Silicon-containing polyphenylsulfonium salt monomolecular resin and photoresist composition thereof

Abstract

The present invention discloses a silicon-containing polyphenylsulfonium salt monomolecular resin and a photoresist composition thereof. The resin comprises a compound represented by formula (I) or formula (II). The compound structure represented by formula (I) or formula (II) contains both a sulfonium salt and a hydroxyl group or an acid-sensitive group. Therefore, the compound can simultaneously have the dual functions of acid generation and acid crosslinking or acid sensitivity. It can serve as both an acid generator for photoresists and a main material for photoresists. The unique structure of the compound represented by formula (I) or formula (II) facilitates the regulation of acid diffusion and effectively reduces edge roughness.

Description

Technical Field

[0001] The present invention belongs to the field of material technology, and relates to a silicon-containing polyphenylsulfonium salt monomolecular resin and a photoresist composition thereof, and specifically relates to a silicon-containing polyphenylsulfonium salt monomolecular resin and a photoresist composition thereof, a photoresist coating and applications thereof. Background Art

[0002] Molecular glasses are a class of functional materials composed of small, monodisperse organic molecules that form stable amorphous glasses at room temperature. Compared to traditional polymer photoresists, molecular glasses feature smaller, monodisperse building blocks, a well-defined molecular weight, and a repeatable stereochemical structure. This allows for precise synthesis and facilitates the production of high-resolution and low LWR / LER patterns.

[0003] Molecular glass photoresists based on CARs can be divided into PAG blended and PAG combined types. Most of the molecular glass CARs reported so far are made by mixing organic molecular glasses with PAGs and other additives. The PAGs in these materials may produce weak phase separation and be distributed unevenly in the film. In order to fully utilize the advantages of molecular glass, produce low photoacid diffusion to increase resolution and reduce line edge roughness (LER), prevent uneven distribution of resist components, and provide an increase in PAG concentration in the resist to maintain high sensitivity, more and more scientific researchers are committed to combining molecules with photoacid generators to synthesize a single-component molecular glass resist to develop resist materials with excellent comprehensive performance. Summary of the Invention

[0004] To solve the above technical problems, the present invention provides a silicon-containing polyphenylsulfonium salt monomolecular resin and a photoresist composition thereof, as well as a method for preparing the monomolecular resin. The monomolecular resin can simultaneously function as a host material and a PAG during photolithography, or can be used alone as a PAG.

[0005] The technical solutions of the present invention are as follows:

[0006] A compound represented by formula (I) or formula (II):

[0007]

[0008] Wherein, in formula (I) or formula (II), R0, R a1 ~R a12 The same or different, each independently selected from hydrogen atom, hydroxyl group, C 1-15 Alkoxy or -OR b , the R b is an acid-sensitive group;

[0009] In formula (I) or formula (II), the sulfonium salt group (ie -SRC1 R C2 Or -SR C3 R C4 ) are independently located at the ortho, para or meta position; R C1 ~R C5 The same or different, each independently selected from unsubstituted or optionally substituted by one, two or more R s1 Substituted with the following groups: C 1-15 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclic group, -C 1-15 Alkyl-C 6-20 Aryl, -C 1-15 Alkyl-5-20 membered 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;

[0010] R s1 Selected from NO2, halogen, C 1-15 Alkyl, C 1-15 Alkoxy, C 3-20 Cycloalkyl, C 6-20 Aryl, 5-20 membered heteroaryl;

[0011] X – is an anion such as a halide, carboxylate, sulfate, alkylsulfonate, haloalkylsulfonate (e.g., trifluoromethanesulfonate, perfluoropropylsulfonate, perfluorobutylsulfonate), p-toluenesulfonate, an anion of a sulfonamide, tetrafluoroborate, hexafluorophosphate or bistrifluoromethanesulfonimide;

[0012] The acid-sensitive group R b It refers to a group that can react under acidic conditions and thus be removed from the main body.

[0013] According to an embodiment of the present invention, the acid-sensitive group is -CR 1 -OR 1 、-CO-OR 1 、-CH2-CO-OR 1 、

[0014] where R 1 The same or different, independently selected from unsubstituted or optionally substituted by one, two or more R s2Substituted with the following groups: C 1-15 Alkyl, C 3-20 Cycloalkyl, C 7-20 bridged ring group; The ring is optionally substituted with one, two or more R s2 Substitution; wherein m is any integer from 1 to 4, Indicates the bond connecting the group to the main structure;

[0015] R s2 The same or different, independently selected from the following groups: C 1-8 Alkyl, C 1-8 Alkoxy, C 3-10 Cycloalkyl.

[0016] Preferably, the acid-sensitive group is selected from the following:

[0017]

[0018] in, Indicates a connection key.

[0019] Preferably, the group R C1 ~R C4 Specifically selected from one of the following structures:

[0020]

[0021] in, Indicates a connection key.

[0022] In one embodiment, R0, R a1 ~R a12 At least one group is hydroxyl or -OR b .

[0023] In one embodiment, R a1 ~R a12 At least one group is hydroxyl or -OR b , for example, at least one-third of the groups are hydroxyl or -OR b .

[0024] In one embodiment, R a1 ~R a12 In each benzene ring, there is at least one group which is a hydroxyl group or -OR b .

[0025] As an example, the compound represented by formula I can be selected from the following compounds:

[0026]

[0027]

[0028] As an example, the compound represented by formula II can be selected from the following compounds:

[0029]

[0030]

[0031] The present invention also provides a method for preparing the compound represented by the above formula (I), comprising:

[0032] (A) Compound (IV) and R C2 -L1 or (R C2 O) 2SO 2, and MX are mixed and reacted to obtain a compound of formula (I), wherein L1 is a leaving group, such as a halogen;

[0033]

[0034] Among them, R0, R C1 ~R C3 、R a1 ~R a12 As defined above,

[0035] or,

[0036] (B) Compound (IV) and R C2 -L1 or (R C2 O) 2SO 2, and MX are mixed to react to obtain a compound of formula (IIA); and then the compound of formula (IIA) is reacted with R C4 -L1 or (R C4 O) 2SO 2, and MX are mixed to obtain a compound of formula (I); L1 is a leaving group, such as halogen;

[0037]

[0038] Among them, R0, R C1 ~R C4 、R a1 ~R a12 As defined above;

[0039] Optionally, when R0, R a1 ~R a12 When independently selected from hydrogen atoms and hydroxyl groups, they can be combined with R d -L2 reacts to prepare R0, R a1 ~R a12 Independently selected from H, C 1-15 Alkoxy or -OR b A compound of formula (I); wherein R d R bor C 1-15 Alkyl, L2 is a leaving group or L2 and R d Composition containing R d anhydride.

[0040] Optionally, the anions can be further ion-exchanged with solutions of corresponding ions to obtain compounds of formula (I) with different anions.

