Hexaphenylbenzene sulfide-based sulfonium salt monomolecular resin photoresist, preparation method and application thereof

Abstract

The application belongs to the technical field of photoetching materials, and particularly relates to a kind of sulfonium salt monomolecular resin photoetching glue based on hexaphenylbenzene sulfide and a preparation method and application thereof.The compound of the application can be used as non-chemical amplification photoetching glue, without using other auxiliary agents such as acid generator and acid diffusion inhibitor, avoiding the problems such as uneven distribution of acid generator and acid diffusion inhibitor in chemical amplification photoetching glue, uneven acid diffusion, etc., 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 type of thioonium salt monomolecular resin photoresist based on hexaphenylphenyl sulfide, its preparation method, and its application. Background Technology

[0002] With the rapid development of the semiconductor industry, the integration density of semiconductor devices is increasing, placing higher demands on the resolution of photolithography technology and higher requirements on the quality of high-resolution photolithographic patterns, especially on the increasingly stringent requirements for linewidth roughness (LWR) and line edge roughness (LER). Photoresist is a key material for transferring photolithographic patterns during semiconductor device fabrication. Photoresist is coated onto different substrates, and after being irradiated with energy such as light beams, electron beams, ion beams, or X-rays, its solubility changes. Then, through development and etching processes, the corresponding pattern is transferred to the substrate. The resolution achievable by the pattern formed by the photoresist has a decisive impact on the integration density of the device, and the overall performance of the photoresist needs to match the current development of photolithography technology.

[0003] Traditional chemically amplified photoresists (CARs) rely on mixing or polymerically bonded photoacid generators (PAGs) to achieve solubility differences. This chemically amplified photoresist system suffers from a number of problems, such as high line edge roughness (LER) and line width roughness (LWR), 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 monomolecular resins. Therefore, developing molecular glass n-CARs with strong lithographic potential is of great significance, particularly for patterned applications with low LER / LWR characteristics. Summary of the Invention

[0004] To improve the above-mentioned technical problems, the present invention first provides thioonium salts based on hexaphenylphenyl sulfide as shown in formula (I), formula (II), or formula (III):

[0005]

[0006]

[0007] in:

[0008] R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from hydrogen, nitro, amino, hydroxyl, CHO, and unsubstituted or optionally substituted by one, two, or more R groups, including the following groups: C 1-12 Alkyl, C 1-12 Alkoxy group, -C(O)-C 1-12 Alkyl, C 3-20 Cycloalkyl or 3-20 membered heterocyclic groups;

[0009] Ra and Rb may be the same or different, and are independently selected from C. 1-12 alkyl;

[0010] Y is selected from halide ions, alkyl sulfonates, haloalkyl sulfonates (such as trifluoromethanesulfonate, perfluoropropyl sulfonate, perfluorobutyl sulfonate), p-toluenesulfonate, tetrafluoroborate, hexafluorophosphate, and bis(trifluoromethanesulfonyl)imide ions.

[0011] According to embodiments of the present invention, R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from hydrogen, amino, and C. 1-6 Alkyl, C 1-6 Alkoxy group, -C(O)-C 1-3 Alkyl or C 3-12 cycloalkyl;

[0012] Ra and Rb may be the same or different, and are independently selected from C. 1-6 alkyl.

[0013] In one embodiment of the present invention, Ra and Rb are the same, and are methyl or ethyl.

[0014] In one embodiment of the present invention, the anion Y - For OTf - .

[0015] In one embodiment of the present invention, R2, R3, R4, and R5 are H, and R1 is selected from methyl, methoxy, isopropyl, tert-butyl, amino, or -COCH3.

[0016] In one embodiment of the present invention, R1 and R2 are methyl groups, and R3, R4, and R5 are H groups.

[0017] In one embodiment of the present invention, R1, R2, and R5 are methyl groups, and R3 and R4 are H groups.

[0018] In one embodiment of the present invention, R2 and R5 are methyl groups, and R1, R3, and R4 are H groups.

[0019] In one embodiment of the present invention, R1, R2, R3, R4, and R5 are all methyl groups.

[0020] As an example, the thioonium salt based on hexaphenylphenyl sulfide is selected from the following compounds:

[0021]

[0022] The present invention also provides a method for preparing a thioonium salt based on hexaphenylphenyl sulfide as described above, comprising: reacting the compound shown in formula (IV) with RaY to obtain the compound shown in formula (I);

[0023]

[0024] Among them, R1, R2, R3, R4, R5, Ra, Y - It has the definition as described above;

[0025] Optionally, the compound shown in formula (I) is reacted with RbY to give the compound shown in formula (II) or formula (III); wherein Rb has the definition described above.

