Sulfonium sulfonate photoacid generator containing carborane structure and application of sulfonium sulfonate photoacid generator

Abstract

The invention discloses a sulfonium sulfonate photoacid generator containing a carborane structure and application of the sulfonium sulfonate photoacid generator, and particularly provides a compound which is composed of anions and cations, the structure of the anions is shown as a formula (I) or a formula (II), and the structure of the cations is shown as a formula (I) or a formula (II). The photoacid generator provided by the invention is novel in structure, high in exposure energy and good in application prospect.

Description

Technical Field

[0001] This invention relates to a sulfonate sulfonate salt containing a carborane structure as a photoacid-generating agent and its application. Background Technology

[0002] The integrated circuit industry is the foundation of modern intelligent and information-based systems, playing a vital role in various fields. Photolithography materials (specifically photoresist), also known as photoresist, are the most critical functional chemical materials involved in the integrated circuit industry. Their main components include resins, photoacid generators (PAGs), and corresponding additives and solvents.

[0003] As the wavelength of the light source in lithography machines continues to decrease and the feature size of integrated circuits (ICs) gradually shrinks, the impact of acid diffusion length on photolithographic patterns becomes increasingly significant, including decreased mask fidelity, deterioration of LWR (linewidth roughness), and degradation of pattern rectangularity. It has been found that the structure of PAG anions plays a crucial role in the overall performance of photoresists by influencing the interactions between PAG and other photoresist components. These interactions affect the diffusion characteristics of photogenerated acids. Therefore, the preparation of photoacid-generating agents (PAGs) with controllable acid diffusion is of paramount importance. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the deficiency of insufficient types of photo-induced acid-producing agents in the prior art, and to provide a novel sulfonium salt photo-induced acid-producing agent with a carbon borane structure and high exposure energy, as well as its application.

[0005] The present invention solves the above-mentioned technical problems through the following technical solution:

[0006] This invention provides a compound consisting of an anion and a cation, wherein the structure of the anion is shown in formula (I) or formula (II):

[0007]

[0008] Where -L1- is C 1-6 Alkylene; the C 1-6 In the alkylene group, one, two, or three -CH2- atoms are independently replaced by -C(O)O-, -O-, -S-, -NH-, or -C(Ra)(Rb)-.

[0009] R a For H, F, or CF3;

[0010] R b For F or CF3;

[0011] R is 1,2-carborane 1,7-Carborane or 1,12-Carborane;

[0012] The structure of the cation is shown in formula (III):

[0013]

[0014] X is S or I.

[0015] When X is I, n is 2; the two R0s are independently C. 1-30 Alkyl, C 3-30 cycloalkyl, C 6-30 aryl, with one or more R e Replacement C 1-30 Alkyl, with one or more R f Replacement C 3-30 cycloalkyl or with one or more R g Replacement C 6-30 Aryl;

[0016] When X is S, n is 3; the three R0s are independently C. 1-30 Alkyl, C 3-30 cycloalkyl, C 6-30 aryl, with one or more R e Replacement C 1-30 Alkyl, with one or more R f Replacement C 3-30 cycloalkyl or with one or more R g Replacement C 6-30 Aryl;

[0017] Alternatively, two R0s together with the adjacent X form a 5-14 quinary heterocycle or are bounded by one or more R0s. h The substituted 5-14 membered heterocycle; another R0 is C. 1-30 Alkyl, C 3-30 cycloalkyl, C 6-30 aryl, with one or more R e Replacement C 1-30 Alkyl, with one or more R f Replacement C 3-30 cycloalkyl or with one or more R g Replacement C 6-30 Aryl;

[0018] R e R f R g and R h Selected independently from halogens and C 1-6 Alkyl, C 1-6 Halogenated alkyl groups and -S-phenyl groups.

[0019] As a preferred embodiment of the present invention, the anion structure is shown in formula (I') or formula (II'):

[0020] As a preferred embodiment of the present invention, -L1- is C 1-6 Alkylene; the C 1-6 In the alkylene group, one, two, or three -CH2- are independently replaced by -C(O)O-, -O-, or -C(Ra)(Rb)-.

[0021] As a preferred embodiment of the present invention, -L1- is ethylene, linear butylene, or linear pentylene; one, two, or three -CH2- groups in the ethylene, linear butylene, or linear pentylene are independently replaced by -C(O)O-, -O-, -S-, -NH-, or -C(Ra)(Rb)-.

[0022] As a preferred embodiment of the present invention, -L1- is ethylene or linear butylene; one or two -CH2- in the ethylene or linear butylene are independently replaced by -C(O)O-, -O- or -C(Ra)(Rb)-.

[0023] As a preferred embodiment of the present invention, the -L1- in the anion is -C(O)OCH2CH2CF2-, -C(O)OCH2-, -C(O)OCH2CH2OC(O)-, -C(O)OCH(CF3)-, -CH2CH2CH2OC(O)-, -CH2CH2OCF2-, -CH2-OC(O)CH2OCF2-, or -C(O)OCH2CH2OCF2-.