[0041] According to the present invention, the compound of formula (IV) can be prepared by the following method, comprising:

[0042]

[0043] Among them, R C1 、R C3 , R0, R a1 ~R a12 As defined above, R0', R a1 '~R a3 'same or different, each independently represents H or C 1-15 alkoxy;

[0044] 1) reacting the compound of formula (VI) with the compound of formula (III) to obtain the compound of formula (IV), wherein R0, R a1 ~R a12 Independently selected from H or C 1-15 alkoxy;

[0045] Optionally, 2) subjecting the compound of formula (IV) to a dealkylation reaction to obtain R0, R a1 ~R a12 A compound of formula (IV) independently selected from H or hydroxy;

[0046] Optionally, 3) the above R0, R a1 ~R a12 The compound of formula (IV) independently selected from H or hydroxyl and the compound R b -L3 reaction to prepare R0, R a1 ~R a12 Independently selected from H or -OR b The compound of formula (I); wherein L3 is a leaving group or L3 and R b Composition containing R b anhydride.

[0047] According to an embodiment of the present invention, the dealkylation reaction may use a reducing agent, such as boron tribromide.

[0048] Furthermore, the present invention also provides a method for preparing a compound of formula (VI), comprising: reacting tetrahalosilane with a phenylene sulfide compound represented by formula (B) and a tribromobenzene compound represented by formula (C) to obtain a compound of formula (VI);

[0049]

[0050] Among them, R0', R C1 、R C2 As defined above; X is halogen.

[0051] The present invention also provides a method for preparing the compound represented by the above formula (II), comprising the following steps: reacting compound (VII) with R C2 -L1 or (R C2 O) 2SO 2, and MX are mixed and reacted to obtain a compound of formula (II); L1 is a leaving group, such as a halogen;

[0052]

[0053] Among them, R C1 、R C2 、R C5 , R0, R a1 ~R a12 As defined above;

[0054] Optionally, when R0, R a1 ~R a12 When independently selected from hydrogen atoms and hydroxyl groups, they can be combined with R d -L2 reacts to prepare R0, R a1 ~R a12 Independently selected from H, C 1-15 Alkoxy or -OR b A compound of formula (II); wherein R d R b or C 1-15 Alkyl, L2 is a leaving group or L2 and R d Composition containing R d anhydride.

[0055] According to the present invention, the compound of formula (VII) can be prepared by the following method, comprising:

[0056]

[0057] Among them, R C1 、R C5 , R0, R a1 ~R a12 As defined above, R0', R a1 '~Ra3 'same or different, each independently represents H or C 1-15 alkoxy;

[0058] 1) reacting a compound of formula (VIII) with a compound of formula (III) to obtain a compound of formula (VII), wherein R0, R a1 ~R a12 Independently selected from H or C 1-15 alkoxy;

[0059] Optionally, 2) subjecting the compound of formula (VII) to a dealkylation reaction to obtain R0, R a1 ~R a12 a compound of formula (VII) independently selected from H or hydroxy;

[0060] Optionally, 3) the above R0, R a1 ~R a12 The compound of formula (VII) independently selected from H or hydroxyl and the compound R b -L3 reaction to prepare R0, R a1 ~R a12 Independently selected from H or -OR b The compound of formula (VII); wherein L3 is a leaving group or L3 and R b Composition containing R b anhydride.

[0061] According to an embodiment of the present invention, the dealkylation reaction may use a reducing agent, such as boron tribromide.

[0062] Furthermore, the present invention also provides a method for preparing a compound of formula (VIII), comprising: reacting a compound of formula (D), a compound of formula (B) and a compound of formula (C) to obtain a compound of formula (VIII);

[0063]

[0064] Among them, R C1 、R C5 As defined above, R0' represents H or methoxy, and X is halogen.

[0065] The present invention also provides the use of the compound represented by the above formula (I) or formula (II), which is used as an acid generator for photoresist and / or a main material for photoresist.

[0066] In one embodiment, the compound of formula (I) or formula (II) of the present invention is used as both a main material of the photoresist (ie, a film-forming resin) and an acid generator of the photoresist.

[0067] In one embodiment, the compound of formula (I) or formula (II) of the present invention is used only as an acid generator.

[0068] The present invention also provides a photoresist composition, which comprises the compound of formula (I) or formula (II).

[0069] According to the present invention, the photoresist composition further comprises a solvent, which is selected from, for example, one, two or more of the following substances: ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol dimethyl ether, ethylene glycol monomethyl ether, cyclohexanone, methyl n-amyl ketone, and methyl isoamyl ketone.

[0070] According to the present invention, the photoresist composition is a positive photoresist composition, which comprises the compound of formula (I) or formula (II) and a photoresist solvent.

[0071] In one embodiment, the photoresist composition is a single-component photoresist, which is composed of a compound of formula (I) or formula (II) and a photoresist solvent, that is, the photoresist composition includes only one component, namely formula (I) or (II), in addition to the photoresist solvent.

[0072] According to the present invention, in the compound of formula (I) or formula (II), R a1 ~R a12 , R0, at least one is -OR b Preferably, R a1 ~R a12 At least one-third of the groups are -OR b Preferably, in the compound of formula (I) or formula (II), R a1 ~R a12 In each benzene ring, at least one group is -OR b .

[0073] Furthermore, in the positive photoresist composition, the mass of the compound of formula (I) or formula (II) accounts for 1 to 10 wt % of the total mass of the positive photoresist composition, and the rest is photoresist solvent.

[0074] In one embodiment, the photoresist composition further comprises one or more other photoresist host materials; the other photoresist host materials may be any photoresist host materials known in the prior art, such as the materials reported in ZL201380000139.X.

[0075] According to the present invention, the photoresist composition may also be a negative photoresist composition, which comprises the compound of formula (I) or formula (II), a cross-linking agent and a photoresist solvent.

[0076] In one embodiment, in the compound of formula (I) or formula (II), the group Ra1 ~R a12 , at least one group in R0 is a hydroxyl group, preferably, R a1 ~R a12 At least one third of the groups are hydroxyl groups, and preferably, at least one group on each benzene ring is a hydroxyl group.

[0077] Furthermore, in the negative photoresist composition, the mass of the compound of formula (I) or formula (II) accounts for 1 to 10 wt % of the total mass of the negative photoresist composition, the crosslinking agent accounts for 0.1 wt % to 1 wt %, and the rest is photoresist solvent.

[0078] In the present invention, the ratio of the sulfonium salt group (ie, the acid generator group) to the acid-sensitive group can be adjusted as needed, and the preferred molar ratio is 1:4-1:14.

[0079] In a preferred embodiment, in the negative photoresist composition, the crosslinking agent is tetramethoxymethyl glycoluril and / or 2,4-dihydroxymethyl-6-methylphenol.

