Polysulfonium-based monomolecular resins and photoresist compositions thereof

Abstract

The application provides a series of novel monomolecular resins based on polysulfonium salt, i.e., compounds shown in formula (I), which are cheap and easy to obtain, and the synthesis process is simple. The compounds shown in formula (I) are used as single-component non-chemical combination photoresist, which avoids the problems of uneven distribution of acid generators and acid diffusion in chemical amplification photoresist, and the obtained pattern has high resolution and low line width roughness.

Description

Technical Field

[0001] This invention belongs to the field of photolithography materials technology, specifically relating to a class of monomolecular resins based on polythionium salts and their photoresist compositions, photoresist coatings and their applications. Background Technology

[0002] Molecular glasses are a class of functional materials composed of small, monodisperse organic molecules that can form stable amorphous glasses at room temperature. Compared to traditional polymer photoresists, molecular glasses possess smaller monodisperse structural blocks, well-defined molecular weights, and reproducible stereochemical structures, enabling precise synthesis and facilitating the acquisition of high-resolution and low-LWR / LER patterns. Traditionally used chemically amplified photoresists (CARs) rely on mixing or polymerically bonded photoacid generators (PAGs) to achieve solubility differences. This chemically amplified system suffers from a number of problems, such as high line edge roughness (LER) and post-exposure instability. To address these issues, research on novel non-chemically amplified photoresists (n-CARs) is receiving increasing attention. n-CARs are radiation-sensitive materials that do not require the addition of PAGs in their formulation, containing only the host material. Therefore, they can effectively solve the compatibility problems between the host material and additives, as well as the problem of uneven acid diffusion after exposure, thereby reducing the LER value. However, compared to the number of CARs reported to date, the number of n-CARs is very limited, especially n-CARs based on molecular glasses. Therefore, it is of great significance to develop molecular glass n-CARs with strong photolithography potential, especially for sub-20nm patterning applications with low LER / LWR characteristics. Summary of the Invention

[0003] To address the aforementioned technical problems, the present invention provides a type of monomolecular resin based on polythionium salts and a photoresist composition comprising the monomolecular resin.

[0004] The technical solution of the present invention is as follows:

[0005] The compound represented by formula (I):

[0006]

[0007] Wherein, A is selected from the following groups, Indicates the connection key:

[0008]

[0009] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R14 R 15 R 16 R 17 R 18 R 19 R 20 Whether the same or different, each is independently selected from -S + R S1 R S2 -OC 1-15 Alkyl-C 6-20 Aryl-S + R S1 R S2 or group Z, wherein group Z is H, unsubstituted, or optionally substituted with one, two, or more R groups. A The following groups are substituted: C 1-15 Alkyl, C 1-15 Alkoxy, C 3-20 cycloalkyl, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclic, -C 1-15 Alkyl-C 6-20 Aryl, -C 1-15 Alkyl-5-20 heteroaryl, -C 1-15 Alkyl-CO-C 6-20 Aryl, -C 1-15 Alkyl-CO-5-20-membered heteroaryl, -C 1-15 Alkyl-CO-C 1-15 Alkyl, -C 1-15 Alkyl-CO-C 3-20 cycloalkyl; R0 is selected from C 1-15 Alkoxy, -OC 6-20 Aryl, -OC 1-15 Alkyl-C 6-20 Aryl, -O-5-20 heteroaryl, -OC 1-15 Alkyl-C 6-20 Aryl-S + R S1 R S2 ;

[0010] R A Selected from =O, NO2, C 1-15 Alkyl, C 1-15 Alkoxy, C 3-20 cycloalkyl, C 6-20 Aryl, 5-20 heteroaryl;

[0011] R S1 R S2 Whether identical or different, each is independently selected from unsubstituted or arbitrarily selected by one, two or more R B The following groups are substituted: C1-15 Alkyl, C 3-20 cycloalkyl, C 6-20 Aryl, 5-20 heteroaryl, -C 1-15 Alkyl-C 6-20 Aryl, deuterated C 1-15 Alkyl groups (such as deuterated methyl groups), or R S1 R S2 Together with the S connected thereto, they form an unsubstituted or optionally substituted group of one, two or more R groups. B The substituted 5-8 member sulfur-containing heterocyclic group; the 5-8 member sulfur-containing heterocyclic group optionally further contains 1-2 oxygen or sulfur atoms; the 5-8 member sulfur-containing heterocyclic group is also optionally fused with one or two benzene rings;

[0012] R B They may be the same or different, and are independently selected from H, oxo (=O), nitro, CN, and C. 1-15 Alkyl, C 1-15 Alkoxy;

[0013] X – It is an anion, such as halide ions, carboxylate ions, sulfate ions, alkyl sulfonates, haloalkyl sulfonates (such as trifluoromethanesulfonate, perfluoropropyl sulfonate, perfluorobutyl sulfonate), p-toluenesulfonate, anions of sulfonamides, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, or bis(trifluoromethanesulfonyl)imide ions.

[0014] n equals the thionium salt group -S in the molecule. + R S1 R S2 S + The number of S + and X – To make the compound as a whole electrically neutral, n is an integer from 2 to 8, that is, the compound of formula (I) has 2 to 8 -S groups. + R S1 R S2 ;

[0015] In some embodiments of the present invention, the compound of formula (I) has 2-6 -S groups. + R S1 R S2 For example, having 2, 3, 4, 5, or 6 -S groups. + R S1 R S2 .

[0016] In some embodiments of the present invention, R1-R 20 It contains 4 groups -S + R S1 R S2 And each phenyl group has one -S group.+ R S1 R S2 .

