Silicon-containing high etch resistant molecular glass photoresist compounds, methods of making and using the same

Abstract

The application belongs to the field of photoetching technology, and particularly relates to a silicon-containing high-etching-resistance molecular glass photoresist compound, a preparation method and application thereof. The compound provided by the application has simple molecular structure, controllable molecular weight, simple synthesis steps, high thermal stability, no precipitation in baking, and no easy denaturation in photoetching. The provided negative molecular glass photoresist has good film forming property, high thermal stability, no easy denaturation in storage, low viscosity, and no need of additional solvent dilution in use. The photoresist prepared from the compound can obtain a uniform thin film on a substrate by a spin coating method, and the formula can be used in modern photoetching technologies such as 365nm photoetching, 248nm photoetching, 193nm photoetching, extreme ultraviolet photoetching and electron beam photoetching. Through electron beam exposure development, the exposed pattern has high contrast, excellent resolution and good sensitivity.

Description

Technical Field

[0001] This invention belongs to the field of photolithography technology, specifically relating to a silicon-containing high etching-resistant molecular glass photoresist compound, its preparation method, and its application. Background Technology

[0002] In the late 1950s, scientists invented germanium and silicon integrated circuits, and the advent of integrated circuits spurred the rapid development of semiconductor technology. Modern electronic devices demand that integrated circuits (chips) become smaller and smaller, with increasingly higher integration density. The smallest feature size of integrated circuits has progressed from the micrometer and submicrometer levels to the nanometer level.

[0003] In 1798, Senefelder first invented lithography, marking the beginning of its development. Bell Labs first used this method to print circuits on wafers around the 1930s. Subsequently, the U.S. Army Diamond Munitions Fuze Laboratory first patented and applied photolithography. In 1961, the technology was officially commercialized. With the gradual development of photolithography, it has evolved from ultraviolet lithography (436nm, 365nm) to deep ultraviolet lithography (248nm, 193nm) and then to smaller-sized electron beam lithography and extreme ultraviolet lithography. Currently, extreme ultraviolet lithography (EUVL) can achieve patterns with a minimum feature size of less than 7nm. In the development of faster and smaller semiconductor devices, new photoresist materials and lithography processes are currently being jointly explored and researched by industry and academia.

[0004] Molecular glasses are low molar mass materials that do not crystallize over time. Amorphous molecular glass materials can form uniform, transparent thin films and exhibit the glass transition process characteristic of polymers. Furthermore, they possess high thermal stability and isotropy. Compared to traditional polymer photoresists with molecular weight distribution, molecular glass photoresists have the advantages of being monodisperse, having a smaller free volume, and lacking intermolecular chain entanglement. Moreover, molecular glass photoresists and photoacid-generating agents have approximately the same molecular size, resulting in good compatibility.

[0005] Etching is an essential process for achieving high-resolution patterns. In this process, oxygen plasma is typically used to transfer the pattern from the upper photoresist layer to the lower layer. Therefore, the upper photoresist layer requires high oxygen plasma etching resistance. There is a need to develop ultra-high resolution molecular glass photoresists with high etching resistance to optimize photolithography performance. Summary of the Invention

[0006] The purpose of this invention is to provide a type of highly etch-resistant molecular glass photoresist and its preparation method.

[0007] Another aspect of the present invention is to provide the application of the above-mentioned highly etch-resistant molecular glass photoresist in extreme ultraviolet lithography, deep ultraviolet lithography, ultraviolet lithography and electron beam lithography.

[0008] To address the aforementioned technical problems, the present invention provides a compound of formula (I):

[0009]

[0010] Each of R1, R2, and R3 may be the same or different, and is independently selected from H, OH, unsubstituted, or optionally substituted by one, two, or more R groups. a The following groups are substituted: C 1-20 Alkyl, C 1-20 Alkoxy, C 1-20 Alkoxy-C(=O)O-, C 1-20 Alkoxy-C 1-20 Alkoxy-, C 6-20 Aryl-C(=O)OC 1-20 Alkoxy-, C 1-20 Alkoxy-C(=O)OC 1-20 Alkoxy-C 1-20 Alkoxy, C 6-20 Aryl-C(=O)OC 1-20 Alkoxy-C 1-20 Alkoxy-, C 3-20 Cycloalkyloxy-C(=O)O-, C 3-20 Cycloalkyloxy-C(=O)-C 1-20 Alkoxy-, C 2-20 alkenyl-C 1-20 Alkoxy-, 3-20 membered heterocyclic -O-, 3-20 membered heterocyclic -C 1-20 alkoxy group -; and R1, R2, and R3 are not simultaneously selected from H, OH, or C. 1-20 The same group in an alkyl group;