[0026] The present invention also provides a method for preparing the compound shown in formula (IV) above, comprising: reacting compound (V) with compound (VI) to obtain the compound shown in formula (IV);

[0027]

[0028] Where X is a leaving group, such as a halogen; R1, R2, R3, R4, and R5 have the definitions described above.

[0029] Optionally, the compound shown in formula (I), formula (II), or formula (III) can be subjected to ion exchange with the corresponding anion solution to obtain the compound shown in formula (I), formula (II), or formula (III) with different anions.

[0030] The present invention also provides the use of the compounds shown in formula (I), or formula (II), or formula (III) as photoresists.

[0031] The present invention also provides a photoresist composition comprising one of the compounds shown in formula (I), or formula (II), or formula (III) as described above and a photoresist solvent.

[0032] According to an embodiment of the present invention, the photoresist solvent is 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.

[0033] According to an embodiment of the present invention, the photoresist composition is a positive or negative photoresist composition.

[0034] In one embodiment, the photoresist composition is a single-component photoresist, which consists of one of the compounds of formula (I), formula (II), or formula (III) and a photoresist solvent. That is, the photoresist composition includes only one component other than the photoresist solvent, namely one of the compounds of formula (I), formula (II), or formula (III).

[0035] The present invention also provides a photoresist coating comprising one of the compounds shown in formula (I), formula (II), or formula (III) as described above.

[0036] The present invention also provides a method for preparing the above-mentioned photoresist coating, comprising: applying the photoresist composition as described above onto a substrate to obtain the coating.

[0037] In one embodiment, the application method is spin coating.

[0038] In one embodiment, the substrate is a silicon wafer substrate.

[0039] Preferably, the photoresist coating is a thin film.

[0040] The present invention also provides the application of the photoresist coating in photolithography.

[0041] According to the present invention, the photoresist coating can be used in modern photolithography technologies such as 436nm photolithography, 365nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet (EUV) photolithography, nanoimprint lithography or electron beam lithography, and is preferably used in ultraviolet, extreme ultraviolet and electron beam lithography technologies.

[0042] Beneficial effects

[0043] (1) The present invention provides a series of novel monomolecular resins based on hexaphenylphenyl sulfide thioonium salts, namely compounds shown in formula (I), or formula (II), or formula (III), wherein the raw materials of the compounds are cheap and readily available and the synthesis process is simple;

[0044] (2) The compound of the present invention can be used as a non-chemical amplification photoresist, without the need for other additives such as acid generating agents and acid diffusing agents, thus avoiding the problems of uneven distribution of acid generating agents and acid diffusing agents and uneven acid diffusion in chemical amplification photoresists. The resulting pattern has high resolution and low line width roughness.

[0045] (3) The thioonium salt monomolecular resin based on hexaphenyl phenyl sulfide described in this invention has a definite molecular structure and a single molecular size, which can well meet the requirements of high-resolution photolithography.

[0046] (4) The thioonium salt based on hexaphenylphenyl sulfide described in this invention has good thermal stability, with a thermal decomposition temperature above 200°C, exhibiting excellent thermal stability. Therefore, it can be photolithographically etched under high-temperature conditions, and the resulting photolithographic pattern is not easily decomposed.

[0047] Terminology Definitions and Explanations

[0048] 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.

[0049] "More than three" means three or more.

[0050] The term "halogen" includes F, Cl, Br, or I.

[0051] Term "C" 1-12 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably C12. 1-6 Alkyl group. "C" 1-6 "alkyl" should be understood to preferably represent a straight-chain or branched saturated monovalent hydrocarbon 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. In particular, the group has 1, 2, or 3 carbon atoms ("C..."). 1-3 Alkyl), such as methyl, ethyl, n-propyl or isopropyl.

[0052] Term "C" 3-20 "Cycloalkyl" should be understood to refer to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C". 3-12 cycloalkyl. The term "C" 3-12 "Cycloalkyl" should be understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. The C... 3-12 Cycloalkyl groups can be monocyclic hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or bicyclic hydrocarbon groups such as decahydronaphthalene ring.

[0053] The term "3-20 membered heterocyclic group" refers to a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O, and S, preferably a "3-12 membered heterocyclic group". The term "3-12 membered heterocyclic group" 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 azirrobutyl or oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoalkyl, 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 hexahydrocyclopentano[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 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. According to the invention, the heterocyclic group is non-aromatic.

