Vinylbenzenesulfonate compounds containing imide structure, homopolymers thereof, and photoresists containing the same

Abstract

The present disclosure relates to vinyl benzene sulfonate compounds containing imide structure, homopolymers thereof, and photoresists containing the homopolymers. The vinyl benzene sulfonate imide compounds have a structure shown in Formula I, wherein R is a divalent organic group selected from substituted or unsubstituted C1-C4 alkylene, substituted or unsubstituted C2-C4 alkenylene, substituted or unsubstituted C4-C6 cycloalkenylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C6-C30 heteroarylene, substituted or unsubstituted norbornylene, and substituted or unsubstituted oxanorbornylene, wherein in the structure shown in Formula I, at least one carbon atom in R is connected to two carbon atoms in the imide group to form a four- to seven-membered heterocyclic ring. Vinyl benzene sulfonate imide polymers formed with the compounds as monomers have good thermal stability and very strong ultraviolet absorption capacity, and can be used as a main body resin for photoresist compositions.

Description

Technical Field

[0001] This application belongs to the field of functional polymer materials, specifically relating to vinylbenzene sulfonate compounds containing imide structures, their homopolymers, their preparation methods, and photoresists containing the homopolymers. Background Technology

[0002] Polystyrene sulfonic acid is a polymer compound with sulfonic acid groups. The benzene ring in its molecular structure provides it with good stability and chemical inertness, while the sulfonic acid groups provide unique electrical, optical, and chemical properties. Due to its excellent electrical conductivity, polystyrene sulfonic acid is widely used in the electronics industry; due to its unique photoelectric properties, it is used as a key material in photoelectric conversion devices. As a highly efficient antistatic agent, polystyrene sulfonic acid can significantly reduce the surface resistance of materials such as plastics, textiles, and coatings, effectively preventing the generation and accumulation of static electricity. Polystyrene sulfonates are also a class of widely used polymer materials, and their unique chemical structure has led to their widespread application in the fields of medicine, optoelectronics, and ion exchange. In contrast, the application of polystyrene sulfonates in plastic products is somewhat limited because the ester bonds are easily hydrolyzed under alkaline conditions. Conversely, by utilizing the easy breakage of its ester bonds, it can be used as a responsive material. For example, stimuli such as pH and ultraviolet light can cause structural changes in polystyrene sulfonates, thereby achieving some special responsive functions. However, further improvements to the properties of polystyrene sulfonates are still needed to better meet their novel applications. Summary of the Invention

[0003] This application provides a novel class of styrene sulfonate homopolymers containing an imide structure. These polymers have side chains containing sulfonate structures that can break under specific conditions (such as irradiation or acid catalysis), allowing them to be converted into polar sulfonic acid polymers through a controlled deprotection reaction. They can serve as responsive polymer precursors, functional polymer intermediates, or specialty polymer raw materials, showing promising applications in controlled polar polymers, environmentally responsive materials, antibacterial materials, and photo-patterning materials. This stable and highly responsive functional polymer material has significant industrial application value. Surprisingly, the styrene sulfonate homopolymers containing an imide structure of this application can be used as the host resin for photoresists. These photoresists can achieve controlled deprotection of the side chains through high-energy electron beam irradiation, utilizing polarity changes to achieve negative pattern development in specific organic solvents. This makes them suitable for high-resolution micro / nano pattern fabrication, showing promising applications in the manufacture of semiconductor devices, micro / nano optical components, and microelectromechanical systems (MEMS).

[0004] In a first aspect, this disclosure provides a vinylbenzene sulfonate imide compound having the structure shown in Formula I: Formula I Wherein R is a divalent organic group selected from substituted or unsubstituted C1-C4 alkylene, substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C4-C6 cycloalkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted norbornyl, substituted or unsubstituted oxanorbornyl, wherein in the structure shown in Formula I, at least one carbon atom in R is connected to two carbon atoms in the imide group to form a four- to seven-membered heterocycle.