[0080] The present invention also provides a photoresist coating, which comprises the compound of formula (I) or formula (II).

[0081] The present invention also provides a method for preparing the above-mentioned photoresist coating, which is prepared by applying the above-mentioned photoresist composition on a substrate.

[0082] Preferably, the application method is spin coating.

[0083] Preferably, the substrate is, for example, a silicon wafer substrate.

[0084] Preferably, the photoresist coating is a thin film.

[0085] The present invention also provides application of the photoresist coating in photolithography.

[0086] The compound of the present invention has a relatively high glass transition temperature (greater than 100° C.) and can be used in photolithography processing.

[0087] According to the present invention, the photoresist coating can be used in modern lithography technologies such as 248nm lithography, 193nm lithography, extreme ultraviolet (EUV) lithography, nanoimprint lithography or electron beam lithography, preferably in EUV lithography.

[0088] The beneficial effects of the present invention are as follows:

[0089] (1) The present invention provides a series of novel monomolecular resins based on sulfonium salts, namely, compounds represented by formula (I) or (II), which can be used as acid generators for photoresists and mixed with other host materials, such as known monomolecular resins (molecular glasses). Because the structures of the compounds described herein are similar to those of conventional photoresist host materials, they can be mixed more evenly, thereby reducing the line edge roughness of photoresists.

[0090] (2) The compound structure of the present invention represented by formula (I) or formula (II) contains both a sulfonium salt and a hydroxyl group or an acid-sensitive group. Therefore, the compound can have the dual functions of acid generation and acid crosslinking or acid sensitivity. It can serve as both an acid generator for photoresist and a main material for photoresist. The unique structure of the compound represented by formula (I) or formula (II) helps to achieve the regulation of acid diffusion and effectively reduce edge roughness.

[0091] (3) The silicon-containing polyphenylsulfonium salt single-molecule resin of the present invention contains silicon atoms. Since silicon has a tetrahedral bonding mode, the silicon-containing polyphenylsulfonium salt single-molecule resin has better solubility and film-forming properties.

[0092] (4) The silicon-containing polyphenylsulfonium salt single-molecule resin of the present invention is connected by silicon atoms as central atoms, so that the photoresist material prepared from the silicon-containing polyphenylsulfonium salt single-molecule resin has higher etching resistance and increases its interaction with the substrate;

[0093] (5) The silicon-containing polyphenylsulfonium salt single-molecule resin of the present invention has a definite molecular structure and a single molecular size, which can well meet the requirements of high-resolution lithography.

[0094] (6) The absorption of silicon atoms in the silicon-containing polyphenylsulfonium salt single-molecule resin of the present invention in the extreme ultraviolet region is smaller than that of other elements, which helps to improve the transmittance of extreme ultraviolet light to the photoresist made from the silicon-containing polyphenylsulfonium salt single-molecule resin, thereby improving the contrast of the photoresist, and thus better meets the requirements of the next generation of extreme ultraviolet lithography. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0096] Figure 1 The differential scanning calorimetry curve and thermogravimetric curve of compound I-1 in Example 5 of the present invention are shown.

[0097] Figure 2 The differential scanning calorimetry curve and thermogravimetric curve of compound II-4 in Example 22 of the present invention are shown.

[0098] Figure 3This is a scanning electron microscope (SEM) image of compound II-3 in Example 13 of the present invention.

[0099] Figure 4 This is an atomic force microscope (AFM) image of compound II-3 in Example 13 of the present invention.

[0100] Figure 5 This is a scanning electron microscope (SEM) image of the photolithography stripes (exposure period of 60 nm) of the positive resist film formed by the main material of compound I-1 in Example 5 of the present invention.

[0101] Figure 6 This is a scanning electron microscope (SEM) image of the photolithography stripes (exposure period of 70 nm) of the positive resist film formed by the main material of compound I-1 in Example 5 of the present invention. DETAILED DESCRIPTION

[0102] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations 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 encompassed within the scope of protection that the present invention is intended to protect.

[0103] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0104] Example 1

[0105] Preparation of bis(3,5-dibromophenyl)-bis(4-methylthiophenyl)silane, the synthetic route is as follows:

[0106]

[0107] To a 500 mL Schlenk flask, add 4-bromothioanisole (8 g, 39.3 mmol, 1 eq) and 80 mL of dry ether. Under a nitrogen atmosphere, cool in a liquid nitrogen bath and freeze-evacuate three times to remove oxygen from the system. In an ice bath, add n-butyllithium in n-hexane (2.5 M, 17.3 mL, 43.2 mmol) dropwise. After reacting at 0°C for 1 hour, add tetrachlorosilane in ether (60 mL, 19.6 mmol) dropwise. Remove the ice bath, return to room temperature, and react for 3 hours to obtain Reaction Solution A.

[0108] Weigh 1,3,5-tribromobenzene (12.4 g, 39.3 mmol, 1.0 eq) and 150 mL of dry ether. Under a nitrogen atmosphere, cool in a liquid nitrogen bath and freeze-evacuate three times to remove oxygen from the system. Add n-butyllithium in n-hexane (2.5 M, 15.7 mL, 39.3 mmol) dropwise to the reaction system at -78°C. After the reaction solution reacts at low temperature for 2 hours, reaction solution A is added dropwise to the system. The reaction solution is then returned to room temperature and reacted for 3 hours. The reaction solution is added to 100 mL of water to quench the reaction, extracted with ether, and concentrated under reduced pressure to remove the solvent. 4.38 g of a white solid is isolated by column chromatography with a yield of 30%. 1 H NMR (400 MHz, CDCl3) δ = 7.77 (s, 2H), 7.50 (s, 4H), 7.36 (d, J = 6.7, 4H), 7.29 (d, J = 6.8, 4H), 2.51 (s, 6H). MS (MALDI-TOF): m / z = 743.7, calculated value C 26 H 20 Br4S2Si + m / z=743.7([M] + ).

[0109] Example 2

[0110] Compound V-1 was prepared by the following synthetic route:

[0111]

[0112] To a 200 mL Schleck reaction flask, add bis(3,5-dibromophenyl)-bis(4-methylthiophenyl)silane (6 g, 8 mmol, 1.0 eq), 3,4-dimethoxyphenylboronic acid (7.3 g, 40 mmol, 5.0 eq), and 80 mL of dioxane. Anhydrous potassium carbonate solid (5.5 g, 40 mmol, 5 eq) was weighed, dissolved in 30 mL of water, and added to the reaction flask. The system was deoxygenated three times under a nitrogen atmosphere. Tetrakis(triphenylphosphine)palladium catalyst (185 mg, 0.16 mmol, 0.02 eq) was added under a nitrogen atmosphere. The mixture was heated at 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. The dichloromethane solution of the product was added dropwise to a large amount of ethanol, stirred at room temperature for 2 h, and filtered and dried to obtain 7.4 g of a white solid in a 95% yield. 1H NMR (400MHz, CDCl3) δ=7.77(s,6H),7.60(d,J=7.6,4H),7.27(d,J=7.6,4H),7.13(d,J=8.0,4H),7.04( s, 4H), 6.92 (d, J = 8.2, 4H), 3.90 (s, 12H), 3.83 (s, 12H), 2.48 (s, 6H); MS (MALDI-TOF): m / z = 972.3, calculated value C 58 H 56 O8S2Si + m / z=972.3([M] + ).

