Sulfonic acid nonionic acid generators based on polysubstituted anthracene-1,9-dicarboximide derivatives

Abstract

The application belongs to the technical field of materials, and particularly relates to a kind of sulfonic acid non-ionic acid generator based on polysubstituted anthracene-1,9-dicarboxylic imide derivative and a photoresist composition thereof.The compound has acid generating efficacy and can be used as an acid generator of photoresist to improve the sensitivity of photoresist.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of materials, and particularly relates to a series of sulfonic acid non-ionic acid generators based on polysubstituted anthracene-1,9-dicarboximide derivatives. BACKGROUND

[0002] Photoresist, also known as photoresist, is a kind of etch-resistant film material whose solubility changes after being irradiated by energy beams such as light beams, electron beams, ion beams or x-rays, and is widely used in the microfabrication of integrated circuits and semiconductor discrete devices. With the rapid development of the semiconductor industry, the resolution required by the photolithography technology is getting higher and higher, and the edge roughness requirement is getting smaller and smaller, which puts forward higher requirements on the comprehensive performance of the photoresist material that can be achieved.

[0003] Since the early 1960s, photoresist has undergone a rapid development process from negative photoresist formulations based on polyvinyl cinnamate with photosensitizer to later i-line (365 nm) positive photoresist formulations of diazonaphthoquinone-novolac (DNQ Novolac) type. Since the 0.25 μm node in the mid-1990s, the demand for higher resolution has driven the application of chemically amplified photoresist (CAR), which has been applied to more advanced technology nodes such as 7 nm or even 5 nm, 3 nm, etc.

[0004] Since IBM proposed the concept of "chemical amplification" in 1982, photo acid generator (PAG) (also known as acid generator) has become a key component in photoresist composition. The so-called "chemical amplification" refers to the decomposition of PAG to generate acid after light irradiation, which initiates a series of chemical reactions, causing the solubility of photoresist material in the light irradiated area and the non-irradiated area to change significantly, and then the pattern transfer can be realized through development, so the acid generation efficiency of photo acid generator and the distribution of photo acid generator in the material have an important role in pattern quality.

[0005] Chemically amplified photoresist has higher exposure sensitivity, which can reduce the dependence on short-wavelength light source output energy such as krypton fluoride (KrF) and argon fluoride (ArF), and can more precisely control the imaging quality such as contrast, depth of focus, and verticality of sidewall profile by controlling the temperature and time of post-exposure bake (PEB), so that the photochemical reaction is more precise and controllable.

[0006] At present, there are many patent reports about ionic photoacid generators of sulfonium salt type. The sulfonium salt type photoacid generators have the advantages of good thermal stability and high acid generation efficiency, but most of the sulfonium salt photoacid generators such as triphenyl sulfonium salt have short absorption wavelength and cannot be used in i-line and g-line photolithography, and the synthesis method is relatively complex. SUMMARY

[0007] To solve the above problems, the present application provides a sulfonic acid non-ionic acid generator based on anthracene-1,9-dicarboximide derivative, which has long absorption wavelength and can be used as an acid generator in 365, 248, 193 nm and extreme ultraviolet and electron beam photolithography.

[0008] The technical scheme of the present application is as follows:

[0009] A compound as shown in the following formula I:

[0010]

[0011] Wherein:

[0012] R1, R3, R4 are the same or different, and are independently selected from H, C 1-12 alkyl, C 2-12 alkenyl or C 2-12 alkynyl;

[0013] m is 1, 2, 3 or 4; n is 1, 2 or 3;

[0014] R2 is selected from the following groups: C 1-12 alkyl, C 3-12 cycloalkyl, C 6-14 aryl, C 1-12 haloalkyl, -C 1-12 alkyl-C 6-14 aryl, -C 1-12 alkyl-C 3-12 cycloalkyl;

[0015] Rs is selected from halogen, C 1-12 alkyl, C 1-12 haloalkyl.

[0016] In one embodiment, R1 is selected from H or C 1-12 alkyl;

[0017] In a preferred embodiment, R1 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, 1-pentyl, isopentyl, tert-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, 1-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 1-nonyl, isononyl, 1-decyl or n-dodecyl.

