 14 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. Add a precipitation solvent to the concentrated reaction solution prepared in S2 for recrystallization, stir for 3 to 5 hours and then filter to obtain a photoacid generator.

[0007] Preferably, the raw material A in step S1 includes any one of triphenylsulfonium chloride and its substituent structure derivatives; The anion resin includes any one or more of a weakly basic anion resin, a strongly basic anion resin, a chloride-type anion resin, and a gel-type strongly basic anion resin, and the added amount is 500 to 1000 wt% of the mass of the raw material A; The solvent includes any one or more of methanol, ethanol, propanol, isopropanol, dichloromethane, water, and ethyl acetate, and the added amount is 500-1500 wt% of the mass of the raw material A, and the reaction temperature is 10-50 °C; The raw material E is sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonate; The intermediate product B includes any one of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt and its substituent structure derivatives; The molar ratio of the raw material A to the raw material E is 1:1 to 3.

[0008] Preferably, the precipitation solvent in steps S1 and S3 includes any one or more of tertiary methyl ether, isopropyl ether, hexane, n-heptane, cyclohexane, ethyl acetate, and tetrahydrofuran; The amount added in step S1 is 200-800 wt% of the mass of raw material A; The addition amount in step S3 is 200-800 wt% of the total mass of the raw material A and the intermediate product B.

[0009] Preferably, the raw material D in step S2 comprises any one of adamantanecarboxylic acid and its substituted structural derivatives; The organic acid includes any one or more of trifluoroacetic acid, tetrafluoropropionic acid, and 2,2,3,4,4,4-hexafluorobutyric acid, and the added amount is 100-700 wt% of the total mass of the intermediate product B and the raw material D; The organic acid anhydride includes any one or more of acetic anhydride, propionic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, tetrafluoropropionic anhydride, and heptafluorobutyric anhydride, and the molar ratio of the intermediate product B to the organic acid anhydride is 1:2 to 7. The organic acid anhydride includes any one or more of trifluoroacetic anhydride, tetrafluoropropionic anhydride, and heptafluorobutyric anhydride, and the molar ratio of the intermediate product B to the organic acid anhydride is 1:2 to 7; The molar ratio of the intermediate product B to the raw material D is 1:1-2.

[0010] Preferably, the photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate and its substituted structural derivatives, and the structural formula is as follows: , Among them, R1, R2, and R3 are any one or more of hydrogen, methyl, tert-butyl, and fluoro, and R4 is any one of hydrogen, oxygen, and halogen.

[0011] Furthermore, the photoacid generator preferably has the following structure: .

[0012] Beneficial effects: Compared with the prior art, the present invention has the following characteristics: The preparation method of the photoacid generator of the present invention first prepares triphenylsulfonium tetrafluorobutanol sulfonate by anion exchange resin, then uses organic acid / organic acid anhydride as an esterification reagent, adds adamantane carboxylic acid to carry out esterification reaction, and obtains the product ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutane sulfonate.

[0013] As a key raw material for semiconductor photoresist, photoacid generator has high industrial value and has high requirements for raw material purity, product purity, synthesis route and overall cost. Triphenylsulfonium salt has good thermal stability, high photoinitiator activity and excellent solubility; adamantane is a symmetrical and highly stable cage hydrocarbon, and its basic carbon skeleton is similar to a lattice unit of diamond. Adamantane carboxylic acid containing adamantane skeleton structure has good thermal stability, chemical stability and optical stability; 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid sodium has a tetrafluoro-substituted butane skeleton, which is relatively stable chemically, and provides an acid center for the sulfonic acid group, has good light absorption ability and thermal stability, and has a high efficiency of decomposing and producing acid under light. Therefore, the above compounds are selected as the raw materials of photoacid generators, which are not only low in price, but also have good material stability, making the synthesis process controllable, and at the same time, the product performance is excellent and the acid production rate is high. In addition, the synthesis route of the present invention firstly prepares the intermediate product triphenylthio tetrafluorobutanol sulfonic acid onium salt by reacting anion exchange resin with triphenylsulfonium salt, and then performs esterification reaction with adamantane carboxylic acid to obtain the final product. The intermediate product triphenylthio tetrafluorobutanol sulfonic acid onium salt has good stability and solubility, so the process is stable during the synthesis process, the operation is simple and stable, and the esterification reagent used is also easy to remove, so that the purity of the final product is high and the acid production efficiency is further improved.