[0113] Example 3

[0114] Preparation of compound IV-1, the synthetic route is as follows:

[0115]

[0116] Compound V-1 (7 g, 7.2 mmol, 1.0 eq) was added to a 250 mL round-bottom flask and dissolved in 50 mL of dichloromethane dried over molecular sieves and placed in an ice bath for a period of time. 50 mL of dry dichloromethane was added to a constant pressure dropping funnel, and 3.6 mL (38.2 mmol, 5.3 eq) of boron tribromide was added to the funnel, mixed well, and then added dropwise. After four hours of reaction, the reaction was quenched with 10 mL of water and filtered to obtain a light yellow solid. The solid was dissolved in ethyl acetate and washed three times with water until neutral, then washed once with saturated brine. The organic phase was dried over anhydrous magnesium sulfate, spin-dried, and dried in a vacuum oven to obtain 6 g of a yellow foamy solid with a yield of 97%. 1 H NMR (400MHz, DMSO) δ=9.08(s,4H),9.01(s,4H),7.69(s,2H),7.55(s,4H),7.51(d,J=6.9Hz,4H),7.37(d,J=7.3H z, 4H), 6.99 (s, 4H), 6.89 (d, J = 7.1Hz, 4H), 6.78 (d, J = 7.6Hz, 4H), 2.51 (s, 6H); MS (MALDI-TOF): m / z = 860.2, calculated value C 50 H 40 O8S2Si + m / z=860.2([M] + ).

[0117] Example 4

[0118] Compound I-1' was prepared by the following synthetic route:

[0119]

[0120] Compound IV-1 (6 g, 7 mmol, 1 eq) was added to a 250 mL single-necked flask, along with 26 mL of dimethyl sulfate. The mixture was reacted at 40°C for 5 h. Afterward, 100 mL of water was added with stirring, followed by extraction with EA / water. The aqueous phases were combined. Potassium perfluorobutanesulfonate (4.3 g, 12.6 mmol, 1.8 eq) was added to the aqueous phase. An oily substance precipitated from the aqueous solution, which was extracted with EA / water. The organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent removed to afford a colloidal product. Drying afforded 6.2 g of a yellow solid in a 60% yield. 1 H NMR (400 MHz, DMSO) δ = 9.08 (s, 4H), 9.01 (s, 4H), 8.15 (d, J = 6.8, 4H), 7.71-7.52 (m, 10H), 7.00 (s, 4H), 6.89 (d, J = 7.9, 4H). 6.79 (d, J = 7.9, 4H), 3.3 (s, 12H); MS (ESI): m / z = 445.12, calculated value C 52 H 46 O8S2Si 2+ m / z=445.12([M] 2+ ); m / z = 298.94, calculated for C4F9SO3 - m / z=298.94([M] - ).

[0121] Example 5

[0122] Compound I-1 was prepared by the following synthetic route:

[0123]

[0124] In the reaction formula, Boc represents Substituents, Indicates a connection key.

[0125] Compound I-1' (6 g, 4 mmol, 1.0 eq), Boc anhydride (di-tert-butyl dicarbonate) (13 g, 60 mmol, 15 eq), and 100 mL of dry tetrahydrofuran were added to a 250 mL three-necked flask. After stirring under a nitrogen atmosphere to dissolve, the catalyst DMAP (4-dimethylaminopyridine) (245 mg, 2 mmol, 0.5 eq) was added to the solution to initiate the reaction. The reaction was stirred at room temperature for 2 h. The solvent was removed by vortexing to obtain a jelly. Tetrahydrofuran was added to dissolve the jelly, and petroleum ether was added dropwise to precipitate the jelly. The solvent was removed by centrifugation and dried to obtain 7.4 g of a white solid product with an 80% yield. 1H NMR (400 MHz, DMSO) δ = 8.04 (s, 2H), 7.84 (s, 4H), 7.77 (d, J = 8.1, 4H), 7.66 (d, J = 8.1, 4H), 7.61 (d, J = 8.5, 4H), 7.50 (s, 4H), 7.40 (d, J = 8.4, 4H), 3.3 (s, 12H), 1.47 (d, J = 5.7, 72H); MS (ESI): m / z = 845.3, calculated value C 92 H 110 O 24 S2Si 2+ m / z=845.3([M] 2+ ); m / z = 298.94, calculated for C4F9SO3 - m / z=298.94([M] - ).

[0126] Example 6

[0127] Compound X-1 was prepared by the following synthetic route:

[0128]

[0129] The specific steps are the same as those in Example 1, except that phenyltrichlorosilane is used instead of tetrachlorosilane, and the reaction yield is 30%. 1 H NMR (400 MHz, CDCl3) δ = 7.77 (s, 2H), 7.50 (s, 4H), 7.47 (d, J = 6.7, 2H), 7.43 (d, J = 7.0, 2H), 7.36 (m, 3H), 7.29 (d, J = 6.8, 2H), 2.51 (s, 3H). MS (MALDI-TOF): m / z = 697.76, calculated value C 25 H 18 Br4SSi + m / z=697.76([M] + ).

[0130] Example 7

[0131] Compound IX-1 was prepared by the following synthetic route:

[0132]

[0133] The specific steps are the same as those in Example 2, except that p-methoxyphenylboronic acid is used instead of 3,4-dimethoxyphenylboronic acid, and compound X-1 is used instead of compound bis(3,5-dibromophenyl)-bis(4-methylthiophenyl)silane. The reaction yield is 90%. 1HNMR (400 MHz, CDCl3) δ = 7.79 (s, 6H), 7.72 (d, J = 7.0, 2H), 7.6 (d, J = 7.6, 2H), 7.42 (d, J = 7.0, 2H), 7.27 (m, 3H), 7.13 (d, J = 8.2, 8H), 6.91 (d, J = 8.2, 8H), 3.82 (s, 12H), 2.51 (s, 3H); MS (MALDI-TOF): m / z = 806.29, calculated value C 53 H 46 O4SSi + m / z=806.29([M] + ).

[0134] Example 8

[0135] Compound VIII-1 was prepared by the following synthetic route:

[0136]

[0137] The specific steps are the same as those in Example 3, except that compound IX-1 is used instead of compound V-1, and the yield is 95%. 1 HNMR (400 MHz, DMSO) δ = 9.05 (s, 4H), 7.71-7.52 (m, 15H), 7.19 (d, J = 7.9, 8H). 6.79 (d, J = 7.9, 8H), 2.51 (s, 3H); MS (MALDI-TOF): m / z = 750.23, calculated value C 79 H 38 O4SSi + m / z=750.23([M] + ).