[0018] In a preferred embodiment, R2is selected from the group consisting of methyl, butyl, chloromethyl, trifluoromethyl, perfluorosubstituted butyl, p-methylphenyl, 2,4,6-triisopropylphenyl benzyl, p-trifluoromethylphenyl, 3,5-di-trifluoromethylphenyl, perfluorosubstituted phenyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoropropyl, 3-bromopropyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, norbornyl tetrafluoroethyl, adamant-1,1,2,2-tetrafluoropropyl, bicyclo[2.2.1]heptane-tetrafluoromethyl.

[0019] In one embodiment, R3, R4are H or methyl. As an example, the compound of formula I is selected from the group consisting of:

[0020]

[0021] The present application also provides a method for preparing the compound of formula I as described above, comprising the following steps:

[0022]

[0023] reacting compound II with R2SO2CI to obtain compound I;

[0024] wherein R1, R2, R3, R4, m and n have the definitions as described above.

[0025] According to an embodiment of the present application, the compound II is prepared by the following method:

[0026]

[0027] wherein R1, R3, R4, m and n have the definitions as described above;

[0028] reacting compound III with hydroxylamine hydrochloride to obtain compound II.

[0029] According to an embodiment of the present application, the compound III is prepared by the following method:

[0030]

[0031] wherein R1, R3, R4, m and n have the definitions as described above;

[0032] reacting compound IV with an oxidizing agent (such as Oxone) to obtain compound III.

[0033] According to an embodiment of the present application, the compound IV is prepared by the following method:

[0034]

[0035] wherein R1, R3, R4, m and n have the meanings as defined above;

[0036] The compound IV is prepared by reacting the compound of formula V with C2CIO2, CS2.

[0037] According to an embodiment of the present application, the compound V is prepared by the following method:

[0038]

[0039] wherein R1, R3, R4, m and n have the meanings as defined above;

[0040] The compound VI is reacted with an alkyl lithium R1-Li to obtain the compound V. The reaction can be carried out in the presence of a catalyst, for example in the presence of Pd(PtBu3)2.

[0041] The present application also provides the use of the compound I as described above in a photoresist.

[0042] In some embodiments, the compound I described in the present application is used as an acid generator.

[0043] The present application also provides a photoresist composition comprising a photoresist main material and the compound I.

[0044] The photoresist composition can comprise one, two or more photoresist main materials. The photoresist main material can be any photoresist main material known in the prior art.

[0045] In some embodiments, the photoresist main material is a monomolecular resin (molecular glass); for example, the compound reported in ZL201380000139.X can be used as a photoresist main material.

[0046] In one embodiment, the ratio of the acid generator (compound I) and the main material can be adjusted as needed, preferably the mass ratio is 1:10-1:20.

[0047] In one embodiment, the photoresist composition further comprises a solvent.

[0048] In some embodiments, the solvent is selected from one, two or more of the following: ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol dimethyl ether, ethylene glycol monomethyl ether, cyclohexanone, methyl n-pentyl ketone, methyl isopentyl ketone.

[0049] The present application also provides a photoresist film comprising the compound of formula I or the photoresist composition as described above.

[0050] In one embodiment, the photoresist film of the present application is composed of the compound of formula I and any host material.

[0051] The present application also provides a method for preparing a photoresist film, comprising spin coating the photoresist composition as described above on a substrate to form a film.

[0052] In one embodiment, the substrate can be a silicon wafer or the like.

[0053] The present application also provides the use of the photoresist composition and the photoresist film as described above in photolithography.

[0054] In one embodiment, the photolithography is 365 nm, 254 nm, and electron beam photolithography. In particular, the photoresist composition and the photoresist film are used in 365 nm photolithography and electron beam photolithography.

[0055] The present application has the following advantages:

[0056] The present application provides a series of novel non-ionic acid generators based on substituted anthracene, i.e. the compound of formula I, which can be used as an acid generator for photoresist, mixed with photoresist host material, for example, mixed with known monomolecular resins (molecular glass). The compound of the present application can be used as an acid generator for i-line photolithography, DUV photolithography, and can also be used as an acid generator for electron beam photolithography and extreme ultraviolet photolithography.