[0005] In some embodiments, the substituents of the substituted C1-C4 alkylene, substituted C2-C4 alkenyl, substituted C4-C6 cycloalkenyl, substituted C6-C30 arylene, substituted C6-C30 heteroarylene, substituted norbornyl, and substituted oxanorbornyl are selected from halogens, C1-C6 alkyl, and C1-C6 alkoxy groups.

[0006] In some embodiments, the C1-C4 alkylene groups are selected from methylene, ethylene, 1,2-propylene, and 1,3-propylene.

[0007] In some embodiments, the C2-C4 alkenyl group is selected from 1,2-vinylene, 1,2-propenylene, and 1,3-propenylene.

[0008] In some embodiments, the C4-C6 cycloene group is selected from cyclobutene-1,2-diyl, cyclobutene-2,3-diyl, cyclobutene-3,4-diyl, cyclopentene-1,2-diyl, cyclopentene-2,3-diyl, cyclopentene-3,4-diyl, cyclohexene-1,2-diyl, cyclohexene-2,3-diyl, cyclohexene-3,4-diyl, and cyclohexene-4,5-diyl.

[0009] In some embodiments, the C6-C30 arylene groups are selected from o-phenylene, o-biphenylene, o-terphenylene, 1,2-naphthylene, 2,3-naphthylene, and 1,8-naphthylene.

[0010] In some embodiments, the C6-C30 heteroaryl group is selected from 2,3-pyridinyl, 3,4-pyridinyl, 3,4-pyridazinyl, 5,6-pyridazinyl, 4,5-pyrimidinyl, 5,6-pyrimidinyl, 2,3-pyridazinyl, 2,3-quinolineyl, 3,4-quinolineyl, 5,6-quinolineyl, 6,7-quinolineyl, 7,8-quinolineyl, and 3,4-isoquinoline. 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 3,4-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 2,3-Isoquinoxalin, 5,6-Isoquinoxalin, 6,7-Isoquinoxalin, 7,8-Isoquinoxalin.

[0011] In some embodiments, the norbornenyl group is selected from 2,3-norbornenyl or 5,6-norbornenyl.

[0012] In some embodiments, the oxa-norbornenyl group is selected from 7-oxa-2,3-norbornenyl or 7-oxa-5,6-norbornenyl.

[0013] In some embodiments, the compound is selected from the group consisting of: .

[0014] Secondly, this disclosure provides a vinylbenzene sulfonate imide polymer, which is polymerized from monomers of Formula I: Formula I R is selected from substituted or unsubstituted C1-C4 alkylene, substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C4-C6 cycloalkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted norbornyl, and substituted or unsubstituted oxanorbornyl. In the structure shown in Formula I, at least one carbon atom in R is connected to two carbon atoms in the imide group to form a four- to seven-membered heterocycle.

[0015] In some embodiments, the substituents of the substituted C1-C4 alkylene, substituted C2-C4 alkenyl, substituted C4-C6 cycloalkenyl, substituted C6-C30 arylene, substituted C6-C30 heteroarylene, substituted norbornyl, and substituted oxanorbornyl are selected from halogens, C1-C6 alkyl, and C1-C6 alkoxy groups.

[0016] In some embodiments, the C1-C4 alkylene groups are selected from methylene, ethylene, 1,2-propylene, and 1,3-propylene.

[0017] In some embodiments, the C2-C4 alkenyl group is selected from 1,2-vinylene, 1,2-propenylene, and 1,3-propenylene.

[0018] In some embodiments, the C4-C6 cycloene group is selected from cyclobutene-1,2-diyl, cyclobutene-2,3-diyl, cyclobutene-3,4-diyl, cyclopentene-1,2-diyl, cyclopentene-2,3-diyl, cyclopentene-3,4-diyl, cyclohexene-1,2-diyl, cyclohexene-2,3-diyl, cyclohexene-3,4-diyl, and cyclohexene-4,5-diyl.

[0019] In some embodiments, the C6-C30 arylene groups are selected from o-phenylene, o-biphenylene, o-terphenylene, 1,2-naphthylene, 2,3-naphthylene, and 1,8-naphthylene.