[0054] The above refers to the term "C" 1-12 The definition of "alkyl" also applies to compounds containing "C". 1-12 Other terms for "alkyl", such as the term "C 1-12 "Alkyloxy" etc. Attached Figure Description

[0055] Figure 1 This is a scanning electron microscope (SEM) image of the thin film of compound I-1 in Example 2 of the present invention.

[0056] Figure 2 This is an AFM image of the thin film of compound I-1 in Example 2 of the present invention.

[0057] Figure 3 This is a thermogravimetric curve of compound I-1 in Example 2 of the present invention.

[0058] Figure 4 The ultraviolet exposure pattern (positive photoresist) is a photoresist containing compound I-1.

[0059] Figure 5 The UV exposure pattern (positive photoresist) is a photoresist containing compound II-1.

[0060] Figure 6The ultraviolet exposure pattern (positive photoresist) is a photoresist containing compound III-1.

[0061] Figure 7 The electron beam exposure pattern (positive photoresist) is a photoresist containing compound I-1. Detailed Implementation

[0062] 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.

[0063] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0064] Example 1

[0065] The synthetic route for preparing compound II-1 is as follows:

[0066]

[0067] Specific steps: Compounds V and VI-1 can be purchased directly. Add compound V (5 g, 1 eq), compound VI-1 (10.13 g, 9 eq), and 90 ml of dry DMF to a 250 mL Shrek flask. Then, evacuate the flask and purge with nitrogen three times, each time for 1 min. Under nitrogen atmosphere and stirring, add anhydrous K₂CO₃ (11.3 g, 9 eq). Reflux the reaction for 40 hours, then extract with water, dry, and recrystallize from toluene to obtain a fluorescent yellow solid product with a yield of 73%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm): 2.27 (s, 18H), 6.93 (d, J = 8.1Hz, 12H), 6.82 (d, J = 8.2Hz, 12H); MS (ESI): m / z = 810.16, calculated C 48 H 42 S6 m / z=810.16.

[0068] Example 2

[0069] The synthetic route for preparing compound I-1 is as follows:

[0070]

[0071] Specific steps: Compound IV-1 (1 g, 1 eq) was added to a 50 ml round-bottom flask, followed by methyl trifluoromethanesulfonate (MeOTf) (1.82 g, 9 eq) and 20 ml of dry DCM under stirring. The mixture was stirred at room temperature for 5 h, and then separated by column chromatography (V... DCM The product was obtained by mixing methanol (15:1) to produce an orange solid product with a yield of 85%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm): 2.27 (s, 18H), 3.27 (s, 3H), 6.93 (d, J = 8.1Hz, 12H), 6.82 (d, J = 8.2Hz, 12H); MS (ESI): m / z = 974.13, calculated C 49 H 45 S6 + m / z = 825.18 ([M]) + m / z = 825.18, calculated value CF3SO3 - m / z = 148.95 ([M]) - ); m / z = 148.95.

[0072] Example 3

[0073] The synthetic route for preparing compound II-1 is as follows:

[0074]

[0075] Specific steps: Compound I-1 (1 g, 1 eq) was added to a 50 ml round-bottom flask, followed by methyl trifluoromethanesulfonate (MeOTf) (1.73 g, 9 eq) and 20 ml of dry DCE under stirring. The mixture was stirred at 80 °C for 12 h under reflux, and then separated by column chromatography (V... DCM The product was obtained by mixing methanol (15:1) to produce an orange solid product with a yield of 80%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm): 2.27 (s, 18H), 3.27 (s, 6H), 6.93 (d, J = 8.1Hz, 12H), 6.82 (d, J = 8.2Hz, 12H); MS (ESI): m / z = 1138.11, calculated C 49 H 45 S6 + m / z = 840.21 ([M]) + m / z = 840.21, calculated value CF3SO3 - m / z = 148.95 ([M]) - ); m / z = 148.95.

[0076] Example 4

[0077] The synthetic route for preparing compound III-1 is as follows:

[0078]

[0079] Specific steps: Compound I-1 (1 g, 1 eq) was added to a 50 ml round-bottom flask, followed by methyl trifluoromethanesulfonate (MeOTf) (1.73 g, 9 eq) and 20 ml of dry DCE under stirring. The mixture was stirred at 80 °C for 12 h under reflux, and then separated by column chromatography (V... DCM The product was obtained by mixing methanol (15:1) to produce an orange solid product with a yield of 80%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm): 2.27 (s, 18H), 3.35 (s, 3H), 3.42 (s, 3H), 6.93 (d, J = 8.1Hz, 12H), 6.82 (d, J = 8.2Hz, 12H); MS (ESI): m / z = 1138.11, calculated C 49 H 45 S6 + m / z = 840.21 ([M]) + m / z = 840.21, calculated value CF3SO3 - m / z = 148.95 ([M]) - ); m / z = 148.95.