[0057] The compound of the present application has good solubility in various polar solvents (such as PGMEA, PGME, cyclopentanone, etc.), and can be used to prepare a good film by spin coating. The polycyclic aromatic ring skeleton structure in the compound can effectively inhibit molecular crystallization and facilitate film formation. At the same time, the compound has a very high glass transition temperature (more than 100℃), and therefore has high thermal stability, which meets the requirements of photolithography process.

[0058] The synthesis process of the compound of the present application is simple, and the intermediates and final products can be separated from the system by recrystallization or precipitation, which is suitable for industrial production.

[0059] Terms and definitions

[0060] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims belongs.

[0061] "More" means three or more.

[0062] The term "halogen" includes F, CI, Br or I.

[0063] The term "C 1-12 "alkyl" is to be understood as meaning a straight-chain or branched saturated monovalent hydrocarbon group having from 1 to 12 carbon atoms, which 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, and the like, or isomers thereof. In particular, the group has 1, 2, 3, 4, 5, 6 carbon atoms ("C 1-6 alkyl"), for example methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly the group has 1, 2, or 3 carbon atoms ("C 1-3 alkyl"), for example methyl, ethyl, n-propyl or isopropyl.

[0064] The term "C 2-12 "alkenyl" is to be understood as meaning a straight-chain or branched monovalent hydrocarbon group which contains one or more double bonds and has 2 to 12 carbon atoms, preferably which contains one or more double bonds and has 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, in particular 2 or 3 carbon atoms ("C 2-3In case the alkenyl group contains more than one double bond, it is to be understood that the double bonds can be isolated from or conjugated to each other. The alkenyl group is for example ethenyl, allyl, (E)-2-methylethenyl, (Z)-2-methylethenyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1 - enyl, (Z)-but-1 -enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1 -enyl, (Z)-pent-1 -enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1 -enyl, (Z)-hex-1 -enyl, isopropenyl, 2-methylprop-2-enyl, 1 -methylprop-2-enyl, 2-methylprop-1 -enyl, (E)-1 -methylprop-1 -enyl, (Z)-1 -methylprop-1 -enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1 -methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1 -methylbut-2-enyl, (Z)-1 -methylbut-2-enyl, (E)-3-methylbut-1 -enyl, (Z)-3-methylbut-1 -enyl, (E)-2-methylbut-1 -enyl, (Z)-2-methylbut-1 -enyl, (E)-1 -methylbut-1 -enyl, (Z)-1 -methylbut-1 -enyl, 1,1 -dimethylprop-2-enyl, 1 -ethylprop-1 -enyl, 1 -propylvinyl, 1 -isopropylvinyl.

[0065] The term "C 2-12"Alkynyl" is to be understood as meaning a straight-chain or branched one- valent hydrocarbon radical which comprises one or more triple bonds and has 2 to 12 carbon atoms, for example 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, in particular 2 or 3 carbon atoms ("C2-C3-alkynyl"). Said alkynyl is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylprop-2-ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent-3-ynyl, 1-methylpent-3-ynyl, 4-methylpent-2-ynyl, 1-methylpent-2-ynyl, 4-methylpent-1-ynyl, 3-methylpent-1-ynyl, 2-ethylbut-3-ynyl, 1-ethylbut-3-ynyl, 1-ethylbut-2-ynyl, 1-propylprop-2-ynyl, 1-isopropylprop-2-ynyl, 2,2-dimethylbut-3-ynyl, 1,1-dimethylbut-3-ynyl, 1,1-dimethylbut-2-ynyl or 3,3-dimethylbut-1-ynyl. In particular, said alkynyl is ethynyl, prop-1-ynyl or prop-2-ynyl.

[0066] The term "C 3-12 "Cycloalkyl" is to be understood as meaning a saturated, one-valent monocyclic, bicyclic or polycyclic hydrocarbon ring (also referred to as fused ring hydrocarbon ring) having 3 to 10 carbon atoms. Bicyclic or polycyclic cycloalkyl includes spirocyclic cycloalkyl, bridged cycloalkyl, spirocyclic cycloalkyl; the term spiro refers to a fused ring structure formed by two or more cyclic structures sharing two adjacent ring atoms with one another (i.e. sharing one bond). The term bridged refers to a fused ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms with one another. The term spiro refers to a fused ring structure formed by two or more cyclic structures sharing one ring atom with one another. For example, the C 3-20 Cycloalkyl can be C 3-8 Monocyclic cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C 7-12 Bicyclic cycloalkyl, such as decalin; can also be C 7-12 Bridged cycloalkyl, such as norbornane, adamantane, bicyclo[2,2,2]octane.