[0020] In some embodiments, the C6-C30 heteroaryl group is selected from 2,3-pyridinyl, 3,4-pyridinyl, 3,4-pyridazinyl, 5,6-pyridazinyl, 4,5-pyrimidinyl, 5,6-pyrimidinyl, 2,3-pyridazinyl, 2,3-quinolineyl, 3,4-quinolineyl, 5,6-quinolineyl, 6,7-quinolineyl, 7,8-quinolineyl, and 3,4-isoquinoline. 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 3,4-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 2,3-Isoquinoxalin, 5,6-Isoquinoxalin, 6,7-Isoquinoxalin, 7,8-Isoquinoxalin.

[0021] In some embodiments, the norbornenyl group is selected from 2,3-norbornenyl or 5,6-norbornenyl.

[0022] In some embodiments, the oxa-norbornenyl group is selected from 7-oxa-2,3-norbornenyl or 7-oxa-5,6-norbornenyl.

[0023] In some embodiments, the polymer is selected from the group consisting of: , Where n = 50 to 100.

[0024] Thirdly, this disclosure provides a photoresist composition comprising the aforementioned polymer.

[0025] Fourthly, this disclosure provides a method for forming a pattern, the method comprising forming a photoresist layer using the above-described photoresist composition. Attached Figure Description

[0026] Figure 1 These are the thermogravimetric analysis spectra of the product samples from Examples 2-2 and 2-3.

[0027] Figure 2 These are the DSC thermal analysis spectra of the product samples from Examples 2-2 and 2-3.

[0028] Figure 3 These are the UV absorption spectra of the product samples from Examples 2-3.

[0029] Figure 4 These are scanning electron microscope images of patterns formed using photoresists from Examples 3-1 and 3-2.

[0030] Figure 5 These are the curves showing the relationship between exposure dose and film thickness for the photoresist in Examples 3-1 and 3-2. Detailed Implementation

[0031] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0032] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0033] In this document, the terms “contains,” “includes,” “containing,” and similar terms encompass the meanings of “basically composed of” and “composed of.” For example, when this document discloses “A contains B and C,” “A is basically composed of B and C” and “A is composed of B and C” should be considered as having been disclosed in this document.

[0034] In this document, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0035] Unless otherwise specified, percentages, ppm, ppb and proportions in this article are all expressed by mass.

[0036] In this article, "alkyl" refers to a monovalent hydrocarbon group formed by the loss of a hydrogen atom from a straight-chain or branched chain alkane.

[0037] In this article, "cycloalkyl" refers to a monovalent hydrocarbon group formed by the loss of a hydrogen atom from a cyclic alkane.

[0038] In this article, "alkylene" refers to a divalent hydrocarbon group formed by the loss of two hydrogen atoms from a straight-chain or branched chain alkane. The two lost hydrogen atoms could originally be located on the same carbon atom or two different carbon atoms.

[0039] In this article, "cycloalkylene" refers to a divalent hydrocarbon group formed by the loss of two hydrogen atoms from a cyclic alkane. The two lost hydrogen atoms could originally be located on the same carbon atom or two different carbon atoms.

[0040] In this article, "alkenyl" refers to a monovalent hydrocarbon group formed by the loss of a hydrogen atom in a straight-chain or branched chain olefin containing a carbon-carbon double bond. The lost hydrogen atom may have originally been located on a saturated or unsaturated carbon atom.

[0041] In this article, "cycloalkenyl" refers to a monovalent hydrocarbon group formed by the loss of a hydrogen atom in a cyclic alkene containing a carbon-carbon double bond. The carbon-carbon double bond is located on the ring, and the lost hydrogen atom could have been located on a saturated or unsaturated carbon atom.

[0042] In this article, "alkenyl" refers to a divalent hydrocarbon group formed by the loss of two hydrogen atoms in a straight-chain or branched chain olefin. The two lost hydrogen atoms could have been located on saturated or unsaturated carbon atoms, and could have been on the same carbon atom or two different carbon atoms.