[0024] As a preferred embodiment of the present invention, the anion is selected from the following structure:

[0025]

[0026] As a preferred embodiment of the present invention, the anion is

[0027]

[0028] In a preferred embodiment of the present invention, X is S; the three R0s are independently C. 1-6 Haloalkyl, C 6-10 aryl or aryl with one or more R g Replacement C 6-10 Aryl;

[0029] Alternatively, the two R0s together with the adjacent X form a 5-14 quinary heterocycle; the other R0 is C. 1-6 Haloalkyl, C 6-10 aryl or aryl with one or more R g Replacement C 6-10 Aryl;

[0030] As a preferred embodiment of the present invention, when X is S and R 0 When it forms a 5-14 member heterocycle together with the connected X, the 5-14 member heterocycle is

[0031] As a preferred embodiment of the present invention, R g Selected from C 1-6 One or more of alkyl and -S-phenyl; for example, one or more selected from methyl, tert-butyl and -S-phenyl.

[0032] As a preferred embodiment of the present invention, the cation is selected from the following structure:

[0033]

[0034] As a preferred embodiment of the present invention, the cation is

[0035] As a preferred embodiment of the present invention, the compound comprises having the following structure:

[0036]

[0037]

[0038] As a preferred embodiment of the present invention, the compound is

[0039]

[0040]

[0041] The present invention also provides the application of any of the foregoing compounds as photoacid generators in the preparation of photoresists.

[0042] the term

[0043] Unless otherwise specified, the terms used in this invention have the following meanings:

[0044] When listing numerical ranges, each value and subranges within that range are included. For example, "C1 to C6" includes C1, C2, C3, C4, C5, C6, C1-C6, C1-C5, C1-C4, C1-C3, C1-C2, C2-C6, C2-C5, C2-C4, C2-C3, C3-C6, C3-C5, C3-C4, C4-C6, C4-C5, and C5-C6 alkyl groups.

[0045] The term "alkyl" refers to a straight-chain or branched alkyl group having a specified number of carbon atoms (e.g., C1 to C6). Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc.

[0046] The term "cycloalkyl" refers to a compound having a specified number of carbon atoms (e.g., C4 to C5). 18 A polycyclic aromatic hydrocarbon (PAH) is a saturated cyclic group consisting solely of carbon atoms, which can be monocyclic, fused, bridged, or spirocyclic. A fused ring is a polycyclic aromatic hydrocarbon that shares two adjacent atoms among its monocyclic rings. A bridged ring is a polycyclic aromatic hydrocarbon that shares two or more atoms among its monocyclic rings. A spirocyclic ring is a polycyclic aromatic hydrocarbon that shares one atom among its monocyclic rings.

[0047] The term "heterocycle" refers to a ring having a specified number of ring atoms (e.g., 5 to 14), a specified number of heteroatoms (e.g., 1, 2 or 3), and a specified type of heteroatom (one or more of N, O and S), which can be monocyclic or polycyclic, and can be saturated or unsaturated heterocycles.

[0048] The term "aryl" refers to an aryl group having a specified number of carbon atoms (e.g., C6 to C5). 10 An aryl group is a cyclic group consisting solely of carbon atoms, which may be monocyclic or polycyclic, and at least one ring is aromatic (conforming to Hückel's rule). An aryl group is linked to other segments of the molecule via an aromatic or non-aromatic ring. Aryl groups include, but are not limited to, phenyl and naphthyl groups.

[0049] The "-" at the end of a group indicates that the group is connected to other segments in the molecule through that site. For example, -CH2-CH2- refers to ethylene.

[0050] The term "multiple" refers to 2, 3, 4, or 5.

[0051] When any variable (e.g., group R) a When these terms appear multiple times in the definition of a compound, their definitions are independent and do not affect each other. For example, a compound defined by three R's... a Replacement of C6~C 10 Aryl refers to C6~C 10 Aromatic compounds will be 3 R a Replace, 3 R aThe definitions are independent of each other and do not affect each other.

[0052] The positive and progressive effects of this invention are as follows:

[0053] (1) The carborane structure contained in the compound of the present invention has a large molecular weight, and the photoacid generator formed therefrom also has a large molecular weight, which can reduce the diffusion of the photoacid generator, which is beneficial to improve edge roughness, reduce line width roughness, and improve resolution.

[0054] (2) The photoacid generator of the present invention contains polar groups, which can increase the lipid solubility of the photoacid generator, making it easier to dissolve in the solvent. Furthermore, the polarity of the photoacid generator and the resin are closer, and the resin and the photoacid generator are mixed more evenly in the solvent, which is beneficial to forming a more uniform photoresist.

[0055] (3) The carborane structure contained in the photo-induced acid-producing agent of the present invention has strong rigidity and stability, and has excellent etching resistance.