[0138] Example 9

[0139] Preparation of compound II-1', the synthetic route is as follows:

[0140]

[0141] The specific steps are the same as those in Example 4, except that compound VIII-1 is used instead of compound IV-1, with a yield of 65%. 1 H NMR (400 MHz, DMSO) δ = 9.05 (s, 4H), 8.15 (d, J = 6.8, 2H), 7.71-7.52 (m, 13H), 7.19 (d, J = 7.9, 8H). 6.79 (d, J = 7.9, 8H), 3.24 (s, 6H); MS (ESI): m / z = 765.25, calculated value C 50 H 41 O4SSi+ m / z=765.25([M] + ); m / z = 298.94, calculated for C4F9SO3 - m / z=298.94([M] - ).

[0142] Example 10

[0143] Preparation of compound II-1, the synthetic route is as follows:

[0144]

[0145] In the reaction formula, NB represents Substituents, Indicates a connection key.

[0146] Compound II-1' (5.3 g, 5 mmol, 1.0 eq), tetrabutylammonium bromide (2.42 g, 7.5 mmol, 1.5 eq), solid K2CO3 (10.3 g, 75 mmol, 15.0 eq), and 50 mL of N-methylpyrrolidone (NMP) were added to a 100 mL three-necked flask. The mixture was stirred at room temperature for 2 hours. A solution of compound NB-Cl (10 g, 50 mmol, 10 eq) in N-methylpyrrolidone (NMP) was slowly added dropwise to the reaction mixture. The temperature was raised to 60°C and the reaction was allowed to proceed for 48 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with ethyl acetate / water. The organic phase was washed once with 3 wt% oxalic acid solution and once with water. The organic layers were combined, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Recrystallization from an ethyl acetate / n-hexane mixture afforded 5.85 g of a white solid with a yield of 70%. 1 H NMR (400 MHz, DMSO): 8.04 (s, 2H), 7.98 (s, 4H), 7.71 (d, J = 7.9, 8H), 7.43-7.46 (m, 9H), 7.1 (d, J = 7.9, 8H), 3.24 (s, 6H), 1.3-2.2 (m, 52H); MS (ESI): m / z = 1373.6, calculated for C 86 H 89 O 12 SSi + m / z=1373.6([M] + ); m / z = 298.94, calculated for C4F9SO3 - m / z=298.94([M] - ).

[0147] Example 11

[0148] Preparation of compound II-2, the synthetic route is as follows:

[0149]

[0150] In the reaction formula, AD represents

[0151] The specific steps are the same as those in Example 10, except that compound AD-Cl is used instead of compound NB-Cl, and the yield is 67%. 1 H NMR (400 MHz, DMSO): 8.04 (s, 2H), 7.98 (s, 4H), 7.71 (d, J = 7.9, 8H), 7.43-7.46 (m, 9H), 7.15 (d, J = 7.9, 8H), 3.25 (s, 6H), 0.8-2.2 (m, 68H); MS (ESI): m / z = 1534.72 calcd. 98 H 105 O 12 SSi + m / z=1534.72([M] + ); m / z = 298.94, calculated for C4F9SO3 - m / z=298.94([M] - ).

[0152] Example 12

[0153] Preparation of compound VII-3, the synthetic route is as follows:

[0154]

[0155] Compound IV-1 (4.3 g, 5 mmol, 1 eq) prepared in Example 3 and Boc anhydride (di-tert-butyl dicarbonate) (13.08 g, 60 mmol, 12 eq) were dissolved in 40 ml of dry tetrahydrofuran. After dissolution, the catalyst DMAP (4-dimethylaminopyridine) (750 mg, 0.5 mmol, 0.1 eq) was added to the solution and allowed to react for 3 h. The reaction solution was spin-dried and then dissolved and clarified in 200 ml of ethanol and 5 ml of THF. Water was then added dropwise to the system while stirring, slowly precipitating a white solid. Excess Boc anhydride was removed by precipitation three times to obtain 7.3 g of a white product with a yield of 88%. 1 H NMR (400 MHz, DMSO) δ 8.05 (s, 2H), 7.86 (s, 4H), 7.80 (s, 4H), 7.64 (d, J = 7.9 Hz, 4H), 7.58 (d, J = 6.8 Hz, 4H), 7.43 (d, J = 7.6 Hz, 4H), 7.38 (d, J = 6.7 Hz, 4H), 2.49 (s, 6H), 1.49 (d, 72H). MS (ESI): m / z = 1660.61, calculated value C 90 H104 O 24 S2Si + m / z=1660.61([M] + ).

[0156] Example 13

[0157] Preparation of compound II-3, the synthetic route is as follows:

[0158]

[0159] To a 250ml round-bottom flask, add compound VII-3 (5g, 3mmol, 1eq) prepared in Example 12 and silver trifluorobutanesulfonate (771mg, 3mmol, 1eq). Dissolve and stir in 40ml of dry dichloromethane. Slowly add 5ml of a dichloromethane solution (468mg, 3.3mmol, 1.1eq) dropwise in an ice bath. After completion of the addition, warm the mixture to room temperature and react in the dark for 3h. Filter the AgI precipitate from the reaction mixture, and completely evaporate the DCM in the filtrate to obtain an oily residue. Recrystallize from n-hexane, centrifuge, discard the supernatant, and dry to obtain a solid in a 60% yield. 1 H NMR (400 MHz, DMSO) δ 8.10 (d, J = 8.2 Hz, 2H), 8.07 (s, 2H), 7.98 (d, J = 8.0 Hz, 2H), 7.87 (s, 4H), 7.81 (s, 4H), 7.65 (d, J = 8.5 Hz, 4H), 7.60 (d, J = 8.0 Hz, 2H), 7.42 (d, J = 8.6 Hz, 4H), 7.40 (d, J = 9.5 Hz, 2H), 3.24 (s, 6H), 2.5 (s, 3H), 1.47 (s, 72H); MS (ESI): m / z = 1675.63, calculated value C 91 H 107 O 24 S2Si + m / z=1675.63([M] + ); m / z = 148.95, calculated for CF3SO3 - m / z=148.95([M] - ).