[0043] In this article, "cycloalkenyl" refers to a divalent hydrocarbon group formed by the loss of two hydrogen atoms from a cyclic olefin. The carbon-carbon double bond is located on the ring, and the two lost hydrogen atoms could originally be located on saturated or unsaturated carbon atoms, and could be located on the same carbon atom or two different carbon atoms.

[0044] In this article, "aryl" refers to a monovalent hydrocarbon group formed by losing a hydrogen atom from an aromatic ring, including monocyclic and fused ring systems.

[0045] In this article, "aryl" refers to a divalent hydrocarbon group formed by losing two hydrogen atoms from an aromatic ring, including monocyclic and fused ring systems.

[0046] In this article, "heteroaryl" refers to a monovalent group formed by losing a hydrogen atom from an aromatic ring, including monocyclic and fused ring systems, wherein at least one aromatic ring includes at least one heteroatom selected from the group consisting of B, N, O, S, Si, P, Se, Te and Ge.

[0047] In this article, "heteroaryl" refers to a divalent group formed by losing two hydrogen atoms from an aromatic ring, including monocyclic and fused ring systems, wherein the aromatic ring includes at least one heteroatom selected from the group consisting of B, N, O, S, Si, P, Se, Te and Ge.

[0048] In this article, the positions where hydrogen atoms are lost are indicated by numbers. For example, 1,1-ethylene represents a divalent group formed by the loss of two hydrogen atoms at position 1 of ethane (CH3CH3). CHCH2), 1,2-ethylene represents a divalent group (–CHCH2–) formed by the loss of one hydrogen atom each at positions 1 and 2 of ethane (CH3CH3).

[0049] In this article, hydrogen includes protium (H) and deuterium (D).

[0050] In this document, when describing embodiments or examples, it should be understood that it is not intended to limit the invention to those embodiments or examples. Rather, all alternatives, modifications, and equivalents of the methods and materials described herein are covered within the scope defined by the claims.

[0051] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0052] This disclosure discloses a vinylbenzene sulfonate homopolymer material containing an imide structure. Using vinylbenzene sulfonate as the polymer matrix and covalently bonded imide functional groups, the monomer is polymerized under controlled conditions via atom transfer radical polymerization to obtain functionalized polystyrene sulfonate homopolymer materials with narrow molecular weight distribution, well-defined structure, and excellent thermal stability. This structure endows the polymer with good chemical stability, structural tunability, and controllable deprotection response characteristics. By optimizing the polymerization process conditions, the target functional homopolymer can be prepared efficiently under mild reaction conditions, with a simple synthetic route and easy product purification. This type of polymer can serve as a structurally controllable responsive functional polymer and organic functional intermediate, possessing broad application potential in responsive materials, photopatterning materials, and other fields.

[0053] The vinylbenzenesulfonate imide compound disclosed herein has the structure shown in Formula I: Formula I R is selected from substituted or unsubstituted C1-C4 alkylene, substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C4-C6 cycloalkenyl, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C6-C30 heteroarylene, substituted or unsubstituted norbornyl, and substituted or unsubstituted oxanorbornyl.

[0054] C1-C4 alkylene refers to an alkylene group containing 1-4 carbon atoms. C1-C4 alkylene can include methylene, ethylene, propylene, and butylene. Ethylene includes 1,1-ethylene and 1,2-ethylene. Propylene includes 1,1-propylene, 1,2-propylene, 2,2-propylene, and 1,3-propylene. Butylene includes 1,1-n-butylene, 1,2-n-butylene, 2,2-n-butylene, 1,3-n-butylene, 2,3-n-butylene, 1,4-n-butylene, 2-methylpropane-1,2-diyl, and 2-methylpropane-1,3-diyl. In some exemplary embodiments, the C1-C4 alkylene is selected from methylene, ethylene, 1,2-propylene, and 1,3-propylene, preferably 1,2-ethylene.