[0056] (4) The synthetic route of the photo-induced acid-producing agent of the present invention is simple and easy to prepare. Detailed Implementation

[0057] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0058] Example 1

[0059] The synthetic route for the photoacid-producing agent PAG-1-PAG-5 is as follows:

[0060]

[0061] The specific steps are as follows:

[0062] Sodium salt 1-1 (7.9 g, 32 mmol) and DMAP (3.9 g, 32 mmol) were weighed into a 500 mL three-necked flask, purged with argon three times, and dissolved in 200 mL anhydrous acetonitrile. Under ice bath conditions, 40 mL of a carborane acyl chloride (7.8 g, 40 mmol) acetonitrile solution was slowly added dropwise. After the ice bath slowly thawed and the mixture was brought to room temperature, the reaction was stirred. After the reaction was complete, the system was evaporated to dryness, extracted with dichloromethane, filtered to remove the solid, washed three times with water, dried and concentrated the organic phase, and then slurried with diethyl ether. The concentrated solution was added dropwise under stirring, resulting in the formation of a white to pale yellow solid. Further slurrying yielded a white solid, ultimately giving esterified product 1-2 (12.1 g, 74%).

[0063] Raw materials 1-2 (1.04 g, 2.0 mmol) and triphenylthionium salt (598 mg, 2.0 mmol) were dissolved in 10 mL of a mixture of chloroform and water and stirred at room temperature for one hour. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and slurried with diethyl ether. A white solid product precipitated, yielding the target product PAG-1 (1.38 g, 100%).

[0064] 1 H NMR (400MHz, Chloroform-d) δ7.88–7.64(m,15H),4.50(t,J=6.2Hz,2H),4.12(s,1H),2.80(tt,J=18.0,6.2Hz,2H),3.18–1.46(m,10H); 19 FNMR(376MHz,Chloroform-d)δ-112.0(tt,J=18.2,5.0Hz),-118.7(d,J=5.0Hz)ppm.

[0065]

[0066] Raw materials 1-2 (1.04 g, 2.0 mmol) and thionium salt (741 mg, 2.0 mmol) were dissolved in 10 mL of a mixture of chloroform and water and stirred at room temperature for one hour. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and slurried with diethyl ether. A white solid product precipitated, yielding the target product PAG-2 (1.29 g, 100%).

[0067] 1 H NMR(400MHz,Chloroform-d)δ7.68(d,J=8.7Hz,2H),7.63(d,J=8.7Hz,2H),4.50(t,J=6.2Hz,2H),4.24–4.08 (m,3H),3.68–3.55(m,2H),2.74(tt,J=17.9,6.2Hz,2H),2.62–2.47(m,4H),3.18–1.46(m,10H),1.31(s,9H); 19 F NMR (376MHz, Chloroform-d) δ -112.1 (tt, J = 17.8, 5.0Hz), -118.5 (d, J = 5.0Hz) ppm.

[0068]

[0069] Raw materials 1-2 (1.04 g, 2.0 mmol) and thionium salt (869 mg, 2.0 mmol) were dissolved in 10 mL of a mixture of chloroform and water and stirred at room temperature for one hour. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and slurried with diethyl ether. A white solid product precipitated, yielding the target product PAG-3 (1.20 g, 97%).

[0070] 1 H NMR(400MHz,Chloroform-d)δ8.52(d,J=8.1Hz,2H),7.91(t,J=7.7Hz,2H),7.84(d,J=8.1Hz,2H),7.74 (t,J=7.7Hz,2H),4.48(t,J=6.1Hz,2H),4.10(s,1H),2.73(tt,J=18.0,6.2Hz,2H),3.18–1.46(m,10H); 19 F NMR (376MHz, Chloroform-d) δ -51.1, -111.9 (tt, J = 17.8, 5.0Hz), -118.4 (d, J = 5.0Hz) ppm.

[0071]

[0072] Raw materials 1-2 (1.04 g, 2.0 mmol) and thioonium salt (772 mg, 2.0 mmol) were dissolved in 10 mL of a mixture of chloroform and water and stirred at room temperature for one hour. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and slurried with diethyl ether. A white solid product precipitated, yielding the target product PAG-4 (1.20 g, 97%).

[0073] 1 H NMR(400MHz,Chloroform-d)δ7.87(d,J=8.7Hz,2H),7.71(d,J=8.7Hz,2H),4.52(t,J=6.2Hz,2H),4.46–4.36(m,2H),4 .23–4.07(m,3H),3.95–3.81(m,2H),3.72–3.58(m,2H),2.76(tt,J=17.9,6.2Hz,2H),3.18–1.46(m,10H),1.35(s,9H); 19 F NMR (376MHz, Chloroform-d) δ -112.0 (tt, J = 17.8, 5.0Hz), -118.5 (d, J = 5.0Hz) ppm.

[0074]

[0075] Raw materials 1-2 (1.04 g, 2.0 mmol) and thionium salt (1.03 g, 2.0 mmol) were dissolved in 10 mL of a mixture of chloroform and water and stirred at room temperature for one hour. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and slurried with diethyl ether. A white solid product precipitated, yielding the target product PAG-5 (1.48 g, 98%).