[0067] The term "C 6-14"Aryl" is to be understood as preferably denoting a monovalent aromatic or partially aromatic, monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 Aryl") having 6 carbon atoms ("C6 aryl"), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 10 Aryl") such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 Aryl") such as fluorenyl, or a ring having 14 carbon atoms ("C 14 Aryl") such as anthryl. When the C 6-20 Aryl" is substituted, it can be mono- or polysubstituted. Also, there is no restriction on the substitution site, such as ortho, para or meta substitution.

[0068] The term "C 1-12 Haloalkyl" is to be understood as the case in which at least one H of the "C 1-12 Alkyl" as described above is replaced by a halogen. BRIEF DESCRIPTION OF DRAWINGS

[0069] Figure 1 UV absorption spectrum of compound 1.

[0070] Figure 2 Atomic force scanning probe microscope (AFM) plan view of a film of compound 1.

[0071] Figure 3 Atomic force scanning probe microscope (AFM) perspective view of a film of compound 1.

[0072] Figure 4 365 nm (i-line) photolithography stripe scanning electron microscope (SEM) image of a photoresist formed from compound 1 as an acid generator and other host materials.

[0073] Figure 5 248 nm photolithography stripe scanning electron microscope (SEM) image of a photoresist formed from compound 1 as an acid generator and other host materials.

[0074] Figure 6 365 nm (i-line) photolithography stripe scanning electron microscope (SEM) image of a photoresist formed from compound 7 as an acid generator and other host materials.

[0075] Figure 7 248 nm photolithography stripe scanning electron microscope (SEM) image of a photoresist formed from compound 7 as an acid generator and other host materials.

[0076] Figure 8 Electron beam lithography line scan SEM of photoresist formed with compound 1 as an acid generator and other host materials.

[0077] Figure 9 Electron beam lithography line scan SEM of photoresist formed with compound 7 as an acid generator and other host materials. DETAILED DESCRIPTION

[0078] In order to more clearly illustrate the application, the following further describes the application with reference to the preferred embodiments and the accompanying drawings. It should be understood by those skilled in the art that the specific description given below is illustrative and not restrictive and is not intended to limit the scope of the application.

[0079] Example 1 Preparation of compound (2)

[0080] Intermediate compound 2-IV was prepared as follows:

[0081]

[0082] To a cold (0°C) stirred solution of compound 2-V (2.34 g) and oxalyl chloride (4.8 mL) in CS2(21 mL) was added anhydrous AICI3(2.13 g), after 2 h more CS2(21 mL) and AICI3(1.6 g) were added and stirring was continued at 0°C for 2 h, then at room temperature overnight. Dilute aqueous hydrochloric acid (2 M) was added and the orange precipitate formed was collected by filtration, washed with water and then digested with 100 mL of 5% NaOH. The solid was washed with water and dried in air to give intermediate compound 2-IV in 80% yield. 1 HNMR (CDCI3, 400 MHz): δ ppm 9.27 (m, 1 H), 8.40 (db, 2 H), 7.85 (b, 1 H), 7.64 (m, 1 H), 7.54 (dt, 2 H), 2.72 (S, 3 H), 2.66 (S, 3 H), 2.62 (S, 3 H). MS (MALDI-TOF): m / z = 274.1, calculated value: (C 19 H 14 O2) m / z = 274.1 ([M] + ).

[0083] Example 2 Preparation of intermediate compound 2-III, synthesis route as follows:

[0084]

[0085] Potassium peroxodisulfate (5.52 g, 4 eq) was added to a solution of compound 2-IV (2.59 g, 1 eq) in methanol (300 mL) and the mixture was refluxed at 70 °C for 72 h. After cooling, water was added and the suspension was collected by filtration, washed with water and dried in air to give compound 2-III in 80% yield. 1 HNMR (CDC13, 400 MHz): δ ppm 8.97 (m, 1H), 8.55 (db, 2H), 8.11 (b, 1H), 7.67 (m, 1H), 7.61 (dt, 2H), 7.64 (m, 1H), 7.54 (dt, 2H), 2.72 (S, 3H), 2.66 (S, 3H), 2.62 (S, 3H). MS (MALDI-TOF): m / z = 305.1, calculated value: (C 19 H 14 O3)m / z = 304.1 ([M + ).

