Compound applied to semiconductor chip etching and preparation method thereof

Abstract

The invention discloses a compound applied to semiconductor chip etching and a preparation method thereof, and the preparation method comprises the following steps: under shielding gas, uniformly mixing 4-tert-butylphenyltetramethylene sulfonium mesylate, 2-(((3r, 5r, 7r)-adamantane-1-carbonyl) oxy)-3, 3, 3-trifluoro-2-(trifluoromethyl) propane-1-sodium sulfonate, an organic solvent and ultrapure water, and stirring uniformly to obtain a mixture A of 4-tert-butylphenyltetramethylene sulfonium mesylate and 2-(((3r, 5r, 7r)-adamantane-1-carbonyl) oxy)-3, 3, 3-trifluoro-2-(trifluoromethyl) propane-1-sodium sulfonate; the preparation method comprises the following steps: adding 2-(4-tert-butylphenyltetramethylene sulfonium)-3, 3, 3, 3-trifluoro-2-(trifluoromethyl) propane-1-sulfonate into a reaction kettle, carrying out stirring and heating reaction, and after the reaction is finished, carrying out post-treatment to obtain the 4-tert-butylphenyltetramethylene sulfonium 2-(((3r, 5r, 7r)-adamantane-1-carbonyl) oxy)-3, 3, 3-trifluoro-2-(trifluoromethyl) propane-1-sulfonate. The preparation method disclosed by the invention is simple, the reaction system is green and environment-friendly, the selectivity is good, the total preparation cost is low, and the yield is high.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic chemical synthesis, and particularly relates to a compound for semiconductor chip etching and a preparation method thereof. Background Art

[0002] Photoacid generators are key components of high-end semiconductor photoresists and have an important impact on the yield, quality, processing accuracy, etc. of photoresists and photolithography products. Sulfonium salt photoacid generators have developed rapidly in the field of photochemistry due to their good solubility in solvents and resin systems, easy tailoring and processing, flexibility, and wide application range. Sulfonium salt photoacid generators have been applied earlier, have good acid generation performance and thermal stability, can quickly initiate electron transfer, and thus can quickly produce more stable active substances during photolysis, reducing the possibility of reverse electron transfer in the polymerization reaction, and have significant advantages in cationic polymerization. Therefore, it has high theoretical significance and practical application value to synthesize 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate efficiently, simply, and at low cost through molecular design.

[0003] The structural formula of 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is as follows: 。 Summary of the Invention In view of this, the present invention aims to provide a compound for semiconductor chip etching and a preparation method thereof to solve at least one technical problem in the background art, with a simple synthesis route, green and environmentally friendly reaction conditions, high product yield, and being suitable for industrial production.

[0005] To achieve the above object, the technical solution of the present invention is realized as follows: A compound for semiconductor chip etching, the compound being 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate, and the structural formula (I) is shown as follows: (Ⅰ)。

[0006] A preparation method of 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate, comprising the following steps: Under a protective gas, 4-tert-butylphenyltetramethylsulfonium methanesulfonate, 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sodium sulfonate, an organic solvent, and ultrapure water are mixed evenly, and stirring and heating reaction is carried out. After the reaction is completed, after post-treatment, 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is obtained, and the structural formula (Ⅰ) is as follows: (Ⅰ)。 (Ⅰ).

[0007] The synthesis route is as follows: 。 .

[0008] Further, the molar ratio of 4-tert-butylphenyltetramethylsulfonium methanesulfonate to 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sodium sulfonate is 1.0:(1.1~1.5).

[0009] Further, the temperature of the stirring and heating reaction is 35 - 54 °C.

[0010] Further, the time of the stirring and heating reaction is 3 - 5 h.

[0011] Further, the organic solvent includes one or more of methyl tert-butyl ether, 2-methyltetrahydrofuran, dichloromethane, dichloroethane, chloroform, and ethyl acetate.

[0012] Further, the protective gas is an inert gas.

[0013] Further, the protective gas is nitrogen.

[0014] Further, the post-treatment includes liquid separation, ultrapure water washing, concentration of the organic phase, crystallization with isopropyl ether, and vacuum drying to obtain 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate.

[0015] The above-mentioned 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate belongs to a photoacid generator and is applied in the field of semiconductor chip etching, such as in the processes of ArF, KrF, electron beam (EB) exposure lithography, or extreme ultraviolet (EUV) exposure lithography, etc.