[0076] 1 H NMR(400MHz,Chloroform-d)δ7.82–7.60(m,10H),7.59–7.40(m,7H),7.31–7.22(m,2H) ,4.50(t,J=6.2Hz,2H),4.12(s,1H),2.78(tt,J=18.0,6.3Hz,2H),3.18–1.46(m,10H); 19 F NMR (376MHz, Chloroform-d) δ -112.0 (tt, J = 17.8, 5.0Hz), -118.6 (d, J = 5.0Hz) ppm.

[0077] Example 2

[0078] The synthetic routes for photoacid-producing agents PAG-6 and PAG-7 are as follows:

[0079]

[0080] The specific steps are as follows:

[0081] In a 250 mL three-necked flask, quaternary ammonium salt 2-1 (2.77 g, 10.0 mmol) and 50 mL of ultra-dry dichloromethane were added, followed by triethylamine (1.11 g, 11.0 mmol) and DMAP (122 mg, 1.0 mmol). Finally, a solution of acyl chloride (3.1 g, 15 mmol) in acetonitrile (15 mL) was added dropwise. The mixture was stirred at room temperature, and the starting materials were observed to gradually dissolve in the solution. The reaction was carried out for 4 hours. After the reaction was complete, a saturated sodium bicarbonate solution was added to the system to separate the organic phase, which was washed three times with water. After drying, the mixture was filtered and concentrated. After adding diethyl ether and slurrying, a large amount of white solid 2-2 precipitated.

[0082] The starting materials, sulfonate 2-2 (876 mg, 2.0 mmol) and triphenylthionium salt (598 mg, 2.0 mmol), were dissolved in 10 mL of a mixture of chloroform and water and stirred at room temperature for one hour. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and slurried with diethyl ether, resulting in the precipitation of a white solid product, PAG-6 (1.04 g, 87%).

[0083] 1H NMR (400MHz, Chloroform-d) δ7.84–7.63 (m, 15H), 4.82 (t, J = 13.2Hz, 1H), 4.38 (s, 2H), 3.20–1.50 (m, 10H); 19 F NMR (376MHz, Chloroform-d) δ-113.6 (t, J = 13.2Hz) ppm.

[0084]

[0085] The raw material substrates sulfonate 2-2 (876 mg, 2.0 mmol) and thioonium salt (772 mg, 2.0 mmol) were dissolved in 10 mL of a mixture of chloroform and water and stirred at room temperature for one hour. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and slurried with diethyl ether, resulting in the precipitation of a white solid product, PAG-7 (1.02 g, 92%).

[0086] 1 H NMR(400MHz,Chloroform-d)δ7.87(d,J=8.7Hz,2H),7.69(d,J=8.7Hz,2H),4.81(t,J=13.4Hz,2H),4.44–4.32( m,2H),4.29(s,1H),4.15–4.06(m,2H),3.96–3.85(m,2H),3.73–3.63(m,2H),3.20–1.50(m,10H),1.34(s,9H); 19 F NMR (376MHz, Chloroform-d) δ-113.6 (t, J = 13.4Hz) ppm.

[0087] Example 3

[0088] The synthetic routes for photoacid-producing agents PAG-8 and PAG-9 are as follows:

[0089]

[0090] The specific steps are as follows:

[0091] Sodium salt 3-1 (969 mg, 4.0 mmol) and DMAP (489 mg, 4.0 mmol) were added to a 250 mL three-necked flask. The flask was purged with argon three times. 60 mL of anhydrous acetonitrile was added and stirred. The solid did not completely dissolve at this point. A solution of anhydrous acetonitrile containing acyl chloride (992 mg, 4.8 mmol) (7 mL) was slowly added dropwise under ice bath conditions. After the addition was complete, the mixture was thawed in the ice bath and slowly brought to room temperature. The reaction system was initially white and turbid; upon standing, the turbidity settled in the lower layer. The reaction system was evaporated to dryness, dissolved in chloroform, washed three times with water, and slurried with diethyl ether. The concentrated solution was slowly added dropwise to diethyl ether to wash away impurities, resulting in the precipitation of a large amount of white solid. The solid was filtered and dried to obtain product 3-2 (1.16 g, 56%).

[0092] Sulfonate 3-2 (410 mg, 0.8 mmol) and triphenylthionium salt (239 mg, 0.8 mmol) were added to a 50 mL round-bottom flask. 10 mL of water and chloroform were added as reaction solvents, and the mixture was stirred at room temperature for 30 minutes. After concentrating the organic phase, the mixture was slurried with diethyl ether to precipitate as much solid as possible. The white solid was collected by filtration and dried to obtain product PAG-8 (571 mg, 87%).

[0093] 1 H NMR(400MHz,Chloroform-d)δ8.11(d,J=6.8Hz,2H),6.80(d,J=6.8Hz,2H),4.61–4.5 2(m,2H),4.52–4.44(m,2H),4.40(s,1H),3.24(d,J=1.7Hz,6H),3.07–1.30(m,10H); 19 F NMR(376MHz,Chloroform-d)δ-110.6.