[0160] Example 14

[0161] Compound I-2 was prepared by the following synthetic route:

[0162]

[0163] In the reaction formula, Boc represents

[0164] Specific steps: Compound VII-3 (5 g, 3 mmol, 1 eq) prepared in Example 12 and sodium trifluoromethanesulfonate (1.57 g, 9 mmol, 3 eq) were added to a 250 ml round-bottom flask, and 80 ml of dry acetone was added. The reaction was stirred at -78 ° C for 20 min, and 1.07 ml of benzyl bromide (1.54 g, 9 mmol, 3.0 eq) was added dropwise. Then, the temperature was slowly raised to room temperature, and the reaction was carried out at 25 ° C for 6 h. The mixture was extracted with dichloromethane / water, the organic layers were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent. The mixture was recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain 3.9 g of a white solid with a yield of 60%. 1 H NMR (400MHz, DMSO) δ = 8.04 (s, 2H), 7.84 (s, 4H), 7.77 (s, 4H), 7.66 (s, 4H), 7.61 (d, J = 8.5, 4H), 7.50 (s, 4H), 7.4 0(d,J=8.4,4H),7.25(s,6H),7.16(s,4H),3.24(m,10H),1.5(t,6H),1.47(d,72H); MS(ESI):m / z=921.86, calculated value C 104 H 118 O 24 S2Si 2+ m / z=921.86([M] 2+ ); m / z = 148.95, calculated for CF3SO3 - m / z=148.95([M] - ).

[0165] Example 15

[0166] Compound I-3 was prepared by the following synthetic route:

[0167]

[0168] To a 250 ml round-bottom flask was added compound VII-3 (5 g, 3 mmol, 1 eq) prepared in Example 12 and sodium trifluoromethanesulfonate (1.57 g, 9 mmol, 3 eq). 80 ml of dry dichloromethane was then added dropwise. Under an ice-water bath, 1.1 ml of cyclohexyl bromide (1.47 g, 9 mmol, 3.0 eq) was added dropwise. The mixture was slowly warmed to room temperature and allowed to react at room temperature for 5 h. After completion of the reaction, the mixture was extracted with dichloromethane / water. The combined organic layers were dried over anhydrous sodium sulfate, concentrated under reduced pressure to remove the solvent, and recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain 4 g of a white solid in a 62% yield. 1H NMR (400 MHz, DMSO) δ = 8.04 (s, 2H), 7.84 (s, 4H), 7.77 (s, 4H), 7.66 (s, 4H), 7.61 (d, J = 8.5, 4H), 7.50 (s, 4H), 7.40 (d, J = 8.4, 4H), 3.7 (s, 2H), 3.24 (s, 6H), 1.68 (m, 8H), 1.5-1.45 (m, 12H), 1.47 (d, 72H); MS (ESI): m / z = 913.89, calculated value C 102 H 126 O 24 S2Si 2+ m / z=913.89([M] 2+ ); m / z = 148.95, calculated for CF3SO3 - m / z=148.95([M] - ).

[0169] Example 16

[0170] Compound I-4 was prepared by the following synthetic route:

[0171]

[0172] The experimental steps were the same as those in Example 15, except that bromobenzene was used instead of bromocyclohexane. The yield was 60%. 1 H NMR (400 MHz, DMSO) δ = 8.04 (s, 2H), 7.84 (s, 4H), 7.77 (d, J = 8.1, 4H), 7.66 (d, J = 8.1, 4H), 7.61 (d, J = 8.5, 4H), 7.50 (s, 4H), 7.40 (d, J = 8.4, 4H), 7.35 (m, 10H), 3.3 (s, 6H), 1.47 (d, J = 5.7, 72H); MS (ESI): m / z = 907.84, calculated value C 102 H 114 O 24 S2Si 2+ m / z=907.84([M] 2+ ); m / z = 298.94, calculated for C4F9SO3 - m / z=298.94([M] - ).

[0173] Example 17

[0174] Compound I-5 was prepared by the following synthetic route:

[0175]

[0176] The experimental steps were the same as those in Example 16, except that compound II-3 was used instead of compound VII-3, with a yield of 70%. 1 HNMR (400 MHz, DMSO) δ = 8.04 (s, 2H), 7.84 (s, 4H), 7.77 (d, J = 8.1, 4H), 7.66 (d, J = 8.1, 4H), 7.61 (d, J = 8.5, 4H), 7.50 (s, 4H), 7.40 (d, J = 8.4, 4H), 7.35 (m, 5H), 3.3 (s, 9H), 1.47 (d, J = 5.7, 72H); MS (ESI): m / z = 876.84, calculated value C 97 H 112 O 24 S2Si 2+ m / z=876.84([M] 2+ ); m / z = 148.95, calculated for CF3SO3 - m / z=148.95([M] - ).

[0177] Example 18

[0178] Compound X-4 was prepared by the following synthetic route:

[0179]

[0180] The specific steps are the same as those in Example 1, except that cyclohexyltrichlorosilane is used instead of tetrachlorosilane, and 4-bromodiphenyl sulfide is used instead of 4-bromothioanisole. The reaction yield is 30%. 1 H NMR (400 MHz, DMSO) δ = 8.08 (s, 2H), 7.65 (s, 4H), 7.48-7.40 (m, 7H), 7.26 (d, J = 6.7, 2H), 1.53-1.24 (m, 11H); MS (ESI): m / z = 765.82, calculated value C 30 H 26 O4SSi + m / z=765.82([M] + ).

[0181] Example 19

[0182] Compound IX-4 was prepared by the following synthetic route:

[0183]

[0184] The specific steps are the same as those in Example 2, except that 3.4.5-trimethoxyphenylboronic acid is used instead of 3,4-dimethoxyphenylboronic acid, and compound X-4 is used instead of bis(3,5-dibromophenyl)-bis(4-methylthiophenyl)silane. The reaction yield is 90%. 1 HNMR (400 MHz, DMSO) δ = 8.04 (s, 2H), 7.98 (s, 4H), 7.48 (d, J = 6.7, 2H), 7.44-7.40 (m, 5H), 7.26 (d, J = 6.7, 2H), 6.62 (s, 8H), 3.83 (s, 24H), 3.71 (s, 12H), 1.53-1.19 (m, 11H); MS (ESI): m / z = 1114.44, calculated value C 66 H 70 O 12 SSi + m / z=1114.44([M] + ).

[0185] Example 20

[0186] Compound VIII-4 was prepared by the following synthetic route:

[0187]

[0188] The specific steps are the same as those in Example 3, except that compound IX-4 is used instead of compound V-1. The reaction yield is 95%. 1 H NMR (400 MHz, DMSO) δ = 9.08 (s, 8H), 8.73 (s, 4H), 7.69 (s, 2H), 7.55 (s, 4H), 7.51 (d, J = 6.9 Hz, 2H), 7.44-7.40 (m, 5H), 7.37 (d, J = 7.3 Hz, 2H), 6.99 (s, 8H), 1.53-1.19 (m, 11H); MS (MALDI-TOF): m / z = 946.25, calculated value C 54 H 46 O 12 SSi + m / z=946.25([M] + ).