[0086] Example 3 Preparation of intermediate compound 2-II, synthesis route as follows:

[0087]

[0088] To a mixture of compound 2-III (1.2 g, 1 eq) and pyridine (10 mL) was added hydroxylamine hydrochloride (272 mg, 1 eq) and the mixture was heated at 100 °C for 15 h. The reaction mixture was poured into 50 mL of 1 M HC1. The precipitate was filtered and washed with water, the crude product was purified by column chromatography (20% ethyl acetate / hexane) to give compound 2-II in 80% yield. 1 HNMR (CDC13, 400 MHz): δ ppm 8.97 (m, 1H), 8.55 (db, 2H), 8.11 (b, 1H), 7.67 (m, 1H), 7.61 (dt, 2H), 7.64 (m, 1H), 7.54 (dt, 2H), 2.72 (S, 3H), 2.66 (S, 3H), 2.62 (S, 3H). MS (MALDI-TOF): m / z = 305.1, calculated value: (C 19 H 15 NO3)m / z = 305.1 ([M + ).

[0089] Example 4 Preparation of compound (2), synthesis route as follows:

[0090]

[0091] To a mixture of trifluoromethylsulfonyl chloride (0.64 mL, 1.5 mmol), compound 2-II (1.14 g, 1 eq) and dry DCM was added dropwise Et3N (2.24 mL, 2 mmol) at 0 °C. The mixture was then stirred at room temperature overnight. After completion of the reaction, it was quenched with cold water, diluted with DCM, the organic layer was separated and dried over Na2S04and the solvent was removed under vacuum to get orange crude sulfonate. The crude product was purified by column chromatography (20% ethyl acetate / hexane) to get compound (2) as an orange solid in 65% yield. 1 HNMR (400 MHz, DMSO-d6) δ (ppm) 9.59 (d, 1H), 9.14 (s, 1H), 8.55-8.67 (m, 2H), 8.19 (d, 1H), 7.79-7.90 (m, 2H), 7.66 (t, 1H), 2.72 (S, 3H), 2.66 (S, 3H), 2.62 (S, 3H). MS (MALDI-TOF): m / z = 421.1, calculated value: (C 20 H 14 F3NO4S)m / z = 421.1 ([M] + )。

[0092] Example 5 Preparation of compound (1)

[0093] The synthesis route is as follows:

[0094]

[0095] Compound 1-II (N-hydroxyanthranilic acid dihydrazide) was also prepared by following the preparation method as in example 1-3 above.

[0096] To a mixture of trifluoromethanesulfonyl chloride (1.5 eq), N-hydroxyanthranilic acid dihydrazide (250 mg, 1 eq) and 5 mL dry dichloromethane was added dropwise Et3N (0.52 mL, 2 eq) under ice bath. The mixture was then stirred at room temperature overnight. After completion of the reaction, it was quenched with 20 mL cold water, diluted with 20 mL dichloromethane, the organic layer was separated and dried over anhydrous Na2S04and the solvent was removed by rotary evaporation to get orange crude product. The crude product was purified by column chromatography (V 二氯甲烷：石油醚 = 1 :3) to get the product as an orange solid in 60% yield. 1 HNMR (DMSO-d6 400 MHz) δ (ppm) 9.59 (d, 1H), 9.14 (s, 1H), 8.55-8.67 (m, 2H), 8.19 (d, 1H), 7.79-7.90 (m, 2H), 7.66 (t, 1H), MS (MALDI-TOF): m / z = 395.0, calculated value: C17 H8F3NO5S m / z = 395.0 ([M] + ).