[0011] Each R4 may be the same or different, and is independently selected from OH, unsubstituted, or optionally substituted by one, two, or more R4 groups. b The following groups are substituted: C 1-20 Alkyl, C 1-20 Alkoxy, C 1-20 Alkoxy-C(=O)O-, C 1-20 Alkoxy-C 1-20 Alkoxy-, C 6-20 Aryl-C(=O)OC 1-20 Alkoxy-, C 1-20 Alkoxy-C(=O)OC 1-20 Alkoxy-C 1-20 Alkoxy-, C 6-20Aryl-C(=O)OC 1-20 Alkoxy-C 1-20 Alkoxy-, C 3-20 Cycloalkyloxy-C(=O)O-, C 3-20 Cycloalkyloxy-C(=O)-C 1-20 Alkoxy-, C 2-20 alkenyl-C 1-20 Alkoxy-, 3-20 membered heterocyclic -O-, 3-20 membered heterocyclic -C 1-20 Alkyl-, -OSi(R) b1 )3; and at least one of R4 is -OSi(R b1 3;

[0012] Each R a R b Whether the two are the same or different, they are independently selected from oxygen (=O) and C. 1-20 Alkyl, C 1-20 Alkoxy, C 3-20 cycloalkyl, C 2-20 alkenyl, 3-20 membered heterocyclic groups, C 6-20 Aryl;

[0013] Each R b1 Same or different, selected independently from C 1-20 Alkyl, C 3-20 cycloalkyl, C 2-20 alkenyl, 3-20 membered heterocyclic groups, C 6-20 Aryl.

[0014] According to an embodiment of the present invention, at least one of the groups R1, R2, and R3 is not H, or at least one of the groups is not OH, or at least one of the groups is not C. 1-20 alkyl.

[0015] According to an embodiment of the present invention, each of R1, R2, and R3 may be the same or different, and is independently selected from H, OH, and C. 1-10 Alkyl, C 1-10 Alkoxy, C 1-10 Alkoxy-C(=O)O-, C 1-10 Alkoxy-C 1-10 Alkoxy-, C 6-20 Aryl-C(=O)OC 1-10 Alkoxy-, C 1-10 Alkoxy-C(=O)OC 1-10 Alkoxy-C 1-10 Alkoxy, C 6-20 Aryl-C(=O)OC 1-10 Alkoxy-C 1-10 Alkoxy-, C 3-12Cycloalkyloxy-C(=O)O-, C 3-12 Cycloalkyloxy-C(=O)-C 1-10 Alkoxy-, C 2-20 alkenyl-C 1-10 Alkoxy-, 3-12 membered heterocyclic group -O-, 3-12 membered heterocyclic group -C 1-10 Alkyloxy-;

[0016] According to an embodiment of the present invention, each of R1, R2, and R3 may be the same or different, and is independently selected from H, OH, and C. 1-8 Alkoxy, C 1-8 Alkoxy-C(=O)O-, C 1-8 Alkoxy-C 1-8 Alkoxy-, C 6-14 Aryl-C(=O)OC 1-8 Alkoxy-, C 1-8 Alkoxy-C(=O)OC 1-8 Alkoxy-C 1-8 Alkoxy, C 6-14 Aryl-C(=O)OC 1-8 Alkoxy-C 1-8 Alkoxy-, C 3-8 Cycloalkyloxy-C(=O)O-, C 3-8 Cycloalkyloxy-C(=O)-C 1-8 Alkoxy-, C 2-8 alkenyl-C 1-8 Alkoxy-, 3-8 membered heterocyclic -O-, 3-8 membered heterocyclic -C 1-8 Alkyloxy-;

[0017] According to embodiments of the present invention, each of R1, R2, and R3 may be the same or different, and is independently selected from H, OH, methoxy, ...

[0018] * indicates a connection point.

[0019] According to an embodiment of the present invention, each R4 may be the same or different, and is independently selected from OH, C 1-20 Alkyl, C 1-20 Alkoxy, (C 1-20 alkyl)3SiO-, (aryl)2(C 1-20 alkyl)SiO-, (aryl)(C 1-20 Alkyl)2SiO-, C 1-20 Alkoxy-C(=O)O-, C 1-20 Alkoxy-C 1-20 Alkoxy, C 6-20 Aryl-C(=O)OC 1-20 Alkoxy, C1-20 Alkoxy-C(=O)OC 1-20 Alkoxy-C 1-20 Alkoxy, C 6-20 Aryl-C(=O)OC 1-20 Alkoxy-C 1-20 Alkoxy, C 3-20 Cycloalkyloxy-C(=O)O-, C 3-20 Cycloalkyloxy-C(=O)-C 1-20 Alkoxy, C 2-20 alkenyl-C 1-20 Alkoxy, 3-20 membered heterocyclic group -O-, 3-20 membered heterocyclic group -C 1-20 alkoxy groups; and at least one of R4 groups is (C 1-20 alkyl)3SiO-, (aryl)2(C 1-20 alkyl)SiO-, (aryl)(C 1-20 alkyl)2SiO-;