[0017] In some embodiments of the present invention, the compound of formula (I) has 2-6 -S groups. + R S1 R S2 Furthermore, E1 and E2 each contain a -S group. + R S1 R S2 .

[0018] In some embodiments of the present invention, the thioonium salt group is located at the ortho, meta, or para position.

[0019] According to an embodiment of the present invention, the thionium salt group -S + R S1 R S2 Selected from the following groups that are unsubstituted or optionally substituted by one, two or more R1':

[0020]

[0021] in, Indicates a connection key; R 1a and R 1b They can be the same or different, each independently selected from no substitution, or by one, two or more R... C The following groups are substituted: C 1-15 Alkyl, C 3-20 cycloalkyl, -C 1-15 Alkyl-C 6-20 Aryl, -C 1-15 Alkyl-5-20 heteroaryl, -C 6-20 Aryl-C 1-15 Alkyl, deuterated C 1-15 Alkyl; R C R1' may be the same or different, and are independently selected from =O, nitro, C 1-15 Alkyl, C 1-15 Alkyl group; m is selected from integers from 0 to 5; Y is selected from CH2, O, S, C(O);

[0022] Preferably, the group R 1a and R 1b Choose one of the following structures:

[0023]

[0024] in, Indicates a connection key.

[0025] In some embodiments of the present invention, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 Whether the two are the same or different, they are each independently selected from H and -S. + R S1 R S2 C 1-6 Alkyl, C 1-6 Alkoxy; R S1 R S2 Selected from C 1-6 Alkyl, C 6-12 Aryl, -C 1-6 Alkyl-C 6-12 Aryl;

[0026] In some preferred embodiments of the present invention, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 Whether they are the same or different, they are each independently selected from H and -S. + (C 1-6 Alkyl)2, -S + (C 6-12 Aryl)2, -S + (-C 1-6 Alkyl C 6-12 Aryl)(C 1-6 alkyl).

[0027] In some embodiments of the present invention, R0 is C. 1-6 Alkoxy, -OC 1-6 Alkyl-C 6-12 Aryl-S + R S1 R S2 -OC 1-6 Alkyl-C 6-12 Aryl; R S1 R S2 Selected from C1-6 Alkyl, C 6-12 Aryl, -C 1-6 Alkyl-C 6-12 Aryl.

[0028] In some preferred embodiments of the present invention, R0 is C. 1-6 Alkoxy, -OC 1-6 Alkyl-C 6-12 Aryl, -OC 1-6 Alkyl-C 6-12 Aryl-S + (C 6-12 Aryl)2, -OC 1-6 Alkyl-C 6-12 Aryl-S + (C 1-6 Alkyl)2.

[0029] In some preferred embodiments of the present invention, X is trifluoromethanesulfonate or hexafluoroantimonate.

[0030] In some preferred embodiments of the present invention, n is 4 or 6.

[0031] As an example, the compound shown in formula (I) is selected from the following compounds:

[0032]

[0033]

[0034] The present invention also provides a method for preparing the compound shown in formula (I) above, comprising the following steps: reacting compound (IV) with R S2 -L and MX are mixed and reacted to give the compound of formula (I); L is a leaving group, such as a halogen; R S2 As defined above, MX is a metal salt;

[0035]

[0036] Where A is defined above, R1', R2', R3', R4', R5', R6', R7', R8', R9', R 10 '、R 11 '、R 12 '、R 13 '、R 14 '、R 15 '、R 16 '、R 17 '、R 18 '、R 19 '、R 20 'for -SR S1 -OC 1-15 Alkyl-C6-20 Aryl-SR S1 Or group Z, where group Z is as defined above, and R0' is selected from C. 1-15 Alkoxy, -OC 6-20 Aryl, -OC 1-15 Alkyl-C 6-20 Aryl, -O-5-20 heteroaryl, -OC 1-15 Alkyl-C 6-20 Aryl-SR S1 .

[0037] According to the present invention, the compound of formula (IV) can be prepared by the following method, comprising:

[0038]

[0039] Among them, A, R0, R1', R2', R3', R4', and R5' are defined as above.

[0040] The present invention also provides another method for preparing the compound shown in formula (I), comprising the following steps: reacting the compound shown in formula (V) with a sulfoxide compound to obtain the compound shown in formula (I);

[0041]

[0042] Among them, R1”, R2”, R3”, R4”, R5”, R6”, R7”, R8”, R9”, R 10 "、R 11 "、R 12 "、R 13 "、R 14 "、R 15 "、R 16 "、R 17 "、R 18 "、R 19 "、R 20 "for H, -OC" 1-15 Alkyl-C 6-20 Aryl or group Z;

[0043] R0” is C 1-15 Alkoxy, -OC 6-20 Aryl, -OC 1-15 Alkyl-C 6-20 Aryl, -O-5-20 heteroaryl.

[0044] Optionally, the compound shown in formula (I) can also undergo ion exchange with the corresponding anion solution to obtain compounds of formula (I) with different anions.

[0045] The sulfoxide compound is R S1 -SO-RS2 .

[0046] According to an embodiment of the present invention, the reaction can be carried out in the presence of a catalyst, which can be trifluoromethanesulfonic anhydride or trifluoromethanesulfonic acid.

[0047] The present invention also provides the use of the compound represented by formula (I) above for the preparation of photoresists.

[0048] According to an embodiment of the present invention, the photoresist is a single-component photoresist that does not contain any active ingredients other than the compound shown in formula (I).