[0014] The raw materials used in the present invention do not contain unexchanged alkali metal ions, and the raw materials have high purity, which is beneficial to the subsequent control of metal ions.

[0015] After synthesizing anion sulfonate onium salt, the invention uses organic acid / organic acid anhydride as esterification reagent and adamantane carboxylic acid as raw material, and the esterification process is stable, the raw materials are cheap and the price is controllable.

[0016] The esterification reagent organic acid and organic acid anhydride used in the present invention have good solubility in water and can be subsequently removed by processes such as water washing and extraction. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 A synthetic route for photoacid generators used in semiconductor photoresists; Figure 2 is the NMR spectrum of the product of Example 1; Figure 3 is the NMR spectrum of the product of Example 2; Figure 4 is the NMR spectrum of the product of Example 3; Figure 5 is the NMR spectrum of the product of Example 4; Figure 6 This is the NMR spectrum of the product of Example 5. DETAILED DESCRIPTION In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples.

[0019] Specific preferred examples are as follows:

[0020] Embodiment 1: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.5 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.5 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.8 g of adamantane carboxylic acid and 621.9 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 126.8 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 174.1 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0021] Embodiment 2:

[0022] A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g (4-fluorophenyl) diphenyl sulfonium chloride and 700 g anion resin were added to a reactor, 1 kg methanol was added as a solvent, stirred for 6 h and filtered, 87.0 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 145.6 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid (4-fluorophenyl) diphenyl sulfonium; S2. The reactor was purged with nitrogen, 145.6 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid (4-fluorophenyl) diphenylsulfonium salt, 57.0 g of adamantane carboxylic acid and 607.9 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 120.8 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of methyl tert-ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 172.1 g of a photoacid generator; The photoacid generator is (((4-fluorophenyl)diphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0023] Embodiment 3:

[0024] A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g (4-tert-butylphenyl) diphenyl sulfonium chloride and 700 g anion resin were added to a reactor, 1 kg methanol was added as a solvent, stirred for 6 h and filtered, 77.7 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and continued to stir for 4 h, the reaction solution was decompressed and dried, 2 kg of tert-methyl ether was added as a precipitation solvent, recrystallized, filtered and vacuum dried to obtain 136.7 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid (4-tert-butylphenyl) diphenyl sulfonium salt; S2. The reactor was purged with nitrogen, 136.7 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid (4-tert-butylphenyl) diphenylsulfonium salt, 49.8 g of adamantane carboxylic acid and 559.5 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 105.5 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 hours. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 163.9 g of a photoacid generator; The photoacid generator is (((4-tert-butylphenyl)diphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0025] Embodiment 4:

[0026] A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of di(4-tert-butylphenyl)-(4-fluorophenyl)sulfonium chloride and 700 g of anion resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 64.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried by spin drying, 2 kg of tert-methyl ether was added as a precipitation solvent, recrystallized, filtered and vacuum dried to obtain 127.6 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid (di(4-tert-butylphenyl)-(4-fluorophenyl))sulfonium chloride; S2. The reactor was purged with nitrogen, 127.6 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid (di(4-tert-butylphenyl)-(4-fluorophenyl)) sulfonium chloride, 40.9 g of adamantanecarboxylic acid and 505.6 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 86.7 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of tertiary methyl ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 152 g of a photoacid generator; The photoacid generator is ((di(4-tert-butylphenyl)-4-fluorophenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0027] Embodiment 5:

[0028] A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g (4-cyclohexanesulfonyl) diphenylsulfonium chloride and 700 g anion resin were added to a reactor, 1 kg methanol was added as a solvent, stirred for 6 h and filtered, 62.0 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 124.4 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid (4-cyclohexanesulfonylphenyl) diphenylsulfonium; S2. The reactor was purged with nitrogen, 124.4 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid (4-cyclohexylsulfonylphenyl) diphenylsulfonium salt, 38.9 g of adamantane carboxylic acid and 489.7 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 82.3 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of tertiary methyl ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 134.5 g of a photoacid generator; The photoacid generator is (((4-cyclohexylsulfonylphenyl)diphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0029] Embodiment 6: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.6 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.6 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.9 g of adamantanecarboxylic acid and 622.7 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -10 °C, 127.0 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of tertiary methyl ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 175.8 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0030] Embodiment 7: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 148.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 148.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 60.0 g of adamantane carboxylic acid and 624.1 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -20 °C, 127.2 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of methyl tert-ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 177.8 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0031] Embodiment 8: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.6 g of adamantane carboxylic acid and 620.0 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 126.4 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 30 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of methyl tert-ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 172.5 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0032] Embodiment 9: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.8 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.8 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.9 g of adamantanecarboxylic acid and 623.4 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -10 °C, 127.1 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 30 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of tertiary methyl ether was added as a precipitating solvent, and recrystallized, stirred for 4 hours, and then filtered to obtain 175.2 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0033] Embodiment 10: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.3 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.3 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.7 g of adamantane carboxylic acid and 621.3 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -20 °C, 126.7 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 30 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 176.0 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0034] Embodiment 11: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 148.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 148.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 60.0 g of adamantane carboxylic acid and 624.1 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 127.2 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 45 °C and reacted for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 175.0 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0035] Embodiment 12: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.6 g of adamantane carboxylic acid and 620.0 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -10 °C, 126.4 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 45 °C and reacted for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of methyl tert-ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 175.4 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0036] Embodiment 13: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.4 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.4 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.8 g of adamantane carboxylic acid and 622.0 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -20 °C, 126.8 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 45 °C and reacted for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 175.7 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0037] Embodiment 14: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 184.6 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 146.5 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 146.5 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.4 g of adamantanecarboxylic acid and 617.9 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 126.0 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of tertiary methyl ether was added as a precipitating solvent, and recrystallized, stirred for 4 hours, and then filtered to obtain 171.3 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0038] Embodiment 15: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 276.9 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 145.7 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 145.7 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.1 g of adamantanecarboxylic acid and 614.4 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 125.3 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 169.4 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0039] Embodiment 16: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.6 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.6 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 89.8 g of adamantane carboxylic acid and 622.7 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 127.0 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 173.6 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0040] Embodiment 17: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.2 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.2 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 119.3 g of adamantane carboxylic acid and 620.6 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 126.5 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of tertiary methyl ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 172.7 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0041] In order to further illustrate the technical effect of the present invention, the present invention also provides a comparative example, which is as follows: Comparative Example 1: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. The reactor was purged with nitrogen, 100 g of sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonate and 504 g of acetonitrile were added, and the mixture was stirred at room temperature until a white suspension appeared. The mixture was cooled to 0 °C, and 102.0 g of triethylamine was added to prepare a mixed solution 1. S2. 120.2 g of raw material adamantanecarbonyl chloride and 373.8 g of acetonitrile (dried) were prepared into a mixed solution in a nitrogen atmosphere, and then added dropwise into the mixed solution 1 at -5 °C. After the addition was completed, the temperature was raised to room temperature and stirred for reaction for 20 h. A large amount of white smoke was generated during the addition. After the addition was completed, the temperature was raised to room temperature (25 °C) and stirred for reaction for 20 h. The reaction solution was decompressed and dried by rotary evaporation. 1 L of dichloromethane was added, and the solution was washed three times with 400 ml of deionized water. The dichloromethane was decompressed and dried by rotary evaporation. 2 kg of methyl tert-butyl ether was added as a precipitation solvent, and then the solution was recrystallized, filtered, and dried in vacuo to obtain 170.1 g of the intermediate product adamantane-1-carboxylic acid-3,3,4,4-tetrafluoro-4-sulfonic acid butyl ester. S3. 118.7 g of the intermediate product adamantane-1-carboxylic acid-3,3,4,4-tetrafluoro-4-butyl sulfonate, 100 g of triphenylsulfonium chloride, 1.2 L of water and 1.2 L of dichloromethane were mixed and stirred at room temperature for 16 h, washed after the reaction was completed, concentrated to remove dichloromethane, and 2 kg of methyl tert-butyl ether was added as a precipitation solvent for recrystallization to obtain 136.2 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0042] Comparative Example 2: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.7 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.7 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 59.8 g of adamantane carboxylic acid and 621.9 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to 5 °C, 126.8 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 107.1 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0043] Comparative Example 3: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 145.1 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 145.1 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 58.9 g of adamantane carboxylic acid and 612.0 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to 25 °C, 124.8 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. In the concentrated reaction solution prepared in S2, 2 kg of tertiary methyl ether was added as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 57.3 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0044] Comparative Example 4: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 369.2 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 120.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 120.0 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 48.7 g of adamantane carboxylic acid and 506.2 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 103.2 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 114.9 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0045] Comparative Example 5: A method for preparing a photoacid generator for semiconductor photoresist comprises the following steps: S1. 100 g of triphenylsulfonium chloride and 700 g of anionic resin were added to a reactor, 1 kg of methanol was added as a solvent, stirred for 6 h and filtered, 92.3 g of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate was added to the filtrate and stirred for 4 h, the reaction solution was decompressed and dried, 2 kg of tertiary methyl ether was added as a precipitation solvent, recrystallized, filtered and dried in vacuo to obtain 147.5 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt; S2. The reactor was purged with nitrogen, 147.5 g of the intermediate product 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt, 179.4 g of adamantane carboxylic acid and 622.0 g of trifluoroacetic acid were added and stirred to dissolve, the reaction temperature was lowered to -5 °C, 126.8 g of trifluoroacetic anhydride was added dropwise, and after the addition was completed, the temperature was raised to 40 °C and the reaction was carried out for 12 h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. 2 kg of tertiary methyl ether was added to the concentrated reaction solution prepared in S2 as a precipitating solvent, and recrystallized, stirred for 4 h, and then filtered to obtain 154.2 g of a photoacid generator; The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate, and the structure is shown below: .