[0016] Compared with the prior art, the compound for semiconductor chip etching and its preparation method according to the present invention have the following advantages: The present invention uses 4-tert-butylphenyltetramethylsulfonium methanesulfonate and sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate as the main raw materials, and uses ultrapure water and organic solvents as the reaction solvents to carry out a coordination substitution reaction to obtain 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate. The reaction steps are simple and safe, the preparation method is easy to implement, the reaction conditions are green and environmentally friendly, there are few side reactions, and the reaction yield is high. Therefore, the preparation method described in the present invention is novel, has good selectivity, is environmentally friendly, has a low overall preparation cost and a high yield, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments and descriptions of the present invention are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings: Figure 1 It is the HPLC chromatogram of 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate described in Example 5 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0018] It should be noted that, without conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0019] The present invention will be described in detail below with reference to the drawings and in combination with the embodiments.

[0020] The synthesis route of 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is as follows: ; Example 1: 4-tert-Butylphenyltetramethylenesulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate and its preparation method, comprising the following steps: The molar ratio of 4-tert-butylphenyltetramethylenesulfonium methanesulfonate to sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is 1.0:1.1. Under nitrogen protection, 500 mL of methyl tert-butyl ether and 500 mL of ultrapure water were added to a 2 L four-necked flask. While stirring, 4-tert-butylphenyltetramethylenesulfonium methanesulfonate (100.0 g, 1.0 eq) and sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate (155.1 g, 1.1 eq) were added. The mixture was stirred and heated to 40 °C, and stirred at 40 °C for 4 hours. After the reaction was completed by HPLC detection, it was allowed to stand for liquid separation, washed with ultrapure water, the organic phase was concentrated, crystallized with isopropyl ether, and dried in vacuo to obtain 186.0 g of 4-tert-butylphenyltetramethylenesulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate, with a yield of 91.3%. The water content was 0.05%. The hydrogen nuclear magnetic resonance spectrum is as follows: 1 H NMR (600MHz, DMSO-d6, δppm) : 1.32 (s, 9H), 1.65 (q, 6H), 1.84 (d,6H), 1.96 (s, 3H), 3.70 (t, 2H), 3.93 (t, 2H), 4.03 (s, 2H), 4.24-4.32 (m,4H), 7.28 (d, 2H), 7.42 (d, 2H). Among them, in the above reaction, in order to make the substrate 4-tert-butylphenyltetramethylenesulfonium methanesulfonate react completely, sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate was in excess and the reaction temperature was 40 °C to make the raw materials react completely to the greatest extent.

[0021] Example 2: 4-tert-Butylphenyltetramethylenesulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate and its preparation method, comprising the following steps: The molar ratio of 4-tert-butylphenyltetramethylsulfonium methylsulfonate to sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is 1.0:1.2. Under nitrogen protection, 600 mL of 2-methyltetrahydrofuran and 500 mL of ultrapure water were added to a 2 L four-necked flask. While stirring, 4-tert-butylphenyltetramethylsulfonium methylsulfonate (100.0 g, 1.0 eq) and sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate (169.2 g, 1.2 eq) were added. The mixture was stirred and heated to 40 °C, and then stirred at 40 °C for 4 hours. After the reaction was completed as detected by HPLC, the mixture was allowed to stand for liquid separation, washed with ultrapure water, the organic phase was concentrated, crystallized with isopropyl ether, and dried under vacuum to obtain 189.9 g of 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate, with a yield of 93.2%. The water content was 0.03%.

[0022] Example 3: A 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate and its preparation method, comprising the following steps: The molar ratio of 4-tert-butylphenyltetramethylsulfonium methylsulfonate to sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is 1.0:1.3. Under nitrogen protection, 500 mL of dichloromethane and 500 mL of ultrapure water were added to a 2 L four-necked flask. While stirring, 4-tert-butylphenyltetramethylsulfonium methylsulfonate (100.0 g, 1.0 eq) and sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate (183.3 g, 1.3 eq) were added. The mixture was stirred and heated to 40 °C, and then stirred at 40 °C for 4 hours. After the reaction was completed as detected by HPLC, the mixture was allowed to stand for liquid separation, washed with ultrapure water, the organic phase was concentrated, crystallized with isopropyl ether, and dried under vacuum to obtain 200.9 g of 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate, with a yield of 98.6%. The water content was 0.02%.