[0049] The present invention also provides a photoresist composition comprising the compound shown in formula (I).

[0050] According to an embodiment of the present invention, the photoresist composition further includes a solvent selected from one, two or more of the following substances: propylene glycol methyl ether acetate (PGMEA), dimethylformamide (DMF), cyclohexanone, ethyl n-pentanone, ethyl isopentanone, ethanol, acetonitrile, isopropanol, acetone, methyl n-pentanone, and methyl isopentanone.

[0051] According to an embodiment of the present invention, the photoresist composition is a positive or negative photoresist composition, comprising the compound shown in formula (I) and a photoresist solvent.

[0052] In one embodiment, the photoresist composition is a single-component photoresist, which consists of the compound shown in formula (I) and a photoresist solvent. That is, the photoresist composition includes only one component other than the photoresist solvent, namely the compound shown in formula (I).

[0053] The present invention also provides a photoresist coating comprising the compound shown in formula (I).

[0054] The present invention also provides a method for preparing the above-mentioned photoresist coating, wherein the above-mentioned photoresist composition is applied to a substrate to prepare the coating.

[0055] Preferably, the application method is spin coating.

[0056] Preferably, the substrate is a silicon wafer substrate.

[0057] Preferably, the photoresist coating is a thin film.

[0058] The present invention also provides the application of the photoresist coating in photolithography.

[0059] The compound shown in formula (I) of this invention has a high glass transition temperature (above 170°C) due to its unique polythionium salt structure, and can be used for photolithography.

[0060] According to an embodiment of the present invention, the photoresist coating can be used in 248nm lithography, 193nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography or electron beam lithography, preferably in extreme ultraviolet and electron beam lithography technologies.

[0061] The beneficial effects of this invention are as follows:

[0062] (1) This invention provides a series of novel monomolecular resins based on polythionium salts, namely the compounds shown in formula (I), whose raw materials are cheap and readily available, and whose synthesis process is simple.

[0063] (2) The compound shown in formula (I) of this invention can be used as a single-component non-chemical photoresist, avoiding the problems of uneven distribution of acid-generating agents and anti-acid diffusion agents and uneven acid diffusion in chemically amplified photoresists. The resulting pattern has high resolution and low line width roughness.

[0064] (3) The sulfur-containing polyphenylthionium salt monomolecular resin of the present invention has a definite molecular structure and a single molecular size, which can well meet the requirements of high-resolution photolithography.

[0065] Terms and Definitions

[0066] Unless otherwise defined, all technical terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains.

[0067] "More than three" means three or more.

[0068] Term "C" 1-15 "Alkyl" should be understood as referring to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 15 carbon atoms. For example, "C 1-6 "Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers.

[0069] Term "C" 1-15 "Alkoxy" should be understood as -OC 1-15 Alkyl, wherein C 1-15 Alkyl groups have the above definition.

[0070] Term "C"3-20 "Cycloalkyl" should be understood as representing a saturated monovalent monocyclic, bicyclic, or polycyclic hydrocarbon ring (also called a fused ring hydrocarbon ring) with 3-20 carbon atoms. Bicyclic or polycyclic cycloalkyl includes fused cycloalkyl, bridged cycloalkyl, and spirocyclic cycloalkyl; fused ring refers to a fused ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing a bond). Bridged ring refers to a fused ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. Spirocyclic refers to a fused ring structure formed by two or more cyclic structures sharing a single ring atom. For example, the C 3-20 Cycloalkyl groups can be C 3-8 Monocyclic cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C 7-12 Circoalkyl, such as decahydronaphthalene ring; or C 7-12 Bridged cycloalkyl groups, such as norbornene, adamantane, and bicyclo[2,2,2]octane.

[0071] The term "3-20 membered heterocyclic group" refers to a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O, and S, preferably a "3-10 membered heterocyclic group". The term "3-10 membered heterocyclic group" also refers to a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3, heteroatoms selected from N, O, and S. The heterocyclic group can be connected to the rest of the molecule via any one of the carbon atoms or a nitrogen atom (if present). Specifically, the heterocyclic group can include, but is not limited to: 4-membered rings, such as azirmonobutyl or oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoyl, pyrazolyl, or pyrrololinyl; or 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazinyl, or trithiaalkyl; or 7-membered rings, such as diazacycloheptyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, for example, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopenta[c]pyrrole-2(1H)-yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl ring. The nitrogen-containing ring may be partially unsaturated, i.e., it may contain one, two, or more double bonds, for example, but not limited to, 2,5-dihydro-1H-pyrrole, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, or it may be benzo-fused, for example, but not limited to, dihydroisoquinolinyl, 1,3-benzooxazolyl, or 1,3-benzodioxacyclopentenyl. According to the invention, the heterocyclic group is non-aromatic.

[0072] Term "C" 6-20"Aryl" should be understood as representing a monocyclic, bicyclic, or tricyclic hydrocarbon ring with 6 to 20 carbon atoms that is monovalent and partially aromatic, preferably "C". 6-14 Aryl. The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20 When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0073] The term "5-20-membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, such as "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and in each case, may be benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc.

[0074] The term "C" above 1-15 The definition of "alkyl" also applies to other C-containing compounds. 1-15 Alkyl groups, such as -C1-15 Alkyl-C 6-20 Aryl, -C 1-15 Alkyl-5-20 heteroaryl, -C 1-15 Alkyl-CO-C 6-20 Aryl, -C 1-15 Alkyl-CO-5-20-membered heteroaryl, -C 1-15 Alkyl-CO-C 1-15 Alkyl, -C 1-15 Alkyl-CO-C 3-20 cycloalkyl, -OC 1-15 Alkyl-C 6-20 Aryl-S + R S1 R S2 wait.