[0046] Table 1 Effects of different synthetic routes on the yields of intermediates and final products

[0047] Table 2 Yields of intermediates and final products of products with different structures

[0048]

[0049] Table 3 Effect of different reaction temperatures on final product yield

[0050] Table 4 Effect of different molar ratios of raw materials A and E on the yields of intermediate products and final products

[0051] Table 5 Effect of different molar ratios of intermediate product B and raw material D on the yield of the final product

[0052] The above are the data of the embodiments and comparative examples: after replacing different sulfonium salts in embodiments 1 / 2 / 3 / 4, the target product can be obtained normally; by comparing embodiments 1 / 6 / 7 and comparative example 2, it can be seen that when the temperature is below 0°C, trifluoroacetic anhydride is added dropwise, the esterification reaction can proceed normally, and the yield can reach more than 80%, and when the temperature reaches above 0°C, the yield is significantly reduced, mainly due to the exothermic esterification process and the increase in temperature, which brings other side reactions, thereby affecting the yield of the final product; by comparing embodiments 1 / 8 / 11 and comparative example 3, it can be seen that after the addition is completed, the reaction temperature needs to reach more than 25°C to ensure the yield; from embodiment 1 and comparative example 1, using two different synthetic routes, the yield of the intermediate is not much different, but the yield of the final product is quite different. The yield in this specification is about 30% higher than that in the comparative example, and the esterification reagent is trifluoroacetic anhydride / trifluoroacetic acid, which has the advantages of low cost, low pollution, and easy storage of raw materials compared to adamantane acyl chloride.