[0189] Example 21

[0190] Compound VII-4 was prepared by the following synthetic route:

[0191]

[0192] The specific steps were the same as those in Example 12, except that compound VIII-4 was used instead of compound IV-1, the amount of Boc anhydride was increased to 16 eq, the amount of DMAP catalyst was increased to 0.2 eq, and the reaction yield was 85%. 1 H NMR (400 MHz, DMSO) δ = 8.05 (s, 2H), 7.86 (s, 4H), 7.80 (s, 8H), 7.58 (d, J = 6.8 Hz, 2H), 7.44-7.40 (m, 5H), 7.38 (d, J = 6.7 Hz, 2H), 1.53-1.19 (m, 11H), 1.49 (d, 108H). MS (ESI): m / z = 2147.88, calculated value C 114 H 142 O 36 SSi + m / z=2147.88([M] + ).

[0193] Example 22

[0194] Preparation of compound II-4, the synthetic route is as follows:

[0195]

[0196] The specific steps are the same as those in Example 16, except that compound VII-4 is used instead of compound VII-3. The reaction yield is 70%. 1 H NMR (400 MHz, DMSO) δ = 8.10 (d, J = 8.2 Hz, 2H), 8.07 (s, 2H), 7.98 (d, J = 8.0 Hz, 2H), 7.87 (s, 4H), 7.81 (s, 8H), 7.35-7.3 (m, 10H), 1.53-1.19 (m, 11H), 1.47 (s, 108H); MS (ESI): m / z = 2224.92, calculated value C 120 H 147 O 36 SSi + m / z=2224.92([M] + ); m / z = 148.95, calculated for CF3SO3 - m / z=148.95([M] - ).

[0197] Example 23

[0198] Compound I-6 was prepared by the following synthetic route:

[0199]

[0200] The experimental steps were the same as those in Example 15, except that compound II-3 was used instead of compound VII-3, and 4-nitrobromobenzene was used instead of bromocyclohexane. The yield was 70%. 1 H NMR (400 MHz, DMSO) δ = 8.12 (d, 2H), 8.04 (s, 2H), 7.84 (s, 4H), 7.77 (d, J = 8.1, 4H), 7.66 (d, J = 8.1, 4H), 7.61 (d, J = 8.5, 4H), 7.50 (s, 4H), 7.45 (d, 2H), 7.40 (d, J = 8.4, 4H), 3.3 (s, 9H), 1.47 (d, J = 5.7, 72H); MS (ESI): m / z = 899.33, calculated value C 97 H 111 NO 26 S2Si 2+ m / z=899.33([M] 2+ ); m / z = 148.95, calculated for CF3SO3 - m / z=148.95([M] - ).

[0201] Example 24

[0202] Preparation of compound II-5, the synthetic route is as follows:

[0203]

[0204] The experimental steps were the same as those in Example 15, except that 1-bromomethyl-4-nitrobenzene was used instead of bromocyclohexane. The yield was 70%. 1 H NMR (400MHz, DMSO) δ8.12(d,2H),8.10(d,J=8.2Hz,2H),8.07(s,2H),7.98(d,J=8.0Hz,2H),7.87(s,4H),7.81(s,4H),7.65(d,J=8.5Hz,4H),7.6 0(d,J=8.0Hz,2H),7.45(d,2H),7.42(d,J=8.6Hz,4H),7.40(d,J=9.5Hz, 2H), 3.24 (s, 5H), 2.5 (s, 3H), 1.47 (s, 72H); MS (ESI): m / z=1679.60, calculated value C 91 H 107 O 24 S2Si + m / z=1679.60([M] + ); m / z = 298.94, calculated for C4F9SO3 - m / z=298.94([M]- ).

[0205] Example 25

[0206] The thermal stability and glass transition temperature of the compounds prepared in Example 5 and Example 22 were measured. The differential scanning calorimetry curve and thermogravimetric analysis of the compound in Example 5 are shown in FIG. Figure 1 The differential scanning calorimetry curve and thermogravimetric analysis of the compound of Example 22 are shown in FIG. Figure 2 The results showed that the glass transition temperatures of the two compounds reached above 100°C, and they had good thermal stability.

[0207] Example 26

[0208] Compound II-3 in Example 13 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a 30 mg / ml solution, which was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The solution was spin-coated on an acid-base treated silicon substrate to form a film. The film uniformity was analyzed using a scanning electron microscope (SEM) and an atomic force microscope (AFM). The results are shown in FIG. Figure 3 and 4 . Figure 3 There is no color or light and dark difference, which means that the film is on the same level and there is no height difference. Figure 4 It can be seen intuitively that there is no obvious height difference in the film, which shows that the prepared film is very uniform.

[0209] Example 27

[0210] A positive photoresist formulation and photolithography: Compound I-1 of Example 5 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a mass concentration of 30 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The solution was spin-coated on a silicon substrate treated with acid and alkali, pre-baked at 100°C for 3 minutes, and the film thickness was measured using an ellipsometer. The prepared film was exposed using an electron beam light source from the National Center for Nanotechnology with an exposure period of 60 nm, resulting in very uniform photolithographic stripes. The test results are shown in FIG. Figure 5 and Figure 6 ,in Figure 5 The photoresist exposure period is P60. Figure 6 The photoresist exposure period is P70. The width of the photoresist stripe is about 25nm, and it has good resolution, contrast and low line edge roughness.

[0211] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A compound, characterized in that It has a structure shown in the following formula (I) or formula (II): Wherein, in formula (I) or formula (II), R0, R a1 ~R a12 The same or different, each independently selected from hydrogen atom, hydroxyl group, C 1-15 Alkoxy or -OR b , the R b is an acid-sensitive group; In formula (I) or formula (II), the sulfonium salt group, i.e. -SR C1 R C2 Or -SR C3 R C4 , independently located at the ortho, para or meta position; R C1 ~R C5 The same or different, each independently selected from unsubstituted or optionally substituted by one, two or more R s1 Substituted with the following groups: C 1-15 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclic group, -C 1-15 Alkyl-C 6-20 Aryl, -C 1-15 Alkyl-5-20 membered 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; R s1 Selected from NO2, halogen, C 1-15 Alkyl, C 1-15 Alkoxy, C 3-20 Cycloalkyl, C 6-20 Aryl, 5-20 membered heteroaryl; X – is an anion selected from the group consisting of a halide ion, a carboxylate, a sulfate, an alkylsulfonate, a haloalkylsulfonate, a p-toluenesulfonate, an anion of a sulfonamide, a tetrafluoroborate, a hexafluorophosphate, or a bis(trifluoromethanesulfonyl)imide ion; The acid-sensitive group is -CR 1 -OR 1 、-CO-OR 1 、-CH2-CO-OR 1 、 where R 1 The same or different, independently selected from unsubstituted or optionally substituted by one, two or more R s2 Substituted with the following groups: C 1-15 Alkyl, C 3-20 Cycloalkyl, C 7-20 bridged ring group; The ring is optionally substituted with one, two or more R s2 Substitution; wherein m is any integer from 1 to 4, Indicates a connection key; R s2 The same or different, independently selected from the following groups: C 1-8 Alkyl, C 1-8 Alkoxy, C 3-10 Cycloalkyl.