[0097] Example 6 Preparation of compound (3)

[0098] The synthetic route is as follows:

[0099]

[0100] To a mixture of perfluorobutylsulfonyl chloride (1.5 eq), 7-II (220 mg, 1 eq) and 5 mL of dry dichloromethane, Et3N (0.52 mL, 2 eq) was added dropwise under ice bath. The mixture was then stirred at room temperature overnight. After the reaction was completed, it was quenched with 20 mL of cold water, diluted with 20 mL of dichloromethane, extracted three times to separate the organic layer, and dried over anhydrous Na2S04, and the solvent was removed by rotary evaporation to obtain orange crude product. The crude product was purified by column chromatography (V 二氯甲烷：石油醚 = 1 :3) to obtain the product as an orange solid with a yield of 60%. 1 HNMR (DMSO-d6 400 MHz) δ (ppm) 9.59 (d, 1H), 9.14 (s, 1H), 8.55-8.67 (m, 2H), 8.19 (d, 1H), 7.79-7.90 (m, 2H), 7.66 (t, 1H), 5.14 (s, 2H), 2.72 (S, 3H), 2.66 (S, 3H), 2.62 (S, 3H). MS (MALDI-TOF): m / z = 417.0, calculated value: C 20 H 16 ClNO5S m / z = 417.0 ([M] + ).

[0101] Example 7 Preparation of compound (7)

[0102] The synthetic route is as follows:

[0103]

[0104] Compound 7-II was also prepared by reference to the preparation method as in Examples 1-3 above.

[0105] To a mixture of perfluorobutylsulfonyl chloride (1.5 eq), 7-II (220 mg, 1 eq) and 5 mL of dry dichloromethane, Et3N (0.52 mL, 2 eq) was added dropwise under ice bath. The mixture was then stirred at room temperature overnight. After the reaction was completed, it was quenched with 20 mL of cold water, diluted with 20 mL of dichloromethane, extracted three times to separate the organic layer, and dried over anhydrous Na2S04, and the solvent was removed by rotary evaporation to obtain orange crude product. The crude product was purified by column chromatography (V二氯甲烷：石油醚 = 1 :3) to give the product as an orange solid in 65% yield. 1 HNMR (DMSO-d6 400 MHz) δ (ppm) 9.23 (d, 1H), 9.02 (s, 1H), 8.55-8.67 (m, 2H), 8.19 (d, 1H), 7.79-7.90 (m, 2H), 7.66 (t, 1H), 3.14 (m, 2H), 2.51 (s, 12H), 2.66 (s, 3H), 2.62 (s, 3H). MS (MALDI-TOF): m / z = 629.5, calculated for C 26 H 20 F9NO5S m / z = 629.5 ([M] + ).

[0106] Example 8 Preparation of compound (8)

[0107] The synthesis route is as follows:

[0108]

[0109] Compound 8-II was also prepared by reference to the preparation method as in Examples 1-3 above.

[0110] To a mixture of methylsulfonyl chloride (1.5 eq), 8-II (240 mg, 1 eq) and 5 mL dry dichloromethane was added dropwise Et3N (0.52 mL, 2 eq) under ice bath. The mixture was then stirred at room temperature overnight. After the reaction was completed, it was quenched with 20 mL cold water, diluted with 20 mL dichloromethane, extracted three times to isolate the organic layer, and dried over anhydrous Na2S04, and the solvent was removed by rotary evaporation to give the crude product as an orange solid. The crude product was purified by column chromatography (V 二氯甲烷：石油醚 = 1 :3) to give the product as an orange solid in 65% yield. 1 HNMR (DMSO-d6 400 MHz) δ (ppm) 9.23 (d, 1H), 9.02 (s, 1H), 8.55-8.67 (m, 2H), 8.19 (d, 1H), 7.79-7.90 (m, 2H), 7.66 (t, 1H), 3.14 (m, 2H), 2.51 (s, 12H), 2.66 (s, 3H), 2.62 (s, 3H). MS (MALDI-TOF): m / z = 629.5, calculated for C 26 H 20 F9NO5S m / z = 629.5 ([M] + ).

[0111] Example 9

[0112] The UV absorption spectrum of the acid generator (compound 1) prepared in Example 5 in acetonitrile was measured, see Figure 1 Figure 1 The results show that it has a higher absorption at i-line, which is very suitable as an acid generator for i-line photolithography.