[0080] Example 5

[0081] The synthetic route for preparing compound IV-2 is as follows:

[0082]

[0083] Specific steps: Compounds V and VI-2 can be purchased directly. Add compound V (5 g, 1 eq), compound VI-2 (11.43 g, 9 eq), and 90 ml of dry DMF to a 250 mL Shrek flask. Then, evacuate the flask and purge with nitrogen three times, each time for 1 min. Under nitrogen atmosphere and stirring, add anhydrous K₂CO₃ (11.3 g, 9 eq). Reflux the reaction for 40 hours, then extract with water, dry, and recrystallize from toluene to obtain a fluorescent yellow solid product with a yield of 70%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm): 3.69 (s, 18H), 6.56–6.48 (m, 12H), 6.63 (ddd, J = 8.3, 2.19, 1.02Hz, 6H), 7.05 (t, J = 8.3Hz, 6H); MS (ESI): m / z = 908.15, calculated C 48 H 42 O6S6+ m / z = 908.15.

[0084] Example 6

[0085] The synthetic route for preparing compound I-2 is as follows:

[0086]

[0087] Specific steps: Compound IV-2 (1 g, 1 eq) was added to a 50 ml round-bottom flask, followed by methyl trifluoromethanesulfonate (MeOTf) (1.65 g, 9 eq) and 20 ml of dry DCM under stirring. The mixture was stirred at room temperature for 5 h, and then separated by column chromatography (V... DCM The product was obtained by mixing methanol (15:1) to produce an orange solid product with a yield of 80%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm): 3.3 (s, 3H), 3.69 (s, 18H), 6.56–6.48 (m, 12H), 6.63 (ddd, J = 8.3, 2.19, 1.02Hz, 6H), 7.05 (t, J = 8.3Hz, 6H). MS (ESI): m / z = 1057.10, calculated C 49 H 45 O6S6 + m / z = 908.15, calculated value CF3SO3 - m / z = 148.95 ([M]) - ); m / z = 148.95.

[0088] Example 7

[0089] The synthetic route for preparing compound IV-3 is as follows:

[0090]

[0091] Specific steps: Compounds V and VI-3 can be purchased directly. Add compound V (5 g, 1 eq), compound VI-3 (12.42 g, 9 eq), and 90 ml of dry DMF to a 250 mL Shrek flask. Then, evacuate the flask and purge with nitrogen three times, each time for 1 min. Under nitrogen atmosphere and stirring, add anhydrous K₂CO₃ (11.3 g, 9 eq). Reflux for 40 hours, then extract with water, dry, and recrystallize from toluene to obtain a fluorescent yellow solid product with a yield of 75%. 1¹H NMR (400MHz, CDCl₃) δ (ppm): 1.09 (d, J = 3.3Hz, 36H), 3.35 (sept, J = 3.3Hz, 6H), 6.56 (dd, J = 7.9, 1.0Hz, 6H), 6.93 (td, J = 7.5, 1.6Hz, 6H), 7.09 (td, J = 7.6, 1.1Hz, 6H), 7.17 (dd, J = 7.8, 1.0Hz, 6H). MS (ESI): m / z = 978.35, calculated value C 60 H 66 S6:m / z=978.35.

[0092] Example 8

[0093] The synthetic route for preparing compound I-3 is as follows:

[0094]

[0095] Specific steps: Compound IV-3 (1 g, 1 eq) was added to a 50 ml round-bottom flask, followed by methyl trifluoromethanesulfonate (MeOTf) (1.53 g, 9 eq) and 20 ml of dry DCM under stirring. The mixture was stirred at room temperature for 5 h, and then separated by column chromatography (V... DCM The product was obtained by mixing methanol (15:1) to produce an orange solid product with a yield of 80%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm): 1.09 (d, J = 3.3Hz, 36H), 3.17 (s, 3H), 3.35 (sept, J = 3.3Hz, 6H), 6.56 (dd, J = 7.9, 1.0Hz, 6H), 6.93 (td, J = 7.5, 1.6Hz, 6H), 7.09 (td, J = 7.6, 1.1Hz, 6H), 7.17 (dd, J = 7.8, 1.0Hz, 6H). MS (ESI): m / z = 1127.30, calculated value C 60 H 66 S6: m / z = 978.35 Calculated value CF3SO3 - m / z = 148.95 ([M]) - ); m / z = 148.95.