[0094]

[0095] Sulfonate 3-2 (410 mg, 0.8 mmol) and thionium salt (309 mg, 0.8 mmol) were added to a 50 mL round-bottom flask. 10 mL of water and chloroform were added as reaction solvents, and the mixture was stirred at room temperature for 30 minutes. After concentrating the organic phase, the mixture was slurried with diethyl ether to precipitate as much solid as possible. The white solid was collected by filtration and dried to obtain product PAG-9 (398 mg, 79%).

[0096] 1H NMR(400MHz, Acetonitrile-d3)δ7.86(d,J=8.4Hz,2H),7.77(d,J=8.4Hz,H),4.90(s,1H),4.52–4.3 9(m,4H),4.39–4.25(m,2H),4.09–3.93(m,2H),3.79–3.62(m,4H),3.09–1.56(m,10H),1.35(s,9H); 19 F NMR(376MHz, Acetonitrile-d3)δ-105.9ppm.

[0097] Example 4

[0098] The synthetic route for the photoacid-producing agent PAG-10 is as follows:

[0099]

[0100] The specific steps are as follows:

[0101] Weigh out sodium salt 4-1 (504 mg, 2.0 mmol) and DMAP (293 mg, 2.4 mmol) into a 100 mL sealed tube, purge with argon three times, dissolve in 10 mL of anhydrous acetonitrile, and slowly add 3 mL of acetonitrile solution of acyl chloride (587 mg, 3.0 mmol) under ice bath conditions. After the ice bath slowly melts and the mixture returns to room temperature, stir and react overnight. The reaction was analyzed; the fluorine spectrum showed a yield of approximately 80%. After the reaction, wash once with hydrochloric acid, once with sodium bicarbonate, and three times with water, finally yielding approximately 0.6 mmol of purified product 3-2. Prepare a 0.2 mol / L chloroform solution in 3 mL.

[0102] In a 25 mL round-bottom flask, the starting materials sulfonate 4-2 (1 mL, 0.2 mmol) and thionium salt (63 mg, 0.21 mmol) were dissolved in a mixture of 1.5 mL chloroform and 1.5 mL water and stirred at room temperature for 20 minutes. The organic phase was washed three times with water, dried over anhydrous magnesium sulfate, filtered, slurried with diethyl ether, and dried under vacuum to obtain a white solid PAG-10 (96 mg, 72%).

[0103] 1 H NMR(400MHz,Chloroform-d)δ7.85–7.53(m,15H),5.96(dqd,J=19.1,6.4,1.4Hz,1H),4.49(s,1H),3.27–1.31(m,10H); 19 F NMR(376MHz,Chloroform-d)δ-58.1–-58.3(m),-96.9–-98.1(m),-105.1–-106.3(m)ppm.

[0104] Example 5

[0105] The synthetic routes for photoacid-producing agents PAG-11 and PAG-12 are as follows:

[0106]

[0107] The specific steps are as follows:

[0108] Under anhydrous and oxygen-free conditions, in a 100 mL Schlenk flask, 1.44 g (10 mmol) of o-carborane was dissolved in 20 mL of anhydrous THF. A 2.4 M n-BuLi solution (5.2 mL, 13 mmol) in n-hexane was slowly added dropwise. The reaction was allowed to proceed at room temperature for approximately 1 hour. The reaction was then placed in an ice bath, and 1.3 mL (20 mmol) of oxetane was slowly added, and the reaction was allowed to proceed at room temperature for 3 hours. TLC was performed using the starting material as a control. Once the starting material was detected by TLC, 5 mL of saturated NH4Cl aqueous solution was added to quench the reaction. 100 mL of water was then added, and the mixture was extracted three times with 100 mL of ethyl acetate. The organic phase was collected and extracted once more with 100 mL of saturated brine. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The mixture was then purified by column chromatography using petroleum ether:ethyl acetate in a ratio of 4:1 to 3:1. After separation, the purified solids were concentrated and dried to yield white solids of carborane propanol and carborane dipropanol.

[0109] Take 10 mL of a dry, sealed tube and place it in a magnetic oscillator. Weigh out 5-1 sulfonate 5-1 (132 mg, 0.3 mmol), dissolve it in 2 mL of anhydrous acetonitrile after purging with argon, and add carbonyl diimidazole (52 mg, 0.32 mmol). Stir at 50 °C for one hour. Dissolve carborane propanol (41 mg, 0.2 mmol) in a small amount of anhydrous acetonitrile and add it dropwise to the system, continuing the reaction for two hours. After the reaction is complete, add 10 mL of ethyl acetate to the system, wash the organic phase three times with 15 mL of water, dry and concentrate, filter, slurry twice with diethyl ether, discard the supernatant, and dry under vacuum to obtain PAG-11 (96 mg, 77%).