[0020] According to an embodiment of the present invention, each R4 may be the same or different, and is independently selected from OH, C 1-8 Alkoxy, C 1-8 Alkoxy-C(=O)O-, C 1-8 Alkoxy-C 1-8 Alkoxy, C 6-14 Aryl-C(=O)OC 1-8 Alkoxy, C 1-8 Alkoxy-C(=O)OC 1-8 Alkoxy-C 1-8 Alkoxy, C 3-8 Cycloalkyloxy-C(=O)O-, C 3-8 Cycloalkyloxy-C(=O)-C 1-8 Alkoxy, C 2-8 alkenyl-C 1-8 Alkoxy, 3-8 membered heterocyclic group -O-, 3-8 membered heterocyclic group -C 1-8 Alkoxy;

[0021] According to embodiments of the present invention, each R4 may be the same or different, and is independently selected from OH, methoxy,

[0022]

[0023] * indicates a connection point.

[0024] In one embodiment of the present invention, in R1, R2, R3, and R4, the heterocyclic group is an oxygen-containing heterocyclic group, such as a 3-8 membered oxehirocyclic alkyl group, such as oxehiropropyl, oxehirobutyl, oxehiropentyl, or oxehirohexyl.

[0025] According to an embodiment of the present invention, the compound shown in formula (I) has the following structure:

[0026]

[0027] The present invention also provides a method for preparing the compound shown in formula (I), comprising the following steps:

[0028]

[0029] (1) Compound (II) reacts with compound R4X or (R4)2NH to give compound (III);

[0030] (2) Compound (III) reacts with compound (IV) to produce the compound shown in formula (I);

[0031] Among them, R1, R2, R3, and R4 independently have the definitions described above; R 41 They are selected independently from OH and C. 1-20 Alkyl or C 1-20 Alkyl groups, wherein at least one of them is an R group. 41 X is -OH; L is OH, Cl, Br or I; L is -B(OH)2 or -B(OC)2. 1-20 Alkyl)2, Each Y1 may be the same or different, and is selected independently from C. 1-20 Alkylenes, each Y2 being identical or different, are independently selected from H or C. 1-20 Alkyl group; L is preferably -B(OH)2.

[0032] According to an embodiment of the present invention, in step (1), when the reactant is R4X, the reaction is carried out under the action of a base, the base being at least one of imidazole, pyridine, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, and potassium hydroxide; the reaction temperature is, for example, room temperature; and the reaction solvent is, for example, at least one of tetrahydrofuran, N-methylpyrrolidone, and acetonitrile.

[0033] According to an embodiment of the present invention, in step (1), when the reactant is (R4)2NH, the reaction is carried out under the action of an acid, such as concentrated H2SO4, and the temperature of the reaction is, for example, 80-120°C.

[0034] According to an embodiment of the present invention, in step (2), the reaction can be carried out under the action of a palladium-containing catalyst, such as at least one of tetra(triphenylphosphine)palladium(0), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride, tetra(triphenylarsine)palladium(0), tetra(tri-tert-butylphosphine)palladium(0), tetra(trimethoxyphosphine)palladium(0), bis(1,2-bis(diphenylphosphine)ethane)palladium(0), and bis(1,3-bis(diphenylphosphine)propane)palladium(0); the reaction is preferably carried out under the action of a base, such as at least one of sodium carbonate, cesium carbonate, potassium acetate, potassium phosphate, tetrabutylammonium fluoride, cesium fluoride, or potassium fluoride; the solvent for the reaction is such as at least one of acetone, toluene, dioxane, tetrahydrofuran, and anisole; the temperature of the reaction can be 60°C to 150°C, for example, 80°C to 120°C.

[0035] According to an embodiment of the present invention, when R1, R2, and R3 are selected from OH or C 1-20 When alkoxy is present, R1, R2, and R3 in the compound shown in formula (I) can further participate in the reaction to obtain R1, R2, and R3 excluding OH or C. 1-20 Compounds of formula (I) with groups other than alkoxy groups;

[0036] According to an embodiment of the present invention, the preparation method further includes the following step (3): when OH is present in R1, R2, and R3 of the compound of formula (I), the OH can be further reacted with R1'X1, R2'X2 and / or R3'X3 to obtain R1, R2, and R3 as other compounds of formula (I) except for OH;

[0037] According to an embodiment of the present invention, the preparation method further includes the following step (4): when C is present in R1, R2, and R3 of compound (I) 1-20 When alkoxy is present, the C 1-20 The alkoxy group can be further reacted to give OH, which can be further reacted in step (3) to give R1, R2, and R3, which are C-free. 1-20 Compounds of formula (I) other than alkoxy groups;

[0038] R1', R2', and R3' are groups formed by R1, R2, and R3 losing an oxygen atom at their connection with the parent nucleus, i.e., R1'-O-, R2'-O-, and R3'-O- represent R1, R2, and R3, respectively; X1, X2, and X3 may be the same or different and are independently selected from OH, Cl, Br, and I.