[0075] Similarly, C 6-20 Aryl, 5-20 heteroaryl, C 3-20 The cycloalkyl group has the same definition throughout the text. Attached Figure Description

[0076] Figure 1 The differential scanning calorimetry (DSC) curve and thermogravimetric curve are shown for compound I-2 in Example 5 of this invention.

[0077] Figure 2 The differential scanning calorimetry (DSC) curve and thermogravimetric curve are shown for compound I-4 in Example 9 of this invention.

[0078] Figure 3 This is an atomic force microscope (AFM) image of compound I-2 in Example 5 of the present invention.

[0079] Figure 4 This is a scanning electron microscope (SEM) image of the photolithographic stripes (exposure periods of 50 nm, 44 nm, and 40 nm) of the negative resist film of the compound I-2 host material in Example 5 of the present invention. Detailed Implementation

[0080] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0081] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0082] Example 1

[0083] The synthetic route for preparing compound III-1 is as follows:

[0084]

[0085] Compound VI-1 (8 g, 14 mmol, 1 eq) and anhydrous potassium carbonate (7.82 g, 57 mmol, 4 eq) were added to a 250 mL round-bottom flask, and 40 mL of dry N,N-dimethylformamide (DMF) was dissolved in the solution. Iodobutane (7.73 g, 42 mmol, 3 eq) was added to the reaction system, and the reaction was carried out at 90 °C for 5 hours. The reaction solution was slowly added dropwise to a large amount of water, which produced a large amount of white precipitate. The precipitate was filtered to obtain a white solid in 80% yield. 1 H NMR (400MHz, CDCl3) δ=8.04(s,4H),4.06(t,J=6.3,4H),1.86(tt,J1=7.0,J2=6.5,4H),1.56(qt,J1=7.4,J2=7.4,4H),0.99(t,J=7.3,6H); MS (EI):m / z=677.70, calculated value C 20 H 22 Br4O4S + m / z = 677.79 ([M]) + ).

[0086] Example 2

[0087] The synthetic route for preparing compound IV-1 is as follows:

[0088]

[0089] In a 200 mL Schleck flask, III-1 (6.1 g, 9 mmol, 1.0 eq), 3-methylthiophenylboronic acid (7.5 g, 45 mmol, 5.0 eq), and tetrahydrofuran (80 mL) were added. Anhydrous potassium carbonate solid (6.2 g, 45 mmol, 5 eq) was weighed, dissolved in 30 mL of water, and added to the flask. The system was deoxygenated three times under a nitrogen atmosphere. Then, tetra(triphenylphosphine)palladium catalyst (208 mg, 0.18 mmol, 0.02 eq) was added under a nitrogen atmosphere, the mixture was heated to reflux for 10 h, cooled to room temperature, and extracted with dichloromethane / water. The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent. A dichloromethane solution of the product was added dropwise to a large amount of ethanol to allow precipitation, and the mixture was stirred at room temperature for 2 h. The product was filtered and dried to give a white solid of 6.5 g (85% yield). 1H NMR (400MHz, CDCl3) δ = 8.0 (s, 4H), 7.41 (s, 4H), 7.34 (d, J = 6.0, 4H), 7.32 (d, J = 6.0, 4H), 7.22-7.24 (m, 4H), 4.06 (t, J = 6.3, 4H) ), 1.86 (tt, J1 = 7.0, J2 = 6.5, 4H), 1.56 (qt, J1 = 7.4, J2 = 7.4, 4H), 0.99 (t, J = 7.3, 6H), 2.45 (s, 12H); MS (ESI): m / z = 887.24, calculated value C 49 H 52 O4S5Na + m / z = 887.24([M+Na]) + ).

[0090] Example 3

[0091] The synthetic route for preparing compound I-1 is as follows:

[0092]

[0093] Compound IV-1 (5.1 g, 6 mmol, 1 eq) and silver trifluoromethanesulfonate (9.2 g, 36 mmol, 6 eq) were added to a 250 mL round-bottom flask and dissolved in 40 mL of dry dichloromethane with stirring. 30 mL (5.1 g, 36 mmol, 6 eq) of a dichloromethane solution of iodomethane was slowly added dropwise. After the addition was complete, the reaction mixture was reacted in the dark for 3 h. The reaction mixture was allowed to stand, and the supernatant was discarded. The solid was dissolved in acetonitrile, and the AgI precipitate was removed by filtration, yielding a colorless solution. After removing a large amount of solvent by rotary evaporation, a white precipitate was obtained by dropwise addition to diethyl ether, with a yield of 85%. 1 H NMR (400MHz, CD3CN) δ8.19(s,4H),8.02(d,J=7.7Hz,4H),7.98(s,4H),7.9(d,J=7.6Hz,4H),7.76(dd,J=7.7,4H),3.20(t,J=5.9, 4H), 3.17 (s, 24H), 1.04 (tt, J1=7.0, J2=7.0, 4H), 0.80 (qt, J1=7.1, J2=7.0, 4H), 0.41 (t, J=7.4, 6H); MS (ESI): m / z=353.09, calculated value C 53 H 62 F3O7S6 3+ m / z = 353.09 ([M]) 3+ m / z = 148.95, calculated value CF3SO3 - m / z = 148.95 ([M]) - ).