[0113] Example 10

[0114] Compound 1 in Example 5 was mixed with the molecular glass host material (SP8-Boc) (SP8-Boc is the structure disclosed in the literature Molecular Glass Resists Based on 9,9'-Spirobifluorene Derivatives: Pendant Effect and Comprehensive Evaluation in Extreme Ultraviolet Lithography. ACS Appl. Polym. Mater. 2019, 1 (3), 526-534) to prepare a solution with a host material concentration of 30 mg / ml (the mass of compound 1 accounts for 10% of the host material) in propylene glycol monomethyl ether acetate (PGMEA), filtered with a microporous filter with a pore size of 0.22 μm to obtain a spin coating liquid, and spin coating on an acid and base treated silicon substrate to prepare a film. The uniformity of the thin film was analyzed by atomic force microscopy (AFM), and the planar and stereoscopic views are shown in Figures 2 Figure 2 and 3 As can be seen from the figure, the obtained film is very uniform. This is mainly due to the polycyclic skeleton structure in the compound, which can effectively inhibit molecular crystallization, and thus is easy to form a film.

[0115] Example 11

[0116] i-line photolithography: Compound 1 in Example 5 was mixed as an acid generator and 2,7,2',7'-tetra-(3,4-di-tert-butyl carbonate phenyl)-9,9'-spirofluorene monomolecular resist reported in patent ZL201380000139.X, and dissolved in propylene glycol monomethyl ether acetate (PGMEA) (compound 1 is completely dissolved in this solvent). The content of the monomolecular resist host material is 30 mg / ml, and the content of the acid generator is 2.25 mg / ml. A microporous filter with a pore size of 0.22 μm was used for filtration to obtain a spin coating liquid, which was spin coated on an acid and base treated silicon substrate to prepare a film. The prepared film was subjected to exposure experiment on a 365 nm exposure machine, and the exposure period was 2 μm. A very uniform photolithography stripe was obtained, as shown in Figure 3 Figure 4 The width of the photolithography stripe is about 1 μm.

[0117] Example 12

[0118] 254nm photolithography: compound 1 in example 5 was mixed as acid generator and 2,7,2',7'-tetra-(3,4-di-tert-butylcarbonate phenyl)-9,9'-spirobifluorene monomolecular resin reported in patent ZL201380000139.X, dissolved in propylene glycol monomethyl ether acetate (PGMEA) (compound 1 is completely dissolved in this solvent). Among them, the content of monomolecular resin main material is 30 mg / ml, the content of acid generator is 2.25 mg / ml, filtered with a microporous filter with a pore size of 0.22 μm to obtain a spin coating liquid, spin coating on a silicon substrate treated with acid and alkali to form a film, and baking at 100°C for 3 minutes. The prepared film was exposed to a 254 nm light source for exposure experiment, and the exposure period was 2 μm. A very uniform photolithography stripe was obtained, as shown in Figure 5 The width of the photolithography stripe was about 1 μm.

[0119] Example 13

[0120] i-line photolithography: compound 1 in example 7 was mixed as acid generator and 2,7,2',7'-tetra-(3,4-di-tert-butylcarbonate phenyl)-9,9'-spirobifluorene monomolecular resin reported in patent ZL201380000139.X, dissolved in propylene glycol monomethyl ether acetate (PGMEA) (compound 1 is completely dissolved in this solvent). Among them, the content of monomolecular resin main material is 30 mg / ml, the content of acid generator is 2.25 mg / ml, filtered with a microporous filter with a pore size of 0.22 μm to obtain a spin coating liquid, spin coating on a silicon substrate treated with acid and alkali to form a film, and baking at 100°C for 3 minutes. The prepared film was exposed to a 365 nm exposure machine for exposure experiment, and the exposure period was 2 μm. A very uniform photolithography stripe was obtained, as shown in Figure 6 The width of the photolithography stripe was about 1 μm.