[0055] C2-C4 alkenyl groups refer to alkenyl groups containing 2-4 carbon atoms. C2-C4 alkenyl groups can include 1,1-vinylene (CH2=C<), 1,2-vinylene (–CH=CH–), 1,1-propenyl (CH3–CH=C<), 1,2-propenyl (–CH=C(CH3)–), 1,3-propenyl (–CH=CH–CH2–), 2,3-propenyl (CH2=C(–)–CH2–), but-1-en-1,1-diyl (CH3CH2–CH=C<), but-1-en-1,2-diyl (CH3CH2–C(–)=CH–), but-1 -en-1,3-diyl (CH3CH(–)–CH=CH–), but-1-en-1,4-diyl (–CH2CH2CH=CH–), but-1-en-2,3-diyl (CH3CH(–)–C(–)=CH2), but-1-en-2,4-diyl (–CH2CH2–C(–)=CH2), but-1-en-3,4-diyl (–CH2CH(–)–CH=CH2), but-1-en-3,3-diyl (CH3–(–)C(–)–CH=CH2), but-1-en-4,4-diyl ( (CH–CH2CH=CH2), but-2-en-1,1-diyl (CH3CH=CHCH<), but-2-en-1,2-diyl (CH3CH=C(–)–CH2–), but-2-en-1,3-diyl (CH3C(–)=CHCH2–), but-2-en-1,4-diyl (–CH2CH=CHCH2–), but-2-en-2,3-diyl (CH3CH(–)=C(–)–CH3), etc. In some exemplary embodiments, the C2-C4 alkenyl group is selected from 1,2-vinylene, 1,2-propenyl, 1,3-propenyl, preferably 1,2-vinylene.

[0056] C4-C6 cycloene-based compounds refer to cycloene-based compounds containing 4-6 carbon atoms. C4-C6 cycloene-based compounds can include cyclobutene-1,2-diyl, cyclobutene-2,3-diyl, cyclobutene-3,4-diyl, cyclobutene-3,3-diyl, cyclopentene-1,2-diyl, cyclopentene-2,3-diyl, cyclopentene-3,4-diyl, cyclopentene-3,3-diyl, cyclopentene-4,4-diyl, cyclohexene-1,2-diyl, cyclohexene-2,3-diyl, cyclohexene-3,4-diyl, cyclohexene-4,5-diyl, cyclohexene-3,3-diyl, and cyclohexene-4,4-diyl. In some exemplary embodiments, the C4-C6 cycloene group is selected from cyclobutene-1,2-diyl, cyclobutene-2,3-diyl, cyclobutene-3,4-diyl, cyclopentene-1,2-diyl, cyclopentene-2,3-diyl, cyclopentene-3,4-diyl, cyclohexene-1,2-diyl, cyclohexene-2,3-diyl, cyclohexene-3,4-diyl, cyclohexene-4,5-diyl, preferably cyclohexene-4,5-diyl.

[0057] C6-C30 arylene refers to an arylene group containing 6-30 carbon atoms. C6-C30 arylene can include phenylene, biphenylene, terphenylene, naphthylene, anthracene, phenanthrene, etc. In some exemplary embodiments, the C6-C30 arylene is selected from o-phenylene, o-biphenylene, o-terphenylene, 1,2-naphthylene, 2,3-naphthylene, and 1,8-naphthylene, preferably o-phenylene and 1,8-naphthylene.

[0058] C6-C30 heteroaryl refers to a heteroaryl group containing 6-30 carbon atoms. In this disclosure, the heteroaryl group preferably contains a nitrogen atom. C6-C30 heteroaryl can include pyridinyl, pyridazinyl, pyrimidinyl, pyridazinyl, quinolineyl, isoquinolineyl, pyrimidinyl, quinoxalinyl, etc. In some exemplary embodiments, the C6-C30 heteroaryl is selected from 2,3-pyridinyl, 3,4-pyridinyl, 3,4-pyridazinyl, 5,6-pyridazinyl, 4,5-pyrimidinyl, 5,6-pyrimidinyl, 2,3-pyridazinyl, 2,3-quinolineyl, 3,4-quinolineyl, 5,6-quinolineyl, 6,7-quinolineyl, 7,8-quinolineyl, 3,4-isoquinolineyl, etc. Linoyl, 5,6-isoquinoline, 6,7-isoquinoline, 7,8-isoquinoline, 3,4-isoquinoline, 5,6-isoquinoline, 6,7-isoquinoline, 7,8-isoquinoline, 5,6-isoquinoline, 6,7-isoquinoline, 7,8-isoquinoline, 2,3-isoquinoxaloline, 5,6-isoquinoxaloline, 6,7-isoquinoxaloline, 7,8-isoquinoxaloline.