[0096] Example 9

[0097] The synthetic route for preparing compound I-10 is as follows:

[0098]

[0099] Specific steps: Compound IV-3 (1 g, 1 eq) was added to a 50 ml round-bottom flask, followed by ethyl trifluoromethanesulfonate CH3CH2OTf (1.42 g, 9 eq) and 20 ml of dry DCM under stirring. The mixture was stirred at room temperature for 5 h, followed by column chromatography (V... DCM Separate the product using a ratio of methanol (15:1) to obtain an orange solid product with a yield of 80%. 1 ¹H NMR (400MHz, CDCl₃) δ (ppm): 0.9 (t, 3H), 1.09 (d, J = 3.3Hz, 36H), 1.4 (dd, J = 7.5, 1.6Hz, 2H), 3.35 (sept, J = 3.3Hz, 5H), 6.56 (dd, J = 7.9, 1.0Hz, 6H), 6.93 (td, J = 7.5, 1.6Hz, 6H), 7.09 (td, J = 7.6, 1.1Hz, 6H), 7.17 (dd, J = 7.8, 1.0Hz, 6H); MS (ESI): m / z = 1156.34, calculated value C 62 H 71 S6: m / z = 1007.39, calculated value CF3SO3 - m / z = 148.95 ([M]) - ); m / z = 148.95.

[0100] Example 10

[0101] The synthetic route for preparing compound III-3 is as follows:

[0102]

[0103] Specific steps: Compound I-10 (1 g, 1 eq) was added to a 50 ml round-bottom flask, followed by ethyl trifluoromethanesulfonate CH3CH2OTf (1.36 g, 9 eq) and 20 ml of dry DCE under stirring. The mixture was stirred and reacted at 80 °C under reflux for 12 h, followed by column chromatography (V... DCM Separate the product using a ratio of methanol (15:1) to obtain an orange solid product with a yield of 80%. 1H NMR (400MHz, CDCl3) δ (ppm): 0.9 (t, 3H), 1.09 (d, J = 3.3Hz, 36H), 1.4 (dd, J = 7.5, 1.6Hz, 2H), 3.35 (sept, J = 3.3Hz, 5H), 3.42 (sept, J = 3.3Hz, 6H) ,6.56(dd,J=7.9,1.0Hz,5H),6.93(td,J=7.5,1.6Hz,6H),7.09(td,J=7.6,1.1Hz,6H),7.17(dd,J=7.8,1.0Hz,6H); MS(ESI): m / z=1156.34, calculated value C 62 H 71 S6: m / z = 1007.39, calculated value CF3SO3 - m / z = 148.95 ([M]) - ); m / z = 148.95.

[0104] Example 10

[0105] Compound I-1 from Example 2 was dissolved in acetonitrile to prepare a solution with a concentration of 15 mg / ml. The solution was then filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. The spin-coating solution was used to spin-coat a silicon substrate to form a film. The uniformity and flatness of the film were analyzed using scanning electron microscopy (SEM) and aerodynamic imaging (AFM), respectively. The results are shown in the appendix. Figure 1 and 2 As can be seen from the figure, the obtained film is very uniform and shows no crystallization, which is beneficial for obtaining a smooth photolithographic pattern.

[0106] Example 9

[0107] The thermal stability of compound I-1 prepared in Example 2 was determined, and the results showed that its decomposition temperature reached above 200℃, indicating excellent thermal stability. (See Appendix) Figure 3 Therefore, using compound I-1 allows for photolithography at high temperatures, and the resulting photolithographic patterns are not easily decomposed.

[0108] Example 10

[0109] A positive photoresist formulation and its application in ultraviolet lithography: Compound I-1 from Example 2 was dissolved in acetonitrile to prepare a 3% (w / w) solution. The solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. The spin-coating solution was used to spin-coat a silicon substrate, baked at 100°C for 3 minutes, and then exposed to an exposure experiment (365 nm UV lamp) for 1 minute. After development with n-hexane and rinsing with water for 30 seconds, very clear stripes were obtained. (See figure). Figure 4 .Depend on Figure 4It can be seen that the width of the photolithographic stripes is 1.03 micrometers.