[0094] Example 4

[0095] The synthetic route for preparing compound V-2 is as follows:

[0096]

[0097] In a 200 mL Schleck flask, add III-1 (5.4 g, 8 mmol, 1.0 eq), phenylboronic acid (7.3 g, 40 mmol, 5.0 eq), and 80 mL of dioxane. Weigh anhydrous potassium carbonate solid (5.5 g, 40 mmol, 5 eq), dissolve it in 30 mL of water, and add it to the flask. Deoxygenate the system three times under a nitrogen atmosphere. Add tetra(triphenylphosphine)palladium catalyst (185 mg, 0.16 mmol, 0.02 eq) under a nitrogen atmosphere, heat under reflux for 10 h, cool to room temperature, and extract with dichloromethane / water. Combine the organic layers, dry with anhydrous sodium sulfate, and concentrate under reduced pressure to remove the solvent. Add a dichloromethane solution of the product dropwise to a large amount of ethanol to precipitate, stir at room temperature for 2 h, filter, and dry to give a white solid of 4.8 g (90% yield). 1 H NMR (400MHz, DMSO-d6) δ=8.0(s,4H),7.57(d,J=7.3,8H),7.48-7.39(m,12H),3.17(t,J=5.8,4H),1.04(tt,J1=6.5,J2=6.4,4H),0.86(qt,J1=7.2,J2=7.2,4H),0.45(t,J=7.3,6H); MS (ESI):m / z=703.28, calculated value C 45 H 44 O4SNa + m / z = 703.28([M+Na]) + ).

[0098] Example 5

[0099] The synthetic route for preparing compound I-2 is as follows:

[0100]

[0101] Compound V-2 (6.5 g, 9.7 mmol, 1 eq) and diphenyl sulfoxide (9.8 g, 48.5 mmol, 5 eq) were added to a 250 mL round-bottom flask and dissolved in 20 mL of dry dichloromethane. The reaction mixture was placed in an acetonitrile bath, and 20 mL of a dichloromethane solution of trifluoromethanesulfonic anhydride (27 g, 97 mmol, 10 eq) was added dropwise. After the addition was complete, the reaction was carried out in the dark for 5 h. Most of the reaction mixture was removed by rotary evaporation. A white precipitate was obtained by adding the precipitate dropwise to diethyl ether, with a yield of 80%. 1H NMR (400MHz, DMSO-d6) δ=8.22(s,4H),7.97-7.77(m,56H),3.18(t,J=5.9,4H),1.04(tt,J1=7.0,J2=7.0,4H),0.80(qt,J1=7.1,J2=7.0,4H),0.41(t,J=7.4,6H); MS (ESI):m / z=518.80, calculated value C 93 H 78 F3O7S6 3+ m / z = 518.80 ([M]) 3+ m / z = 148.95, calculated value CF3SO3 - m / z = 148.95 ([M]) - ).

[0102] Example 6

[0103] The synthetic route for preparing compound III-3 is as follows:

[0104]

[0105] Compound VI-1 (8 g, 14 mmol, 1 eq) and anhydrous potassium carbonate (7.82 g, 57 mmol, 4 eq) were added to a 250 mL round-bottom flask and dissolved in 40 mL of dry acetone. 10 mL of a dichloromethane solution of iodomethane (5.96 g, 42 mmol, 3 eq) was added to the reaction system, and the mixture was refluxed at 60 °C for 5 hours. The reaction solution was evaporated to dryness, extracted and washed with water / DCM, and the organic phase was dried to remove a large amount of solvent. The concentrated solution was added dropwise to ethanol, producing a large amount of white precipitate. The precipitate was filtered and dried to obtain a white solid with a yield of 90%. 1 H NMR (400MHz, CDCl3) δ=8.04(s,4H), 4.06(s,6H); MS (EI): m / z=593.70, calculated C 14 H 10 Br4O4S + m / z = 593.70 ([M]) + ).

[0106] Example 7

[0107] The synthetic route for preparing compound V-3 is as follows:

[0108]

[0109] The specific steps are the same as in Example 4, except that compound III-1 is replaced with compound III-3. The reaction yield is 90%. 1H NMR (400MHz, DMSO-d6) δ=8.0(s,4H),7.57(d,J=7.3,8H),7.48-7.39(m,12H),3.27(s,6H); MS (ESI):m / z=605.18, calculated C 38 H 30 O4SNa + m / z = 605.18([M+Na]) + ).

[0110] Example 8

[0111] The synthetic route for preparing compound I-3 is as follows:

[0112]

[0113] The specific steps are the same as in Example 5, except that compound V-2 is replaced with V-3, and the yield is 87%. 1 H NMR (400MHz, DMSO-d6) δ=8.22(s,4H),7.97-7.77(m,56H),3.28(s,6H); MS (ESI): m / z=490.44, calculated C 87 H 66 F3O7S6 3+ m / z = 490.44 ([M]) 3+ m / z = 148.95, calculated value CF3SO3 - m / z = 148.95 ([M]) - ).

[0114] Example 9

[0115] The synthetic route for preparing compound I-4 is as follows:

[0116]

[0117] The specific steps are the same as in Example 3, except that iodomethane is replaced with benzyl bromo, and the yield is 87%. 1¹H NMR (400MHz, CD3CN) δ=8.06–7.96(m, 12H), 7.81–7.67(m, 8H), 7.36(q, J=7.6Hz, 4H), 7.32–7.28(m, 8H), 7.22(d, J=7.5Hz, 8H), 4.92(d, J=12.7Hz, 4H), 4.77(d, J=12.7Hz, 4H), 3.20(t, J=5.9, 4H), 3.17(s, 12H), 1.04(tt, J1=7.0, J2=7.0, 4H), 0.80(qt, J1=7.1, J2=7.0, 4H), 0.41(t, J=7.4, 6H); MS (ESI): m / z=454.47, calculated value C 77 H 78 F3O7S6 3+ m / z = 454.47 ([M]) 3+ m / z = 148.95, calculated value CF3SO3 - m / z = 148.95 ([M]) - ).