[0023] Example 4: 4-tert-Butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate and its preparation method, comprising the following steps: The molar ratio of 4-tert-butylphenyltetramethylsulfonium methanesulfonate to sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is 1.0:1.4. Under nitrogen protection, 500 mL of chloroform and 500 mL of ultrapure water are added to a 2 L four-necked flask. While stirring, 4-tert-butylphenyltetramethylsulfonium methanesulfonate (100.0 g, 1.0 eq) and sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate (197.5 g, 1.4 eq) are added. The mixture is stirred and heated to 40 °C, and then stirred at 40 °C for 4 hours. After the reaction is completed by HPLC detection, it is allowed to stand for liquid separation, washed with ultrapure water, the organic phase is concentrated, crystallized with isopropyl ether, and dried in vacuo to obtain 193.7 g of 4-tert-butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate. The yield is 95.1%. The water content is 0.05%.

[0024] Example 5: 4-tert-Butylphenyltetramethylsulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate and its preparation method, comprising the following steps: The molar ratio of 4-tert-butylphenyltetramethylenesulfonium methanesulfonate to sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is 1.0:1.5. Under nitrogen protection, 600 mL of ethyl acetate and 500 mL of ultrapure water were added to a 2 L four-necked flask. While stirring, 4-tert-butylphenyltetramethylenesulfonium methanesulfonate (100.0 g, 1.0 eq) and sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate (211.6 g, 1.5 eq) were added. The mixture was stirred and heated to 40 °C, and then stirred at 40 °C for 4 hours. After the reaction was completed as detected by HPLC, the mixture was allowed to stand for liquid separation, washed with ultrapure water, the organic phase was concentrated, crystallized with isopropyl ether, and dried in vacuo to obtain 189.3 g of 4-tert-butylphenyltetramethylenesulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate, with a yield of 92.9%. The water content is 0.04%.

[0025] 4-tert-butylphenyltetramethylenesulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate was prepared according to the method described in Example 3. 4-tert-butylphenyltetramethylenesulfonium methanesulfonate and sodium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate were added to a mixed system of dichloromethane and ultrapure water, and a coordination substitution reaction occurred to obtain 4-tert-butylphenyltetramethylenesulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate. The HPLC chromatogram of the 4-tert-butylphenyltetramethylenesulfonium 2-(((3r,5r,7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate synthesized in this example is as shown in Figure 1 shown.

[0026] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A compound used for etching semiconductor chips, characterized in that: The compound is 4-tert-butylphenyltetramethylenesulfonium 2-(((3r, 5r, 7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate, The structural formula (I) is shown below: （Ⅰ）。 2. The method for preparing a compound for semiconductor chip etching according to claim 1, characterized in that: The method comprises the following steps: under protective gas, uniformly mixing 4-tert-butylphenyl tetramethylene sulfonium methanesulfonate, 2-(((3r, 5r, 7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sodium sulfonate, an organic solvent and ultrapure water, stirring and heating the mixture for reaction, and after the reaction is completed, post-treating the mixture to obtain 4-tert-butylphenyl tetramethylene sulfonium 2-(((3r, 5r, 7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate.

3. The method for preparing a compound for semiconductor chip etching according to claim 2, characterized in that: The molar ratio of 4-tert-butylphenyltetramethylenesulfonium methanesulfonate and sodium 2-(((3r, 5r, 7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate is 1.0:(1.1-1.5).

4. The method for preparing a compound for semiconductor chip etching according to claim 2, characterized in that: The temperature of the stirring and heating reaction is 35-54°C.

5. The method for preparing a compound for semiconductor chip etching according to claim 2, characterized in that: The stirring and heating reaction time is 3-5h.

6. The method for preparing a compound for semiconductor chip etching according to claim 2, characterized in that: The organic solvent includes one or more of methyl tert-butyl ether, 2-methyltetrahydrofuran, dichloromethane, dichloroethane, chloroform and ethyl acetate.

7. A method for preparing 4-tert-butylphenyltetramethylenesulfonium 2-(((3r, 5r, 7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate according to claim 2, characterized in that: The protective gas is inert gas.

8. A method for preparing 4-tert-butylphenyltetramethylenesulfonium 2-(((3r, 5r, 7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate according to claim 2, characterized in that: The protective gas is nitrogen.

9. The method for preparing 4-tert-butylphenyltetramethylenesulfonium 2-(((3r, 5r, 7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate according to claim 2, characterized in that: The post-treatment includes liquid separation, ultrapure water washing, organic phase concentration, isopropyl ether crystallization, and vacuum drying to obtain 4-tert-butylphenyltetramethylenesulfonium 2-(((3r, 5r, 7r)-adamantane-1-carbonyl)oxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate.

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