[0059] Norbornene has the structure shown in the following formula:

[0060] In this document, norbornyl refers to a divalent group formed by the loss of two hydrogen atoms from norbornene. In some exemplary embodiments, the norbornyl is selected from 2,3-norbornyl and 5,6-norbornyl.

[0061] In this document, oxa-norbornene is a compound formed by replacing the methylene (CH2) at the 7-position of norbornene with an oxygen atom (O). Oxa-norbornene is a divalent group formed by the loss of two hydrogen atoms from oxa-norbornene. In some exemplary embodiments, the oxa-norbornene group is selected from 7-oxa-2,3-norbornene and 7-oxa-5,6-norbornene.

[0062] In the structure shown in Formula I, at least one carbon atom in R is connected to two carbon atoms in the imide group to form a four- to seven-membered heterocycle (i.e., a nitrogen-containing heterocycle). Specifically, when one carbon atom in R is connected to two carbon atoms in the imide group, that carbon atom, together with the nitrogen atom and two carbonyl carbon atoms, forms a four-membered ring; when the two carbon atoms in R (C A and C B When a carbon atom is attached to two carbon atoms in an imide group, a five-membered ring (C) can be formed. A and C B (No carbon atoms between them), a six-membered ring (C) A and C B There is a carbon atom between them) or even a seven-membered ring (C A and C B There are two carbon atoms between them.

[0063] In embodiments of this disclosure, the substituents of the substituted C1-C4 alkylene, substituted C2-C4 alkenyl, substituted C4-C6 cycloalkenyl, substituted C6-C30 aryl, substituted C6-C30 heteroaryl, substituted norbornenyl, and substituted oxanorbornenyl are selected from halogens, C1-C6 alkyl groups, and C1-C6 alkoxy groups. Halogens (X) include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). C1-C6 alkyl groups refer to alkyl groups comprising 1-6 carbon atoms. C1-C6 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl, and 2,2-dimethylbutyl. C1-C6 alkoxy groups refer to alkoxy groups containing 1-6 carbon atoms. C1-C6 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, neopentoxy, n-hexyloxy, 2-methylpentoxy, 3-methylpentoxy, 2,3-dimethylbutoxy, and 2,2-dimethylbutoxy.

[0064] In the vinylbenzene sulfonate imide compounds disclosed herein, the vinyl (CH2=CH–) and sulfonate groups (–SO3–) linked to the benzene ring can be located in the ortho, meta, or para positions, preferably in the para position.

[0065] As an example, the vinylbenzenesulfonate imide compounds disclosed herein may include: .

[0066] The vinylbenzene sulfonate imide compounds disclosed herein can be prepared by first reacting a vinylbenzene sulfonate (such as sodium vinylbenzene sulfonate) with a dihalosulfonyl sulfoxide (such as sulfonyl chloride) to generate a vinylbenzene sulfonyl halide (such as vinylbenzene sulfonyl chloride), and then reacting the vinylbenzene sulfonyl halide with an imine alcohol (containing N–OH, i.e., an N-hydroxyimide). Taking sodium vinylbenzene sulfonate and sulfonyl chloride as an example, the reaction formula is as follows: Reaction (1) Reaction (2) The definition of R is the same as above.