[0039] According to an embodiment of the present invention, in step (3), the reaction is preferably carried out in the presence of a catalyst, such as at least one of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), potassium carbonate, 4-dimethylaminopyridine (DMAP), or sodium hydride; the reaction temperature is, for example, room temperature; the reaction time is, for example, 2-12 h; the reaction can be carried out in the presence of a solvent, such as at least one of tetrahydrofuran or acetone.

[0040] According to an embodiment of the present invention, in step (3), when the molar ratio of the compound of formula (I) used as a raw material to the total amount of R1'X1, R2'X2 and / or R3'X3 is 1:1 to 1.2, a compound of formula (I) with fully protected hydroxyl groups can be obtained; when the molar ratio of the compound of formula (I) used as a raw material to R1'X1, R2'X2 and / or R3'X3 is 1:0.2 to 0.8, a compound of formula (I) with partially protected hydroxyl groups can be obtained.

[0041] According to an embodiment of the present invention, in step (4), R1, R2, and R3 of the compound of formula (I) used as raw materials can generate OH under the action of Lewis acid, wherein the Lewis acid is, for example, at least one of boron tribromide, boron triiodide, N,N-diethylaniline complexed boron triiodide, boron tribromide-dimethyl sulfide, 9-bromo-9-boron bicyclo[3.3.0]nonane, and catechol boron bromide (catalyzed by boron trifluoride diethyl ether), and the solvent for the reaction is, for example, dichloromethane or 1,2-dichloroethane.

[0042] The present invention also provides the use of the compound represented by formula (I) in photolithography, such as in photoresist.

[0043] The present invention also provides a photoresist composition comprising a compound of formula (I).

[0044] According to an embodiment of the present invention, the photoresist composition may be a positive photoresist composition or a negative photoresist composition.

[0045] In one embodiment of the present invention, the photoresist composition is a positive photoresist composition a, comprising compound (Ia), wherein compound (Ia) is a compound of formula (I), wherein at least one of R1, R2, R3, and R4 is unsubstituted or optionally substituted by one, two, or more R groups. a The following groups are substituted: C 1-20 Alkoxy, C 1-20 Alkoxy-C(=O)O-, C 1-20 Alkoxy-C 1-20 Alkoxy, C 6-20 Aryl-C(=O)OC 1-20Alkoxy, C 1-20 Alkoxy-C(=O)OC 1-20 Alkoxy-C 1-20 Alkoxy, C 6-20 Aryl-C(=O)OC 1-20 Alkoxy-C 1-20 Alkoxy, C 3-20 Cycloalkyloxy-C(=O)O-, C 3-20 Cycloalkyloxy-C(=O)-C 1-20 Alkoxy, C 2-20 alkenyl-C 1-20 alkoxy-, 3-20 membered heterocyclic group -O- or 3-20 membered heterocyclic group -C 1-20 Compounds of formula (I) with an alkoxy group and at most one of R1, R2, R3, and R4 having an OH group.

[0046] According to an embodiment of the present invention, the positive photoresist composition a comprises (Ia) compound, photoresist solvent, and photoacid-generating agent. That is, the positive photoresist composition a is a positive monomolecular photoresist.

[0047] Preferably, the positive photoresist composition a contains, by mass fraction, 0.1% to 10% of (Ia) compound and 0.01% to 1% of photoacid-generating agent.

[0048] According to an embodiment of the present invention, the positive photoresist composition a may also selectively contain other photoresists, acid diffusion inhibitors, etc.

[0049] Preferably, the positive photoresist composition a contains, by mass fraction, 0% to 5% of other photoresists and 0% to 0.1% of acid diffusion inhibitors.

[0050] In one embodiment of the present invention, the photoresist composition is a negative photoresist composition b, comprising a (Ib) compound, wherein the (Ib) compound is a compound of formula (I) in which R1, R2, R3, and R4 contain at least two -OH groups.

[0051] According to an embodiment of the present invention, the negative photoresist composition b comprises an (Ib) compound, a photoresist solvent, a photoacid-generating agent, and a crosslinking agent. That is, the negative photoresist composition b is a negative monomolecular photoresist.

[0052] Preferably, the negative photoresist composition b contains, by mass fraction, 0.1% to 10% of (Ib) compound, 0.01% to 1% of photoacid generator, and 0.01% to 5% of crosslinking agent.

[0053] According to an embodiment of the present invention, the negative photoresist composition b may also selectively contain other photoresists, acid diffusion inhibitors, etc.

[0054] Preferably, the negative photoresist composition b contains 0% to 5% of other photoresists and 0% to 0.1% of an acid diffusion inhibitor.

[0055] In one embodiment of the present invention, the photoresist composition is a negative photoresist composition c, comprising a (Ic) compound, wherein the (Ic) compound is a compound of formula (I) in which at least one of R1, R2, R3, and R4 is a C group. 2-20 alkenyl-C 1-20 Alkoxy, 3-8 membered heterocyclic group -O-, 3-8 membered heterocyclic group -C 1-8 Compounds of formula (I) with alkoxy groups.