[0110] 1 H NMR (500MHz, Chloroform-d) δ7.80–7.57(m,15H),4.25(t,J=5.6Hz,2H),4.10(s,1H),2.46–2.39(m,2H),1.87–1.79(m,2H),2.95–1.36(m,10H); 19 F NMR(376MHz,Chloroform-d)δ-111.1ppm.

[0111] Take 10 mL of a dry, sealed tube and place it in a magnetic oscillator. Weigh out 5-1 sulfonate 5-1 (132 mg, 0.3 mmol), dissolve it in 2 mL of anhydrous acetonitrile after purging with argon, and add carbonyl diimidazole (52 mg, 0.32 mmol). Stir at 50 °C for one hour. Dissolve carborane propylene glycol (23 mg, 0.2 mmol) in a small amount of anhydrous acetonitrile and add it dropwise to the system, continuing the reaction for two hours. After the reaction is complete, add 10 mL of ethyl acetate to the system, wash the organic phase three times with 15 mL of water, dry and concentrate, filter, slurry twice with diethyl ether, discard the supernatant, and dry under vacuum to obtain PAG-12 (101 mg, 91%).

[0112] 1 H NMR(400MHz,Chloroform-d)δ7.81–7.51(m,30H),4.25(t,J=6.0Hz,4H),2.39–2.29(m,4H),1.87–1.76(m,4H).2.93–1.32(m,10H); 13 C NMR (126MHz, Chloroform-d) δ162.3 (t, J = 29.8 Hz), 134.7, 131.6, 131.1, 124.2, 113.4 (t, J = 286.2 Hz), 79.8, 65.3, 30.8, 28.6; 19 F NMR(376MHz,Chloroform-d)δ-111.8ppm.

[0113] Example 6

[0114] The synthetic route for the photoacid-producing agent PAG-13-PAG-16 is as follows:

[0115]

[0116] The specific steps are as follows:

[0117] First, carborane (14.4 g, 100 mmol) was dissolved in 250 mL of anhydrous THF. Then, a 2.5 M n-BuLi (46 mL, 115 mmol) solution of n-hexane was slowly added dropwise at 0 °C. The reaction was allowed to proceed at room temperature for approximately 30 minutes. The reaction was then placed in an ice bath to lower the temperature to 0 °C, and liquid ethylene oxide (7.5 mL, 150 mmol) was slowly added. The reaction was allowed to proceed at room temperature for 3 hours. After TLC showed the disappearance of the starting material, 100 mL of saturated NH4Cl aqueous solution was added to quench the reaction. Then, 300 mL of water was added, and the mixture was extracted three times with 300 mL of ethyl acetate. The organic phase was collected and extracted once more with 300 mL of saturated brine. The organic phases were combined and purified by column chromatography using petroleum ether:ethyl acetate as the eluent (4:1). The purified product was a white solid carborane ethanol (14.8 g, 78%).

[0118] In a 100 mL sealed tube, the substrate carborane in ethanol (2.82 g, 15.0 mmol) was dissolved in 30 mL of ultra-dry dichloromethane. Imidazole (1.23 g, 18.0 mmol) and PPh3 (4.33 g, 16.5 mmol) were added sequentially under argon atmosphere at 0 °C, followed by I2 (4.19 g, 16.5 mmol). After addition, the system changed from colorless and transparent to yellowish-brown and opaque. The temperature was gradually reduced from 0 °C to room temperature for one hour. After the reaction, the system was a brown solution with a yellow solid formed, which was quenched with Na2S2O3 solution. After quenching, the system became colorless and transparent. The combined organic phases were extracted, dried over anhydrous sodium sulfate, and the mother liquor was concentrated. Column chromatography was performed using n-hexane as eluent to obtain the product, finally yielding a white solid, iodoethyl carborane (3.9 g, 87%).

[0119] Under argon atmosphere, 1.52 g (12.0 mmol) of AgF was weighed into a 100 mL sealed tube, 15 mL of THF was added, and tetrafluorosulfonyl lactone (2.70 g, 15.0 mmol) was added at 0 °C. After the addition was complete, the ice bath was removed, and the reaction was allowed to proceed at room temperature for two hours until the system became a yellow, transparent liquid. Iodide (1.79 g, 6.0 mmol) was added, and the reaction continued at room temperature. A brown precipitate formed, and the reaction was monitored after two hours, indicating that the reaction was essentially complete. After the reaction was complete, the mixture was filtered through diatomaceous earth. Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. This extraction was repeated three times, followed by washing once with saturated sodium chloride solution. The organic phases were combined, dried over anhydrous sodium sulfate, and evaporated to dryness. Column chromatography was performed using petroleum ether:ethyl acetate (20:1) as the eluent to purify the product, yielding a colorless, oily liquid sulfonyl fluoride (1.82 g, 82%).