[0067] Reaction (1) is carried out in an organic solvent (such as N,N-dimethylformamide), where the concentration of sodium vinylbenzenesulfonate in the organic solvent can be 1.0-2.0 mol / L (e.g., 1.0 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, 1.8 mol / L, 1.9 mol / L, 2.0 mol / L, etc.). A polymerization inhibitor (such as 2,6-di-tert-butyl-p-cresol) can be added to prevent the polymerization of sodium vinylbenzenesulfonate. The polymerization inhibitor can be 0.1-1.0 wt% of sodium vinylbenzenesulfonate (e.g., 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, etc.). The molar ratio of sodium vinylbenzenesulfonate to thionyl chloride can be from 1:4 to 1:10 (e.g., 1:4, 1:5, 1:6, 1:7, etc.). The reaction is carried out at room temperature for 10-20 hours. After the reaction is complete, the mixture is quenched with ice water, and the product is extracted with an extractant (such as dichloromethane). The organic phase is washed, dried, and the resulting vinylbenzenesulfonyl chloride is obtained.

[0068] In reaction (2), N-hydroxyimide and triethylamine (acid-binding agent) are dissolved in an organic solvent (such as dichloromethane). The concentration of N-hydroxyimide in the solvent is typically 0.1-1 mol / L (e.g., 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L, etc.). Then, the vinylbenzenesulfonyl chloride synthesized above is added (dropwise under an ice-water bath). The molar ratio of N-hydroxyimide, triethylamine, and vinylbenzenesulfonyl chloride can be 1:(1.2-1.8):(1-1.4), for example, 1:1.5:1.2. The reaction is carried out at room temperature for 10-20 hours, monitored by thin-layer chromatography. After the reaction is complete, the reaction solution is filtered or washed with water depending on the solubility of the product, and finally purified by silica gel column chromatography.

[0069] N-hydroxyimides can be purchased commercially or prepared by methods known in the art, such as by reacting the corresponding cyclic anhydride with a hydroxylamine or its salt.

[0070] The vinylbenzenesulfonate imide polymer disclosed herein can be synthesized using the vinylbenzenesulfonate imide compound shown in Formula I as a monomer. Specifically, the monomer, chain transfer agent, and thermal initiator are dissolved in a solvent and mixed thoroughly. The polymerization reaction is carried out at a temperature of 65-90 °C (e.g., 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, etc.) for a typical reaction time of 10-18 hours. After the reaction is complete, the polymer is diluted according to its solubility. The reaction solution is added dropwise to methanol, diethyl ether, or other unsuitable solvents. After filtration and washing of the solid, the solid is dried in a vacuum oven to obtain the polymer material.

[0071] The ratio of monomer to chain transfer agent is determined by the expected molecular weight. The molar ratio of thermal initiator to chain transfer agent can be (0.01-0.1):1 (e.g., 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, etc.).

[0072] The chain transfer agent can be selected from trisulfides. Preferred chain transfer agents are... R1 can be a hydrophobic group such as dodecyl, and Z can be a cyano, carboxylic acid, etc.

[0073] The thermal initiator can be selected from azo initiators such as azobisisobutyronitrile and azobisisoheptanenitrile.

[0074] The solvent system used for the reaction can be common solvents such as tetrahydrofuran, acetonitrile, and N,N-dimethylformamide.

[0075] In the vinylbenzene sulfonate imide homopolymers disclosed herein, the degree of polymerization of the monomers can be from 10 to 100, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 and any combination thereof.

[0076] The molecular weight distribution index (PDI) of the vinylbenzene sulfonate imide homopolymer disclosed herein can be from 1.01 to 1.10, for example, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, and any combination thereof. The molecular weight distribution index refers to the ratio of the polymer's weight-average molecular weight to its number-average molecular weight.

[0077] As an example, the vinylbenzenesulfonate imide polymers disclosed herein may include: , Where n = 10 to 100, for example 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 and any two of them.

[0078] This disclosure employs a simple method to prepare vinylbenzenesulfonate imide monomers, and utilizes a mature atom transfer radical reaction to synthesize vinylbenzenesulfonate imide homopolymers. With appropriate reagent ratios, the preparation process is simple, and the resulting material exhibits controllable molecular weight and an extremely narrow molecular weight distribution. This type of homopolymer material possesses good thermal stability, with a decomposition temperature exceeding 300°C and a glass transition temperature around 130°C. Furthermore, it demonstrates extremely strong ultraviolet absorption in the 200-300 nm range, showing promising commercial applications and economic value.