2. The compound according to claim 1, characterized in that The acid-sensitive group is selected from the following: in, Indicates a connection key.

3. The compound according to claim 1, characterized in that Group R C1 ~R C4 Specifically selected from one of the following structures: in, Indicates a connection key.

4. The compound according to claim 1, characterized in that R0, R a1 ~R a12 At least one group is hydroxyl or -OR b .

5. The compound according to claim 4, characterized in that R a1 ~R a12 At least one-third of the groups are hydroxyl or -OR b .

6. The compound according to claim 4, characterized in that R a1 ~R a12 In each benzene ring, there is at least one group which is a hydroxyl group or -OR b .

7. The compound according to claim 1, characterized in that The compound represented by formula I is selected from the following compounds:

8. The compound according to claim 1, characterized in that The compound represented by formula II is selected from the following compounds:

9. A method for preparing the compound according to any one of claims 1 to 8, wherein: The method of preparing the compound of formula (I) comprises the following steps: (A) Compound (IV) and R C2 -L1 or (R C2 O) 2SO 2, and MX are mixed and reacted to obtain a compound of formula (I), wherein L1 is a leaving group; Among them, R0, R C1 ~R C3 、R a1 ~R a12 As defined in any one of claims 1 to 3, or, (B) Compound (IV) and R C2 -L1 or (R C2 O) 2SO 2, and MX are mixed to react to obtain a compound of formula (IIA); and then the compound of formula (IIA) is reacted with R C4 -L1 or (R C4 O) 2SO 2, and MX are mixed to obtain a compound of formula (I); L1 is a leaving group; Among them, R0, R C1 ~R C4 、R a1 ~R a12 As defined in any one of claims 1 to 3; The MX is selected from at least one of potassium perfluorobutanesulfonate, silver trifluorobutanesulfonate, and sodium trifluoromethanesulfonate; Optionally, when R0, R a1 ~R a12 When independently selected from hydrogen atoms, hydroxyl groups, and R d -L2 reacts to prepare R0, R a1 ~R a12 Independently selected from H, C 1-15 Alkoxy or -OR b A compound of formula (I); wherein R d R b or C 1-15 Alkyl, L2 is a leaving group or L2 and R d Composition containing R d anhydride; Optionally, the anion can be further ion-exchanged with a solution of the corresponding ion to obtain a compound of formula (I) with a different anion; Alternatively, the preparation method of the compound of formula (II) comprises the following steps: Compound (VII) and R C2 -L1 or (R C2 O) 2SO 2, and MX are mixed and reacted to obtain a compound of formula (II); L1 is a leaving group; Among them, R C1 、R C2 、R C5 , R0, R a1 ~R a12 As defined in any one of claims 1 to 3; Optionally, when R0, R a1 ~R a12 When independently selected from hydrogen atoms, hydroxyl groups, and R d -L2 reacts to prepare R0, R a1 ~R a12 Independently selected from H, C 1-15 Alkoxy or -OR b A compound of formula (II); wherein R d R b or C 1-15 Alkyl, L2 is a leaving group or L2 and R d Composition containing R d anhydride.

10. The method according to claim 9, characterized in that L1 is a leaving group, which is halogen.

11. Use of the compound represented by formula (I) or formula (II) according to any one of claims 1 to 8 as an acid generator and / or a main material of a photoresist.

12. A photoresist composition, characterized in that The photoresist composition comprises the compound represented by formula (I) or formula (II) according to any one of claims 1 to 8.

13. The photoresist composition according to claim 12, wherein The photoresist composition further includes a solvent.

14. The photoresist composition according to claim 13, wherein The solvent is selected from one, two or more of the following substances: ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, ethylene glycol monomethyl ether, cyclohexanone, methyl n-amyl ketone, and methyl isoamyl ketone.

15. The photoresist composition according to claim 12, wherein The photoresist composition is a positive photoresist composition, and the positive photoresist composition comprises the compound of formula (I) or formula (II) and a photoresist solvent.

16. The photoresist composition according to claim 15, characterized in that In the compound of formula (I) or formula (II), R a1 ~R a12 , R0, at least one is -OR b .

17. The photoresist composition according to claim 15, wherein In the compound of formula (I) or formula (II), R a1 ~R a12 At least one-third of the groups are -OR b .

18. The photoresist composition according to claim 15, wherein In the compound of formula (I) or formula (II), R a1 ~R a12 In each benzene ring, at least one group is -OR b .

19. The photoresist composition according to claim 12, wherein The photoresist composition is a single-component photoresist, which is composed of a compound of formula (I) or (II) and a photoresist solvent. That is, the photoresist composition includes only one component, namely, the compound of formula (I) or (II), in addition to the photoresist solvent.

20. The photoresist composition according to claim 15, wherein The mass of the compound of formula (I) or formula (II) accounts for 1 to 10 wt % of the total mass of the positive photoresist composition, and the rest is photoresist solvent.

21. The photoresist composition according to claim 20, wherein The photoresist composition further includes one or more other photoresist host materials.

22. The photoresist composition according to claim 12, wherein The photoresist composition is a negative photoresist composition, and the negative photoresist composition comprises the compound of formula (I) or formula (II), a cross-linking agent, and a photoresist solvent; 23. The photoresist composition according to claim 22, wherein In the negative photoresist composition, the mass of the compound of formula (I) or formula (II) accounts for 1 to 10 wt % of the total mass of the negative photoresist composition, the cross-linking agent accounts for 0.1 wt % to 1 wt %, and the rest is a photoresist solvent; 24. The photoresist composition according to claim 23, wherein In the compound of formula (I) or formula (II), the group R a1 ~R a12 , at least one group in R0 is a hydroxyl group.

25. The photoresist composition according to claim 24, wherein R a1 ~R a12 At least one third of the groups are hydroxyl groups.

26. The photoresist composition according to claim 24, wherein At least one group on each benzene ring is a hydroxyl group.

27. The photoresist composition according to claim 22, wherein The cross-linking agent is tetramethoxymethyl glycoluril and / or 2,4-dihydroxymethyl-6-methylphenol.

28. A photoresist coating, characterized in that The coating comprises the compound of formula (I) or formula (II) according to any one of claims 1 to 8.

29. Use of the photoresist composition according to any one of claims 13 to 27 or the photoresist coating according to claim 28 in photolithography.

30. The use according to claim 29, characterized in that The photoresist coating is used in 248nm photolithography, 193nm photolithography, extreme ultraviolet photolithography, nanoimprint photolithography or electron beam photolithography.

Images