[0056] According to an embodiment of the present invention, the negative photoresist composition c comprises an (Ic) compound, a photoresist solvent, and a photoacid-generating agent. That is, the negative photoresist composition c is another type of negative monomolecular photoresist.

[0057] Preferably, the negative photoresist composition c contains, by mass fraction, 0.1% to 10% of (Ic) compound and 0.01% to 1% of photoacid generator.

[0058] According to an embodiment of the present invention, the negative photoresist composition c may also selectively contain photoresist, acid diffusion inhibitor, crosslinking agent, etc.

[0059] Preferably, the negative photoresist composition c contains, by mass fraction, 0% to 5% photoresist, 0% to 0.1% acid diffusion inhibitor, and 0.01% to 5% crosslinking agent.

[0060] According to embodiments of the present invention, the other photoresist may be a photoresist known in the prior art, such as the photoresist disclosed in patent documents 201210156675.6, 201210070713.6, 201611105094.4, 201911329042.9, 201911167289.5, and 202010803879.9.

[0061] According to an embodiment of the present invention, the photoacid-generating agent can be ionic or nonionic, such as at least one selected from triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutylsulfonate, di(4-tert-butylphenyl)iodonium p-toluenesulfonate, N-hydroxynaphthalimide trifluoromethanesulfonate, 2-phenyl-(4-phenylthio)phenylthiohexafluoroantimonate, benzyl(4-hydroxyphenyl)methylthiodonium hexafluoroantimonate, and mixed salts of hexafluoroantimonate.

[0062] According to an embodiment of the present invention, the photoresist solvent may be selected from at least one of propylene glycol methyl ether acetate (PGMEA), ethyl lactate, ethylene glycol monomethyl ether, cyclohexanone, etc.

[0063] According to an embodiment of the present invention, the acid diffusion inhibitor may be selected from n-octylamine, tri-n-octylamine, N-methyldi-n-octylamine, tert-octylamine, etc.

[0064] According to an embodiment of the present invention, the crosslinking agent may be selected from at least one of tetramethoxymethyl glycourea, bisphenol A type glycidyl ether, etc.

[0065] According to embodiments of the present invention, the photoresist composition may further include other additives, such as sensitizers, surfactants, dyes, stabilizers, cosolvents, etc.

[0066] The present invention further provides the application of the compound shown in formula (I) or the photoresist composition thereon in photolithography processes such as 365nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet (EUV) photolithography or electron beam lithography (EBL).

[0067] The present invention also provides a photoresist coating comprising the compound shown in formula (I).

[0068] The present invention also provides a method for preparing the photoresist coating, comprising applying the photoresist composition onto a substrate (e.g., spin coating).

[0069] Preferably, the coating method is to spin-coat the substrate using a spin coater.

[0070] Preferably, the substrate can be a silicon wafer, a silicon dioxide wafer, or a compound semiconductor wafer. The silicon wafer is preferably a silicon wafer that has undergone hydrophobic treatment.

[0071] Beneficial effects

[0072] 1. This invention introduces silicon-containing groups into the molecules of the photoresist host material, thereby obtaining a photoresist material with high etching resistance.

[0073] 2. The compound represented by general formula (I) of this invention is a stereoasymmetric amorphous small molecule compound with a simple molecular structure, controllable molecular weight, simple synthesis steps, and high thermal stability. It does not precipitate during baking, is not easily denatured during photolithography, and has a high melting point and glass transition temperature (both melting points are above 100°C), which can meet the requirements of photolithography technology. The film structure does not change during high-temperature baking.

[0074] 3. The photoresist composition of the present invention can prepare uniform thin films with good resolution, photosensitivity, and adhesion. These films are easy to store, and the molecular glass, serving as the matrix component, does not precipitate during film formation. The negative photoresist composition prepared by the present invention exhibits good film-forming properties, high thermal stability, minimal degradation during storage, and low viscosity, requiring no additional solvent dilution during use. After electron beam exposure and development, the exposed pattern exhibits high contrast, excellent resolution, and good sensitivity, achieving a lithographic linewidth of 25-30 nm. Attached Figure Description

[0075] Figure 1 The TGA curve of compound (IB) shows that the decomposition content is less than 10% at 300℃, indicating that compound (IB) has high thermal stability.

[0076] Figure 2 SEM results of electron beam exposure of compound (IB) with 60 nm periodic dense lines.

[0077] Figure 3 SEM results of electron beam exposure of 60 nm periodic lines for compound (IB-2).

[0078] Terminology Definitions and Explanations

[0079] Unless otherwise stated, the definitions of groups and terms recorded in this application specification and claims, including definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, and definitions of specific compounds in the examples, can be arbitrarily combined and combined with each other. Such combinations and combinations of group definitions and compound structures should be understood as being within the scope of this application specification and / or claims.