[0118] Example 10

[0119] The synthetic route for preparing compound I-5 is as follows:

[0120]

[0121] The specific steps are the same as in Example 3, except that iodomethane is replaced with benzyl bromo, and silver trifluoromethanesulfonate is replaced with silver hexafluoroantimonate, with a yield of 87%. 1 ¹H NMR (400MHz, CD3CN) δ=8.06–7.96(m, 12H), 7.81–7.67(m, 8H), 7.36(q, J=7.6Hz, 4H), 7.32–7.28(m, 8H), 7.22(d, J=7.5Hz, 8H), 4.92(d, J=12.7Hz, 4H), 4.77(d, J=12.7Hz, 4H), 3.20(t, J=5.9, 4H), 3.17(s, 12H), 1.04(tt, J1=7.0, J2=7.0, 4H), 0.80(qt, J1=7.1, J2=7.0, 4H), 0.41(t, J=7.4, 6H); MS (ESI): m / z=454.47, calculated value C 77 H 78 F3O7S6 3+ m / z = 454.47 ([M]) 3+ m / z = 234.89, calculated value SbF6 - m / z = 234.89 ([M])- ).

[0122] Example 11

[0123] The synthetic route for preparing compound III-6 is as follows:

[0124]

[0125] Compound VI-1 (8 g, 14 mmol, 1 eq), anhydrous potassium carbonate (7.82 g, 57 mmol, 4 eq), and 18-crown ether-6 (740 mg, 2.8 mmol, 0.2 eq) were added to a 250 mL round-bottom flask and dissolved in 40 mL of dry acetone. Benzyl bromide (5.98 g, 35 mmol, 2.5 eq) was added to the reaction mixture, and the mixture was refluxed at 60 °C for 5 hours. The reaction solution was evaporated to dryness, washed with water / DCM, and dried to remove a large amount of solvent. The concentrated solution was added dropwise to ethanol, producing a large amount of white precipitate. The precipitate was filtered and dried to obtain a white solid in 90% yield. 1 H NMR (400MHz, CDCl3) δ=8.04(s,4H),7.15(t,J=7.3,2H),7.05(t,J=7.3,4H),6.57(d,J=7.4,4H),4.18(s,4H); MS (EI):m / z=745.76, calculated value C 26 H 18 Br4O4S + m / z = 745.76 ([M]) + ).

[0126] Example 12

[0127] The synthetic route for preparing compound V-6 is as follows:

[0128]

[0129] The specific steps are the same as in Example 4, except that compound III-1 is replaced with III-6, and the reaction yield is 90%. 1 ¹H NMR (400MHz, DMSO-d⁶) δ = 8.0 (s, 4H), 7.57 (d, J = 7.3, 8H), 7.48–7.39 (m, 12H), 7.15 (t, J = 7.3, 2H), 7.05 (t, J = 7.3, 4H), 6.57 (d, J = 7.4, 4H), 4.18 (s, 4H); MS (ESI): m / z = 757.24. Calculated value C. 50 H 38 O4SNa + m / z = 757.24([M+Na]) + ).

[0130] Example 13

[0131] The synthetic route for preparing compound I-6 is as follows:

[0132]

[0133] The specific steps are the same as in Example 5, except that compound V-2 is replaced with V-6, and the yield is 87%. 1 H NMR (400MHz, DMSO-d6) δ=8.22(s,4H), 7.97-7.77(m,84H), 4.18(s,4H); MS (ESI): m / z=764.12, calculated value C 125 H 92 F9O 13 S 10 3+ m / z = 764.12 ([M]) 3+ m / z = 148.95, calculated value CF3SO3 - m / z = 148.95 ([M]) - ).

[0134] Example 14

[0135] The synthetic route for preparing compound III-7 is as follows:

[0136]

[0137] The specific steps are the same as in Example 11, except that the compound benzyl bromide is replaced with 4-methylthio-benzyl bromide, and the reaction yield is 90%. 1 H NMR (400MHz, CDCl3) δ=8.04(s,4H),7.34(d,J=7.4,4H),6.57(d,J=7.4,4H),4.18(s,4H),2.5(s,6H); MS (EI): m / z=837.74, calculated C 28 H 22 Br4O4S3 + m / z = 837.74 ([M]) + ).

[0138] Example 15

[0139] The synthetic route for preparing compound IV-7 is as follows:

[0140]

[0141] The specific steps are the same as in Example 4, except that compound III-1 is replaced with III-7, and the reaction yield is 90%.1 H NMR (400MHz, CDCl3) δ=8.0(s,4H),7.57(d,J=7.3,8H),7.48-7.39(m,12H),7.34(d,J=7.3,4H),6.57(d,J=7.4,4H),4.18(s,4H),2.5(s,6H); MS (ESI):m / z=849.21 Calculated value C 52 H 42 O4S3Na + m / z = 849.21([M+Na]) + ).