[0120] In a 50 mL round-bottom flask, sulfonyl fluoride (741 mg, 2.0 mmol) was dissolved in 10 mL of chloroform, and 10 mL of water was added. NEt3 (445 mg, 4.4 mmol) was added under stirring, and the mixture was stirred at room temperature for 5 minutes. Ion exchange was then initiated by adding thionium salt (627 mg, 2.1 mmol). After the reaction was complete, the mixture was washed three times with water. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated. The solution was then slurried with diethyl ether, resulting in the precipitation of a white solid. The solid was filtered and washed with diethyl ether to obtain the target photoacid-producing molecule PAG-13 (1.11 g, 88%).

[0121] 1 H NMR (400MHz, Chloroform-d) δ7.84–7.62(m,15H),4.76(s,1H),4.09(t,J=5.4Hz,2H),2.65(t,J=5.4Hz,2H),3.14–1.36(m,10H); 19F NMR (376MHz, Chloroform-d) δ -86.5 (t, J = 5.5Hz), -117.4 (t, J = 5.5Hz) ppm.

[0122]

[0123] In a 50 mL round-bottom flask, sulfonyl fluoride (741 mg, 2.0 mmol) was dissolved in 10 mL of chloroform, and 10 mL of water was added. NEt3 (445 mg, 4.4 mmol) was added under stirring, and the mixture was stirred at room temperature for 5 minutes. Ion exchange was then initiated by adding thionium salt (772 mg, 2.0 mmol). After the reaction was complete, the mixture was washed three times with water. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated. The solution was then slurried with diethyl ether, resulting in the precipitation of a white solid. The solid was filtered and washed with diethyl ether to obtain the target photoacid-producing molecule PAG-14 (1.09 g, 90%).

[0124] 1 H NMR(400MHz,Chloroform-d)δ7.87(d,J=8.4Hz,2H),7.69(d,J=8.4Hz,2H),4.60(s,1H),4.36(dt,J=13.8,3.4Hz,2H), 4.17–4.02(m,4H),3.90(d,J=11.8Hz,2H),3.77–3.61(m,2H),2.65(t,J=5.5Hz,2H),3.14–1.36(m,10H),1.34(s,9H); 19 F NMR (376MHz, Chloroform-d) δ -86.4 (t, J = 5.2Hz), -117.5 (t, J = 5.2Hz) ppm.

[0125]

[0126] In a 50 mL round-bottom flask, sulfonyl fluoride (598 mg, 1.0 mmol) was dissolved in 10 mL of chloroform, and 10 mL of water was added. NEt3 (445 mg, 4.4 mmol) was added under stirring, and the mixture was stirred at room temperature for 5 minutes. A thionium salt (772 mg, 2.0 mmol) was then added for ion exchange. After the reaction was complete, the mixture was washed three times with water. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated. The solution was then slurried with diethyl ether, resulting in the precipitation of a white solid. The solid was filtered and washed with diethyl ether to obtain the target photoacid-producing molecule PAG-15 (464 mg, 87%).

[0127] 1H NMR(400MHz,Chloroform-d)δ7.87(d,J=8.4Hz,4H),7.65(d,J=8.4Hz,4H),4.37–4.21(m,4H),4.17–3. 97(m,8H),3.98–3.80(m,4H),3.79–3.61(m,4H),2.73–2.57(m,4H),1.31(s,18H),3.11–1.38(m,10H); 19 F NMR(376MHz,Chloroform-d)δ-85.4,-116.8ppm.

[0128]

[0129] In a 50 mL round-bottom flask, sulfonyl fluoride (598 mg, 1.0 mmol) was dissolved in 10 mL of chloroform, and 10 mL of water was added. NEt3 (445 mg, 4.4 mmol) was added under stirring, and the mixture was stirred at room temperature for 5 minutes. A thionium salt (598 mg, 2.0 mmol) was then added for ion exchange. After the reaction was complete, the mixture was washed three times with water. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated. The mixture was then slurried with diethyl ether, resulting in the precipitation of a white solid. The solid was filtered and washed with diethyl ether to obtain the target photoacid-producing molecule PAG-16 (480 mg, 86%).

[0130] 1 H NMR(400MHz, Acetonitrile-d3)δ7.85(t,J=7.3Hz,12H),7.74(t,J=7.9Hz,12H),7.6 9(d,J=7.8Hz,6H),4.12(t,J=6.1Hz,4H),2.70(t,J=6.1Hz,4H),3.11–1.38(m,10H); 19 F NMR(376MHz, Acetonitrile-d3)δ-85.9,-117.4ppm.

[0131] Example 7

[0132] We conducted exposure tests on some of the synthesized photoacid-generating agents. Test method: A mixed solvent was prepared using 180g propylene glycol methyl ether acetate (PGMEA, electronic grade), 90g propylene glycol methyl ether (PGME, electronic grade), and 30.0g γ-butyrolactone (GBL, electronic grade). 15.0g of acrylic resin was added to the above mixed solvent system and stirred overnight until fully dissolved. 375mg of quenching agent (2,6-diisopropylaniline) (as shown in the table below) was added to the system, and the mixture was stirred for 3 hours. The system was filtered through a PTFE membrane (0.22μm) to obtain the photoresist. 10.0028g of the system was taken, and the solvent was evaporated to dryness to obtain...