[0110] Example 11

[0111] A positive photoresist formulation and its application in ultraviolet lithography: Compound II-1 from Example 3 was dissolved in acetonitrile to prepare a 3% (w / w) solution. The solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. The spin-coating solution was spin-coated onto a silicon substrate, baked at 100°C for 3 minutes, and then exposed to an exposure experiment (365 nm UV lamp) for 1 minute. After development with n-hexane and rinsing with water for 30 seconds, very clear stripes were obtained. (See figure). Figure 5 .Depend on Figure 5 It can be seen that the width of the photolithographic stripes is 1.03 micrometers.

[0112] Example 12

[0113] A positive photoresist formulation and its application in ultraviolet lithography: Compound III-1 was dissolved in acetonitrile to prepare a 3% (w / w) solution. The solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. The spin-coating solution was then spin-coated onto a silicon substrate, baked at 100°C for 3 minutes, and the resulting film was exposed (using a 365 nm UV lamp) for 1 minute. After development with n-hexane and rinsing with water for 30 seconds, very clear stripes were obtained. (See figure). Figure 6 .Depend on Figure 6 It can be seen that the width of the photolithographic stripes is 2.02 micrometers.

[0114] Example 12

[0115] A positive photoresist formulation and its application in electron beam lithography: Compound I-1 from Example 2 was dissolved in acetonitrile to prepare a 2% (w / w) solution, which was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. The spin-coating solution was used to spin-coat a silicon substrate, baked at 100°C for 3 minutes, and then the prepared film was subjected to electron beam exposure, developed with n-hexane, and rinsed with water to obtain very clear stripes (38 nm). See [link to relevant documentation]. Figure 7 .

[0116] 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. A compound, characterized in that, The thionium salts based on hexaphenylphenyl sulfide shown in formula (I), formula (II), or formula (III): in: R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from hydrogen and C. 1-12 Alkyl, C 1-12 Alkoxy; Ra and Rb may be the same or different, and are independently selected from C. 1-12 alkyl; Y is selected from alkyl sulfonate or haloalkyl sulfonate.

2. The compound according to claim 1, characterized in that, R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from hydrogen and C. 1-6 Alkyl, C 1-6 Alkoxy; Ra and Rb may be the same or different, and are independently selected from C. 1-6 alkyl.

3. The compound according to claim 1 or 2, characterized in that, Ra and Rb are the same, and can be either methyl or ethyl.

4. The compound according to claim 1 or 2, characterized in that, anion Y - For OTf - .

5. The compound according to claim 1 or 2, characterized in that, R2, R3, R4, and R5 are H, and R1 is selected from methyl, methoxy, isopropyl, and tert-butyl; or, R1 and R2 are methyl groups, and R3, R4, and R5 are hydrogen atoms; or, R1, R2, and R5 are methyl groups, and R3 and R4 are hydrogen atoms; or... R2 and R5 are methyl groups, and R1, R3, and R4 are hydrogen atoms; or, R1, R2, R3, R4, and R5 are all methyl groups.

6. The compound according to claim 1 or 2, characterized in that, The thioonium salt based on hexaphenylphenyl sulfide is selected from the following compounds:

7. A method for preparing the compound according to any one of claims 1-6, characterized in that, include: The compound shown in formula (IV) was reacted with RaY to give the compound shown in formula (I); Among them, R1, R2, R3, R4, R5, Ra, Y - It has the definition of any one of claims 1-6; Optionally, the compound shown in formula (I) is reacted with RbY to give the compound shown in formula (II) or formula (III); wherein Rb has the definition as described in any one of claims 1-6.

8. A photoresist composition, characterized in that, Includes one of the compounds of formula (I), formula (II), or formula (III) as described in any one of claims 1-6.

9. The photoresist composition according to claim 8, characterized in that, 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.

10. The photoresist composition according to claim 8 or 9, characterized in that, The photoresist composition is a positive or negative photoresist composition.

11. A photoresist coating comprising one of the compounds of formula (I), formula (II), or formula (III) as described in any one of claims 1-6.

12. The method for preparing the photoresist coating according to claim 11, characterized in that, The photoresist composition according to any one of claims 8-10 is prepared by applying it onto a substrate.

13. The use of one of the compounds of formula (I), (II), or (III) as described in any one of claims 1-6, or the photoresist coating of claim 11 in photolithography.

14. The application according to claim 13, wherein, The photolithography is 436nm photolithography, 365nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet photolithography, nanoimprint lithography, or electron beam lithography.

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