[0142] Example 16

[0143] The synthetic route for preparing compound I-7 is as follows:

[0144]

[0145] The specific experimental steps are the same as in Example 3, except that compound IV-1 is replaced with IV-7, with a yield of 85%. 1 ¹H NMR (400MHz, CDCN) δ = 8.24 (s, 4H), 7.9 (d, J = 7.2, 4H), 7.81 (d, J = 7.3, 8H), 7.75 (d, J = 7.2, 4H), 7.72–7.63 (m, 12H), 4.18 (s, 4H), 3.14 (s, 12H); MS (ESI): m / z = 428.14; Calculated C 54 H 48 O4S3 2+ m / z = 428.14 ([M]) 2+ ).

[0146] Example 17

[0147] The synthetic route for preparing compound IV-8 is as follows:

[0148]

[0149] The specific steps are the same as in Example 2, except that compound III-1 is replaced with III-3, and the reaction yield is 85%. 1 H NMR (400MHz, CDCl3) δ=8.0(s,4H),7.41(s,4H),7.34(d,J=6.0,4H),7.32(d,J=6.0,4H),7.22-7.24(m,4H),3.27(s,6H),2.45(s,12H); MS (ESI): m / z=789.13, calculated value C 42 H 38 O4S5Na+ m / z = 789.13([M+Na]) + ).

[0150] Example 18

[0151] The synthetic route for preparing compound I-8 is as follows:

[0152]

[0153] The specific experimental steps are the same as in Example 3, except that compound IV-1 is replaced with IV-8, with a yield of 85%. 1 ¹H NMR (400MHz, CD₃CN) δ 8.19 (s, 4H), 8.02 (d, J = 7.7Hz, 4H), 7.98 (s, 4H), 7.9 (d, J = 7.6Hz, 4H), 7.76 (dd, J = 7.7, 4H), 3.20 (s, 6H), 3.17 (s, 24H); MS (ESI): m / z = 325.06, calculated C 47 H 50 F3O7S6 3+ m / z = 325.06 ([M]) 3+ m / z = 148.95, calculated value CF3SO3 - m / z = 148.95 ([M]) - ).

[0154] Example 19

[0155] The synthetic route for preparing compound III-9 is as follows:

[0156]

[0157] The specific experimental steps are the same as in Example 1, except that compound VI-1 is replaced with VI-9, with a yield of 75%. 1 H NMR (400MHz, CDCl3) δ=8.04(s,4H),4.06(t,J=6.3,4H),1.86(tt,J1=7.0,J2=6.5,4H),1.56(qt,J1=7.4,J2=7.4,4H),0.99(t,J=7.3,6H); MS (EI):m / z=661.80, calculated value C 20 H 22 Br4O3S + m / z = 661.80 ([M]) + ).

[0158] Example 20

[0159] The synthetic route for preparing compound V-9 is as follows:

[0160]

[0161] The specific steps are the same as in Example 4, except that compound III-1 is replaced with III-9, and the reaction yield is 90%. 1 H NMR (400MHz, DMSO-d6) δ=8.0(s,4H),7.57(d,J=7.3,8H),7.48-7.39(m,12H),3.17(t,J=5.8,4H),1.04(tt,J1=6.5,J2=6.4,4H),0.86(qt,J1=7.2,J2=7.2,4H),0.45(t,J=7.3,6H); MS (ESI):m / z=687.29, calculated value C 45 H 44 O3SNa + m / z = 687.29([M+Na]) + ).

[0162] Example 21

[0163] The synthetic route for preparing compound I-9 is as follows:

[0164]

[0165] The specific steps are the same as in Example 5, except that compound V-2 is replaced with V-9, and the yield is 87%. 1 H NMR (400MHz, DMSO-d6) δ=8.22(s,4H),7.97-7.77(m,56H),3.18(t,J=5.9,4H),1.04(tt,J1=7.0,J2=7.0,4H),0.80(qt,J1=7.1,J2=7.0,4H),0.41(t,J=7.4,6H); MS (ESI):m / z=513.47, calculated value C 93 H 78 F3O6S6 3+ m / z = 513.47 ([M]) 3+ m / z = 148.95, calculated value CF3SO3 - m / z = 148.95 ([M]) - ).

[0166] Example 22

[0167] The synthetic route for preparing compound IV-10 is as follows:

[0168]

[0169] The specific steps are the same as in Example 2, except that compound III-1 is replaced with III-9, and the reaction yield is 85%. 1 H NMR (400MHz, CDCl3) δ = 8.0 (s, 4H), 7.41 (s, 4H), 7.34 (d, J = 6.0, 4H), 7.32 (d, J = 6.0, 4H), 7.22-7.24 (m, 4H), 4.06 (t, J = 6.3, 4H) ), 1.86 (tt, J1 = 7.0, J2 = 6.5, 4H), 1.56 (qt, J1 = 7.4, J2 = 7.4, 4H), 0.99 (t, J = 7.3, 6H), 2.45 (s, 12H); MS (ESI): m / z = 871.24, calculated value C 49 H 52 O3S5Na + m / z = 871.24([M+Na]) + ).

[0170] Example 23

[0171] The synthetic route for preparing compound I-10 is as follows:

[0172]

[0173] The specific experimental steps are the same as in Example 3, except that compound IV-1 is replaced with IV-10, with a yield of 85%. 1 H NMR (400MHz, CD3CN) δ8.19(s,4H),8.02(d,J=7.7Hz,4H),7.98(s,4H),7.9(d,J=7.6Hz,4H),7.76(dd,J=7.7,4H),3.20(t,J=5.9, 4H), 3.17 (s, 24H), 1.04 (tt, J1=7.0, J2=7.0, 4H), 0.80 (qt, J1=7.1, J2=7.0, 4H), 0.41 (t, J=7.4, 6H); MS (ESI): m / z=347.76, calculated value C 53 H 62 F3O6S6 3+ m / z = 347.76 ([M]) 3+ m / z = 148.95, calculated value CF3SO3 - m / z = 148.95 ([M]) - ).