[0080] Unless otherwise stated, the numerical ranges described in this specification and claims are equivalent to describing at least each specific integer value therein. For example, the numerical range "1-20" is equivalent to describing each integer value in the numerical range "1-20", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0081] Term "C" 1-20 "alkyl" should be understood to refer to straight-chain and branched alkyl groups having 1 to 20 carbon atoms, preferably "C". 1-8 Alkyl group. "C" 1-8 "Alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. 1-6"Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers.

[0082] Term "C" 3-20 "Cycloalkyl" should be understood to refer to saturated monovalent monocyclic, bicyclic (such as fused ring, bridged ring, spiro ring) hydrocarbon rings or tricyclic alkanes, having 3 to 29 carbon atoms, preferably "C". 3-12 "Cycloalkyl", more preferably "C" 3-8 cycloalkyl. The term "C" 3-12 "Cycloalkyl" should be understood to refer to a saturated monovalent monocyclic, bicyclic (e.g., bridged, spirocyclic) hydrocarbon ring or tricyclic alkane 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 borneolyl, indolyl, hexahydroindolyl, tetrahydronaphthyl, decahydronaphthyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]heptenyl, 6,6-dimethylbicyclo[3.1.1]heptyl, 2,6,6-trimethylbicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl, 2,7-diazaspiro[3,5]nonyl, 2,6-diazaspiro[3,4]octyl; or tricyclic hydrocarbon groups, such as adamantyl.

[0083] Term "C" 2-20 "Alkenyl" should be understood as representing a straight-chain or branched monovalent hydrocarbon group containing one or more double bonds and having 2 to 20 carbon atoms, preferably "C". 2-10 "Alkenyl". "C" 2-10 "Alkenyl" should be understood to preferably represent a straight or branched monovalent hydrocarbon group containing one or more double bonds and having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, more preferably "C 2-8 "Alkenyl". "C" 2-10 "Alkenyl" should be understood to preferably represent a straight or branched monovalent hydrocarbon group containing one or more double bonds and having 2, 3, 4, 5, 6, 7 or 8 carbon atoms, for example, having 2, 3, 4, 5 or 6 carbon atoms (i.e., C... 2-6alkenyl), having 2 or 3 carbon atoms (i.e., C24, C34, C4 ... 2-3 Alkenyl). It should be understood that when the alkenyl group contains more than one double bond, the double bonds may be separable or conjugated. The alkenyl group is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (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)- Pentyl-1-enyl, (Z)-pentyl-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-methyl But-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.

[0084] The term "3-20 membered heterocyclic group" refers to a saturated or unsaturated non-aromatic ring or ring system, for example, a 4-, 5-, 6-, or 7-membered monocyclic ring, a 7-, 8-, 9-, 10-, 11-, or 12-membered bicyclic ring (such as a fused ring, bridged ring, or spirocyclic ring), or a 10-, 11-, 12-, 13-, 14-, or 15-membered tricyclic ring system, and contains at least one, for example, 1, 2, 3, 4, 5, or more heteroatoms selected from O, S, and N, wherein N and S may optionally be oxidized to various oxidation states to form nitrides, -S(O)-, or -S(O)2- states. Preferably, the heterocyclic group may be selected from "3-10 membered heterocyclic groups". The term "3-10 membered heterocyclic group" means a saturated or unsaturated non-aromatic ring or ring system containing at least one heteroatom selected from O, S, and N. 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). The heterocyclic group can include fused or bridged rings and spirocyclic rings. 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.

[0085] Term "C" 6-20 "Aryl" should preferably be understood to represent a monocyclic, bicyclic (such as fused ring, bridged ring, spiro ring), or tricyclic hydrocarbon ring having 6 to 20 carbon atoms and possessing monovalent aromaticity or partial aromaticity. It can be a monoaromatic ring or a polyaromatic ring fused together, preferably "C". 6-14 Aryl. The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20 When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0086] The term "5-20-membered heteroaryl" should be understood to include monocyclic, bicyclic (e.g., fused, bridged, spirocyclic), or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, for example, "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and in each case, may be benzo[a]fused. "Hyperaryl" also refers to a group in which the heteroaryl ring is fused with one or more aryl, alicyclic, or heterocyclic rings, wherein the root or point of the connection is on the heteroaryl ring. Detailed Implementation

[0087] 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.

[0088] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0089] Example 1: Synthesis and preparation of compound P1

[0090]

[0091] Weigh 5.44 g (10 mmol) of tetrabromobisphenol A and 1.7 g (25 mmol) of imidazole and add them to a 100 mL two-necked flask. After evacuating the air three times, measure 50 mL of DMF and add it to the flask. Stir to dissolve the DMF, then slowly add 6.9 g (25 mmol) of tert-butyldiphenylchlorosilane (TBDPSCl). React at room temperature for 3 h. After the reaction is complete, dilute the reactants with dichloromethane and wash three times successively with dilute hydrochloric acid and deionized water. Dry in MgSO4 for 4 hours, then exchange with ethanol solvent and dry under vacuum at 60 °C for 8 h to obtain compound P1.