[0121] Example 14

[0122] 254nm photolithography: compound 7 in example 7 was mixed as acid generator and 2,7,2',7'-tetra-(3,4-di-tert-butylcarbonate phenyl)-9,9'-spirobifluorene monomolecular resin reported in patent ZL201380000139.X, dissolved in propylene glycol monomethyl ether acetate (PGMEA) (compound 1 is completely dissolved in this solvent). Among them, the content of monomolecular resin main material is 30 mg / ml, the content of acid generator is 2.25 mg / ml, filtered with a microporous filter with a pore size of 0.22 μm to obtain a spin coating liquid, spin coating on a silicon substrate treated with acid and alkali to form a film, and baking at 100°C for 3 minutes. The prepared film was exposed to a 254 nm light source for exposure experiment, and the exposure period was 2 μm. A very uniform photolithography stripe was obtained, as shown in Figure 7 The width of the photolithography stripe was about 1 μm.

[0123] Example 15

[0124] Electron beam lithography: compound 1 in example 5 was mixed with 2,7,2',7'-tetra-(3,4-di-tert-butylcarbonate phenyl)-9,9'-spirobifluorene monomolecular resin reported in patent ZL201380000139.X as an acid generator and dissolved in propylene glycol monomethyl ether acetate (PGMEA). The content of monomolecular resin host material was 30 mg / ml, and the content of acid generator was 2.25 mg / ml. The photoresist solution was filtered with a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The spin coating film was prepared on an acid and alkali treated silicon substrate, baked at 100°C for 3 minutes, and the prepared film was subjected to electron beam exposure experiment. The exposure period was 80 nm, and very uniform lithography stripes were obtained, as shown in Figure 8 , the width of the lithography stripes was about 32 nm.

[0125] Example 16

[0126] Electron beam lithography: compound 7 in example 7 was mixed with 2,7,2',7'-tetra-(3,4-di-tert-butylcarbonate phenyl)-9,9'-spirobifluorene monomolecular resin reported in patent ZL201380000139.X as an acid generator and dissolved in propylene glycol monomethyl ether acetate (PGMEA). The content of monomolecular resin host material was 30 mg / ml, and the content of acid generator was 2.25 mg / ml. The photoresist solution was filtered with a microporous filter with a pore size of 0.22 μm to obtain a spin coating solution. The spin coating film was prepared on an acid and alkali treated silicon substrate, baked at 100°C for 3 minutes, and the prepared film was subjected to electron beam exposure experiment. The exposure period was 100 nm, and very uniform lithography stripes were obtained, as shown in Figure 9 , the width of the lithography stripes was about 45 nm.

[0127] The above describes the embodiments of the present application. However, the present application is not limited to the above described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. The compound shown in Formula I: I in: R1, R3, and R4 may be the same or different, and are independently selected from H or C. 1-12 alkyl; m is 1, 2, 3 or 4; n is 1, 2 or 3; R2 is selected from C 1-12 Halogenated alkyl groups.

2. The compound according to claim 1, wherein, R1 is selected from H or C. 1-6 alkyl.

3. The compound according to claim 1, wherein, R2 is selected from C 1-6 Halogenated alkyl groups.

4. The compound according to claim 1, wherein, R1 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, 1-pentyl, isopentyl, tert-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, 1-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 1-nonyl, isononyl, 1-decyl, or n-dodecyl. R2 is selected from chloromethyl, trifluoromethyl, perfluorosubstituted butyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoropropyl, 3-bromopropyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, and 2,2,3,3,3-pentafluoropropyl. R3 and R4 are H or methyl groups.

5. The compound according to any one of claims 1-4, wherein, The compound is selected from the following compounds:

6. A method for preparing the compound according to any one of claims 1-5, wherein, Includes the following steps: Compound II reacts with R2SO2Cl to give the compound shown in Formula I; Wherein, R1, R2, R3, R4, m and n have the definitions described in any one of claims 1-5.

7. The use of the compound according to any one of claims 1-5 in photoresist; said compound is used as an acid-generating agent in photoresist.

8. A photoresist composition, wherein, Includes the compound according to any one of claims 1-5.

9. The photoresist composition according to claim 8, wherein, The photoresist composition further includes a solvent; 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-pentanone, and methyl isopentanone.

10. A photoresist film, characterized in that, Includes the compound according to any one of claims 1-5.

11. The application of the photoresist composition of claim 8 or 9, or the photoresist film of claim 10, in photolithography; The lithography used is 365nm, 248nm, 193nm, as well as extreme ultraviolet and electron beam lithography.

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