[0174] Example 24

[0175] The thermal stability of the compounds prepared in Examples 5 and 9 was determined. The differential scanning calorimetry (DSC) and thermogravimetric analysis of the compound in Example 5 are shown in [reference needed]. Figure 1 Differential scanning calorimetry (DSC) and thermogravimetric analysis of the compound in Example 9 are shown in [reference needed]. Figure 2 The results showed that both compounds exhibited high thermal stability. The thermal decomposition temperatures of the compounds in Examples 5 and 9 reached 223°C and 175°C, respectively, demonstrating excellent thermal stability.

[0176] Example 25

[0177] Compound I-2 from Example 5 was dissolved in acetonitrile to prepare a solution of 18 mg / mL. This solution was filtered through a 0.2 μm microporous filter to obtain a spin-coating solution. This solution was then spin-coated onto an untreated silicon substrate. The uniformity of the film was analyzed using atomic force microscopy (AFM). The results are shown in [Figure number missing]. Figure 3 . Figure 3 It can be visually observed that the film does not exhibit significant height differences, and its surface roughness (RMS) is only 0.374 nm, indicating a very smooth film surface. Therefore, the prepared film is highly uniform.

[0178] Example 26

[0179] A negative photoresist formulation and its use in photolithography: Compound I-2 from Example 5 was dissolved in acetonitrile to prepare a solution with a mass concentration of 20 mg / mL. The solution was filtered through a microporous filter with a pore size of 0.2 μm to obtain a spin-coating solution. This solution was then spin-coated onto an untreated silicon substrate. The substrate was pre-baked at 80°C for 3 minutes, and the film thickness was measured using an ellipsometer. The prepared film was then exposed using an electron beam light source at the National Center for Nanoscience and Technology with exposure periods of 50 nm, 44 nm, and 40 nm. Very uniform lithographic stripes were obtained. The test results are shown in [Figure number missing]. Figure 4 The results show that the widths of the lithographic stripes are 25, 22, and 20 nm, respectively, while exhibiting high resolution and low line edge roughness (LER < 2.5).

[0180] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. The compound represented by formula (I): in, A is selected from the following groups. Indicates the connection key: Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 Whether the same or different, each is independently selected from -S + R S1 R S2 Or a group Z, wherein the group Z is H or C. 1-15 Alkyl or C 1-15 Alkoxy; R0 is selected from C 1-15 Alkoxy; R S1 R S2 Whether the two are the same or different, each is independently selected from C. 6-20 Aryl, 5-20 heteroaryl; X – It can be a halide ion, carboxylate ion, sulfate ion, alkyl sulfonate ion, haloalkyl sulfonate ion, p-toluenesulfonate ion, sulfonamide anion, tetrafluoroborate ion, hexafluoroantimonate ion, hexafluorophosphate ion or bis(trifluoromethanesulfonyl)imide ion. n equals the thionium salt group -S in the molecule. + R S1 R S2 S + The number of S + and X – To make the compound electrically neutral as a whole, where n is an integer from 2 to 4; The compound shown in formula (I) has 2-4 thioonium salt groups -S + R S1 R S2 .

2. The compound according to claim 1, characterized in that, X – It consists of trifluoromethanesulfonate, perfluoropropylsulfonate, and perfluorobutylsulfonate.

3. The compound according to claim 1, characterized in that, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 Whether they are the same or different, they are each independently selected from H and -S. + R S1 R S2 C 1-6 Alkyl, C 1-6 Alkyl group.

4. The compound according to claim 1, characterized in that, n is 2 or 4.

5. The compound according to claim 1, characterized in that, R S1 R S2 Selected from C 6-12 Aryl.

6. The compound according to claim 1, characterized in that, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 Whether the two are the same or different, they are each independently selected from H or -S. + (C 6-12 Aryl)2.

7. The compound according to claim 1, characterized in that, R0 is C 1-6 Alkyl group.

8. The following compounds: 。 9. Use of the compound according to any one of claims 1-8 in the preparation of photoresists.

10. A photoresist composition comprising the compound according to any one of claims 1-8.

11. The photoresist composition according to claim 10, wherein, The photoresist composition further includes a solvent selected from one, two or more of the following substances: propylene glycol methyl ether acetate, dimethylformamide, cyclohexanone, ethyl n-pentanone, ethyl isopentanone, ethanol, acetonitrile, isopropanol, acetone, methyl n-pentanone, and methyl isopentanone.

12. The photoresist composition according to claim 10, wherein, The photoresist composition is a positive or negative photoresist composition.

13. The photoresist composition according to claim 10, wherein, The photoresist composition is a one-component photoresist composition, containing only the compounds described in any one of claims 1-8, except for the solvent.

14. A photoresist coating comprising the compound of any one of claims 1-8.

15. The method for preparing the photoresist coating according to claim 14, characterized in that, include: The photoresist composition according to any one of claims 10-13 is prepared by applying it onto a substrate.

16. The application of the compound of any one of claims 1-8, or the photoresist composition of any one of claims 10-13, or the photoresist coating of claim 14 in photolithography.

17. The application according to claim 16, wherein, The photolithography is 248nm photolithography, 193nm photolithography, extreme ultraviolet photolithography, nanoimprint lithography, or electron beam lithography.

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