[0092] Example 2: Synthesis and preparation of compound P2

[0093]

[0094] 10.2 g (10 mmol) of compound P1 and 6.84 g (45 mmol) of 4-methoxyphenylboronic acid were weighed and added sequentially to a 500 mL three-necked flask. 150 mL of 1,4-dioxane was added and stirred thoroughly to dissolve. Under stirring, 80 mL of 40 wt.% potassium carbonate solution was added, and the mixture was heated to 90 °C. Then, 1.138 g of tetrakis(triphenylphosphine)palladium was added. The mixture was refluxed at 90 °C for 6 h. After the reaction was complete, the reaction mixture was diluted with dichloromethane, washed three times with saturated brine, dried with MgSO4 for 4 h, and compound P2 was precipitated using ethanol as a poor solvent. The precipitated compound P2 was then dried under vacuum at 60 °C for 8 h.

[0095] Example 3: Synthesis and preparation of compound (IA)

[0096]

[0097] 11.3 g (10 mmol) of compound P2 was dissolved in 100 mL of dichloromethane, and the solution was transferred to a constant-pressure dropping funnel. 100 mL of dichloromethane was added to a 500 mL three-necked flask, and 4.1 mL (45 mmol) of BBr3 was added and stirred under ice-water bath conditions. The reaction temperature was controlled at 0 °C, and the solution in the constant-pressure dropping funnel was slowly added to the three-necked flask. After 3 h of reaction, the reaction solution in the three-necked flask was collected in a constant-pressure dropping funnel. 200 mL of deionized water was added to a 1000 mL three-necked flask, and the reaction temperature was controlled at 0 °C. The reaction solution in the constant-pressure dropping funnel was added to the three-necked flask to quench excess BBr3. After the reaction was complete, the mixture was extracted with ethyl acetate, washed three times with deionized water, dried over MgSO4 for 4 h, and then compound (IA) was precipitated using n-hexane as a poor solvent. After drying under vacuum at 60 °C for 8 h, compound (IA) was obtained. MALDI-TOF(C 71 H 68 NaO6Si2)m / z:[M+Na]1095.44

[0098] Example 4: Synthesis and preparation of compound (IB)

[0099]

[0100] Weigh 2.15 g (2 mmol) of compound (IA) and 2.24 g (40 mmol) of KOH, and add them sequentially to a 50 mL two-necked flask. Then add 1.37 g (10 mmol) of bromopropylene oxide, followed by 10 mL of N-methylpyrrolidone. React at 65 °C for 4 h. After the reaction is complete, dilute the reaction mixture with dichloromethane, wash three times with deionized water, dry with anhydrous MgSO4 for 4 h, and then perform silica gel column chromatography (eluent: tetrahydrofuran:petroleum ether = 2:1). Collect the product, evaporate to dryness, and dry in a vacuum oven at 60 °C for 8 h to obtain compound (IB), 1.244 g, yield 48%. MALDI-TOF (C 83 H 84 NaO 10 Si2)m / z:1319.55. 1 H NMR (300MHz, DMSO) δ7.10 (s, 28H), 6.91 (s, 4H), 6.63 (d, J = 8.4Hz, 8H), 4.23 (d, J = 11.4Hz, 5H) ,3.73(dd,J=11.5,6.3Hz,5H),2.84(t,J=4.5Hz,5H),2.70(s,5H),1.62(s,6H),0.47(s,18H).

[0101] Example 5: The synthesis method of compound (IB-2) is the same as in Examples 1-4. By changing the tert-butyldiphenylsilyl group to a tert-butyldimethylsilyl group, compound (IB-2) was prepared. The molecular formula is as follows: MALDI-TOF(C 83 H 84 NaO 10 Si2)m / z:1048.497. 1 H NMR (300MHz, DMSO) δ7.42(d,J=8.5Hz,8H),7.09(s,4H),6.95(d,J=8.6Hz,8H),4.34(dd,J=11.4,2.1Hz,4H),3.82(dd,J=11 .4,6.6Hz,4H),2.84(t,J=4.6Hz,4H),2.71(dd,J=5.0,2.6Hz,4H),1.74(s,6H),1.35(s,4H),0.66(s,18H),-0.78(s,12H).

[0102]

[0103] Example 6: Preparation of a negative photoresist composition containing compound (IB)

[0104] Weigh 100 mg of compound (IB), 7.5 mg of the photoacid-generating agent benzyl(4-hydroxyphenyl)methylthionyl hexafluoroantimonate, and 7.5 mg of additives. Measure 5 mL of the photoresist solvent propylene glycol methyl ether acetate (PGMEA) to prepare a photoresist solution with a concentration of 20 mg / mL. After ultrasonic treatment for 30 min, filter three times through a 0.20 μm polytetrafluoroethylene membrane to prepare a negative photoresist composition.