[0133] Solid content: 471.4 mg, solid content of the system: 4.72%. The photoresist was spin-coated onto the test wafer, baked at 80 degrees Celsius for 1 minute, and then exposed to an exposure instrument. If an exposure pattern appeared, it indicates acid formation, and the exposure energy was obtained.

[0134]

[0135]

[0136] The results show that the photoacid-generating agent obtained in this application can generate acid through photosensitivity and has suitable exposure energy.

[0137] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.

Claims

1. A compound comprising an anion and a cation, wherein the structure of the anion is shown in formula (I) or formula (II): in, -L1- is independent for C 1-6 Alkylene; the C 1-6 One, two, or three -CH2- groups in the alkylene group are independently surrounded by -C(O)O-, -O-, -S-, -NH-, or -C(R-). a (R) b - Replaced by; R a For H, F, or CF3; R b For F or CF3; R is 1,2-carborane, 1,7-carborane, or 1,12-carborane; The structure of the cation is shown in formula (III): X is S or I. When X is I, n is 2; the two R0s are independently C. 1-30 Alkyl, C 3-30 cycloalkyl, C 6-30 aryl, with one or more R e Replacement C 1-30 Alkyl, with one or more R f Replacement C 3-30 cycloalkyl or with one or more R g Replacement C 6-30 Aryl; When X is S, n is 3; the three R0s are independently C. 1-30 Alkyl, C 3-30 cycloalkyl, C 6-30 aryl, with one or more R e Replacement C 1-30 Alkyl, with one or more R f Replacement C 3-30 cycloalkyl or with one or more R g Replacement C 6-30 Aryl; Alternatively, two R0s together with the adjacent X form a 5-14 quinary heterocycle or are bounded by one or more R0s. h The substituted 5-14 membered heterocycle; another R0 is C. 1-30 Alkyl, C 3-30 cycloalkyl, C 6-30 aryl, with one or more R e Replacement C 1-30 Alkyl, with one or more R f Replacement C 3-30 cycloalkyl or with one or more R g Replacement C 6-30 Aryl; R e R f R g and R h Independently selected from halogens, C 1-6 Alkyl, C 1-6 Halogenated alkyl groups and -S-phenyl groups.

2. The compound according to claim 1, characterized in that, It meets one or more of the following conditions: (1) The anion structure is shown in formula (I') or formula (II'): (2)-L1- is independently C 1-6 Alkylene; the C 1-6 In an alkylene group, one, two, or three -CH2- atoms are independently surrounded by -C(O)O-, -O-, or -C(R-). a (R) b - Replaced by; (3) X is S; the three R0s are independently C. 1-6 Haloalkyl, C 6-10 aryl or aryl with one or more R g Replacement C 6-10 Aryl; Alternatively, the two R0s together with the adjacent X form a 5-14 quinary heterocycle; the other R0 is C. 1-6 Haloalkyl, C 6-10 aryl or aryl with one or more R g Replacement C 6-10 Aryl; and (4)R g Selected from C 1-6 One or more of alkyl and -S-phenyl.

3. The compound according to claim 1, characterized in that, It meets one or more of the following conditions: (1) -L1- is independently ethylidene, linear butylidene, or linear pentylene; wherein one, two, or three -CH2- groups of the ethylidene, linear butylidene, or linear pentylene are independently converted by -C(O)O-, -O-, -S-, -NH-, or -C(R a (R) b - Replaced by; (2) When X is S, and the two R0s together with the connected X form a 5-14 member heterocycle, the 5-14 member heterocycle is and (3)R g It is selected from one or more of methyl, tert-butyl and -S-phenyl.

4. The compound according to claim 1, characterized in that, -L1- is independently ethylidene or linear butylidene; one or two -CH2- groups in the ethylidene or linear butylidene group are independently converted by -C(O)O-, -O- or -C(R a (R) b )- Replaced.

5. The compound according to claim 1, characterized in that, -L1- is -C(O)OCH2CH2CF2-, -C(O)OCH2-, -C(O)OCH2CH2OC(O)-, -C(O)OCH(CF3)-, -CH2CH2CH2OC(O)-, -CH2CH2OCF2-, -CH2-OC(O)CH2OCF2- or -C(O)OCH2CH2OCF2-.

6. The compound according to claim 1, characterized in that, It meets one or two of the following conditions: (1) The anion is selected from the following structure: The cations described in (2) are selected from the following structures:

7. The compound according to claim 1, characterized in that, It meets one or two of the following conditions: (1) The anion is The cations described in (2) are 8. The compound according to claim 1, characterized in that, The compounds include those having the following structure:

9. The compound according to claim 1, characterized in that, The compound is 10. The use of a compound as a photoacid-generating agent in the preparation of photoresists, as described in any one of claims 1-9.

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