[0053] In summary, the present invention uses a new synthetic route to successfully obtain the target product, and the synthetic route is safe and controllable, the raw materials are cheap, and the waste generated in the experiment has less environmental pollution.

Claims

1. A method for preparing a photoacid generator for semiconductor photoresist, characterized in that: The following steps are involved: S1. Add raw material A and anionic resin to a reactor, add solvent, stir for 5 to 7 h and filter, add raw material E to the filtrate and continue stirring for 3 to 5 h, decompress the reaction solution and spin dry, add precipitation solvent, recrystallize, filter and vacuum dry to obtain intermediate product B; S2. The reactor was purged with nitrogen, the intermediate product B, the raw material D and the organic acid were added and stirred to dissolve, the reaction temperature was lowered to -20 ~ 0 ° C, the organic anhydride solution was added dropwise, and after the addition was completed, the temperature was raised to 25 ~ 45 ° C and the reaction was carried out for 10 ~ 14h. After the reaction was completed, the reaction was distilled under reduced pressure to obtain a concentrated reaction solution; S3. Add a precipitation solvent to the concentrated reaction solution prepared in S2 for recrystallization, stir for 3 to 5 hours and then filter to obtain a photoacid generator.

2. The method for preparing a photoacid generator for semiconductor photoresist according to claim 1, characterized in that: The raw material A in step S1 includes any one of triphenylsulfonium chloride and its substituent structure derivatives; The anion resin includes any one or more of a weakly basic anion resin, a strongly basic anion resin, a chloride-type anion resin, and a gel-type strongly basic anion resin, and the added amount is 500 to 1000 wt% of the mass of the raw material A; The solvent includes any one or more of methanol, ethanol, propanol, isopropanol, dichloromethane, water, and ethyl acetate, and the added amount is 500-1500 wt% of the mass of the raw material A, and the reaction temperature is 10-50 °C; The raw material E is sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonate; The intermediate product B includes any one of 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid triphenylsulfonium salt and its substituent structure derivatives; The molar ratio of the raw material A to the raw material E is 1:1 to 3.

3. The method for preparing a photoacid generator for semiconductor photoresist according to claim 1, characterized in that: The precipitation solvent in steps S1 and S3 includes any one or more of tertiary methyl ether, isopropyl ether, hexane, n-heptane, cyclohexane, ethyl acetate, and tetrahydrofuran; The amount added in step S1 is 200-800 wt% of the mass of raw material A; The addition amount in step S3 is 200-800 wt% of the total mass of the raw material A and the intermediate product B.

4. The method for preparing a photoacid generator for semiconductor photoresist according to claim 1, characterized in that: The raw material D in step S2 includes any one of adamantanecarboxylic acid and its substituted structural derivatives; The organic acid includes any one or more of trifluoroacetic acid, tetrafluoropropionic acid, and 2,2,3,4,4,4-hexafluorobutyric acid, and the added amount is 100-700 wt% of the total mass of the intermediate product B and the raw material D; The organic acid anhydride includes any one or more of acetic anhydride, propionic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, tetrafluoropropionic anhydride, and heptafluorobutyric anhydride, and the molar ratio of the intermediate product B to the organic acid anhydride is 1:2 to 7; The molar ratio of the intermediate product B to the raw material D is 1:1-2. 5 . The photoacid generator for semiconductor photoresist obtained according to the preparation method of the photoacid generator for semiconductor photoresist according to claim 1 .

6. The photoacid generator for semiconductor photoresist according to claim 5, characterized in that: The photoacid generator is ((triphenylsulfonium, adamantane-1-carbonyl)oxy)-tetrafluorobutanesulfonate and its substituted structural derivatives, and the structural formula is as follows: ， Among them, R1, R2, and R3 are any one or more of hydrogen, methyl, tert-butyl, fluoro, and cyclohexylsulfonyl, and R4 is any one of hydrogen, oxygen, and halogen.

7. The photoacid generator for semiconductor photoresist according to claim 5, characterized in that: The photoacid generator preferably has the following structure: 。

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