[0105]

[0106] Example 7: Preparation of a negative photoresist composition containing compound (IB-2)

[0107] Following the basic principle of Example 6, compound (IB-2) was replaced with compound (IB). A negative photoresist composition of 30 mg / mL was prepared.

[0108] Example 8: Photolithographic properties of a negative photoresist composition containing compound (IB)

[0109] Untreated blank silicon wafers were selected, and the surface dust was removed by blowing with a nitrogen gun. The negative photoresist composition prepared in Example 6 was spin-coated onto the silicon wafer, with spin-coating parameters set to 2800 rpm / 90 s and pre-baking parameters set to 80°C / 180 s. The film thickness was measured using an optical ellipsometry and found to be 43 nm. Exposure was performed using an electron beam with an accelerating voltage of 100 kV, and post-baking parameters were set to 90°C / 120 s. Development was then performed with a developer solution of methyl isobutyl ketone:isopropanol = 5:1 for 60 s, followed by isopropanol rinsing for 60 s. After development, SEM images were acquired using a Hitachi 8230 scanning electron microscope. The specific photolithography results are shown below. Figure 2 As shown. By Figure 2 It is known that the photoresist composition can achieve 30nm photolithographic stripes and has high sensitivity (166μC / cm). 2 (and high contrast).

[0110] Example 9: Photolithographic properties of a negative photoresist composition containing compound (IB-2)

[0111] Untreated blank silicon wafers were selected, and the surface dust was removed by blowing with a nitrogen gun. The negative photoresist composition prepared in Example 7 was spin-coated onto the silicon wafer, with spin-coating parameters set to 4500 rpm / 90 s and pre-baking parameters set to 80°C / 180 s. The film thickness was measured to be 41.2 nm using an optical ellipsometry. Exposure was performed using an electron beam with an accelerating voltage of 100 kV, and the post-baking parameters were set to 90°C / 120 s. Development was performed with methyl isobutyl ketone developer for 60 s, followed by rinsing with isopropanol for 60 s. After development, SEM images were acquired using a Hitachi 8230 scanning electron microscope. The specific photolithography results are shown below. Figure 3 As shown. By Figure 3It is known that the photoresist composition can achieve 30nm photolithographic stripes and has high sensitivity (320μC / cm). 2 (and high contrast).

[0112] The embodiments of the technical solution of the present invention have been described above by way of example. It should be understood that the protection scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the protection scope of the claims of this application.

Claims

1. A type of compound represented by formula (I): ； in, R1 is selected from a 3-8 membered heterocyclic group -C 1-8 Alkyloxy-; Each R2 and R3 may be the same or different, and they are independently selected from H, 3-8 membered heterocyclic groups -C. 1-8 Alkyloxy-; The 3-8 membered heterocyclic group is a 3-8 membered oxoheterocyclic alkyl group; R4 is selected from -OSi(R b1 3; Each R b1 Same or different, selected independently from C 1-8 Alkyl, C 6-14 Aryl.

2. The compound according to claim 1, characterized in that, R1 is selected from ; * indicates a connection point; Each R2 and R3 may be the same or different, and they are independently selected from H. * indicates a connection point.

3. The compound according to claim 1, characterized in that, Each R4 may be the same or different, and is selected independently from each other. , , , * indicates a connection point.

4. The compound according to claim 1, characterized in that, The 3-8 membered oxecycloalkyl group is selected from oxecyclopropyl, oxecyclobutyl, oxecyclopentyl, and oxecyclohexyl.

5. The compound according to claim 1, characterized in that, The compound shown in formula (I) has the following structure: ； ； IB-2.

6. A method for preparing the compound according to any one of claims 1-5, comprising the following steps: ； (1) Compound (II) reacts with compound R4X to give compound (III); (2) Compound (III) reacts with compound (IV) to produce the compound shown in formula (I); Wherein, R1, R2, R3, and R4 independently have the definitions described in any one of claims 1-5; R 41 X is OH; L is Cl, Br, or I; L is -B(OH)2. , or .

7. The use of the compound according to any one of claims 1-5 in the preparation of negative photoresists.

8. A negative photoresist composition comprising the compound according to any one of claims 1-5.

9. The photoresist composition according to claim 8, characterized in that, The photoresist composition is selected from the following negative photoresist composition c: The negative photoresist composition c consists of the compound of formula (I) as described in any one of claims 1-5, a photoresist solvent, and a photoacid-generating agent.

10. The photoresist composition according to claim 9, characterized in that, The negative photoresist composition c contains, by mass fraction, 0.1% to 10% of the compound represented by formula (I) and 0.01% to 1% of a photoacid-generating agent.

11. The use of the photoresist composition of claim 8 in 365nm lithography, 248nm lithography, 193nm lithography, extreme ultraviolet lithography or electron beam lithography processes.

12. A photoresist coating comprising the photoresist composition of claim 8.

13. The method for preparing the photoresist coating of claim 12, comprising coating the photoresist composition onto a substrate.

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