[0079] As one of the important applications, the vinylbenzene sulfonate imide homopolymer disclosed herein can be used in photoresists, especially electron beam photoresists.

[0080] The photoresist composition disclosed herein uses a vinylbenzene sulfonate imide homopolymer as the main resin, combined with a solvent and optional additives, and is prepared by uniform mixing, degassing, and filtration. The main resin is the aforementioned vinylbenzene sulfonate imide homopolymer containing imide side chains. The imide structure of its side chains endows the photoresist with excellent thermal and chemical stability, and can synergistically regulate the irradiation response sensitivity of the main resin. The sulfonate structure can undergo a controlled deprotection reaction under electron beam irradiation to generate polystyrene sulfonic acid with significantly enhanced polarity, providing a basis for negative development.

[0081] In the photoresist composition disclosed herein, the solvent is selected from solvents capable of dissolving such homopolymers, such as acetonitrile, tetrahydrofuran, etc., and the additives are selected from defoamers, antioxidants, and other reagents that do not affect the development and electron beam deprotection reaction.

[0082] Photoresist is prepared by dissolving dried polymer raw materials and additives in a solvent in a specific ratio. The polymer concentration in the solvent is typically 0.1-20 wt%, which can be adjusted according to the required spin-coating film thickness and the polymer's solubility. The number-average molecular weight of the polymer can range from 3000 to 30000, selected based on solubility and the desired final effect. The prepared liquid can be ultrasonically defoamed and dissolved, with the ultrasonic time determined by the liquid volume. After complete dissolution, the liquid is filtered through 0.22 μm and 0.10 μm filter membranes, the number of filtrations depending on the number of particles in the liquid, to obtain a clear and transparent photoresist mixture.

[0083] The photoresist coating-developing process typically includes the following steps: (1) The photoresist prepared above is uniformly coated on the surface of a substrate such as a silicon wafer, glass or metal by spin coating or coating method. The amount of coating liquid is determined according to the size of the substrate.

[0084] (2) Dry the coated photoresist, and select the drying temperature and drying time according to the thermal stability of the solvent and polymer.

[0085] (3) After the photoresist in step (2) is exposed, the unexposed area is developed using the solvent used to prepare the photoresist or other solvents that can dissolve the polymer but not polystyrene sulfonic acid as a developing solution to obtain a negative pattern.

[0086] The negative photoresist based on vinylbenzenesulfonate imide homopolymer disclosed herein solves the technical problems of existing negative photoresists, such as low pattern fidelity, poor development contrast, insufficient process stability, and limited types of dedicated negative photoresists suitable for electron beam lithography, which make it difficult to meet the requirements for high-resolution micro-nano pattern fabrication.

[0087] Example

[0088] The present invention will be described below by way of specific embodiments. It should be understood that these embodiments are merely illustrative and are not intended to limit the scope of the invention. The methods, reagents, and materials used in the embodiments are conventional methods, reagents, and materials in the art, unless otherwise stated. The raw material compounds in the embodiments are all commercially available.

[0089] (a) Monomer Preparation Example

[0090] Example 1-1 Preparation of 1,8-naphthalenediamide p-vinylbenzenesulfonate

[0091] Sodium p-vinylbenzenesulfonate (3 g) and 2,6-di-tert-butyl-p-cresol (0.03 g) were dissolved in N,N-dimethylformamide (10 mL), and sulfoxide (7.37 mL, 101.5 mmol) was added dropwise at 0 °C. The reaction was stirred overnight at room temperature, followed by quenching with 50 mL of ice water. The resulting aqueous solution was extracted with 50 mL of dichloromethane, washed with water, and dried over anhydrous magnesium sulfate. Dichloromethane was removed by rotary evaporation to give a yellow liquid product, p-vinylbenzenesulfonyl chloride.

[0092] N-hydroxy-1,8-naphthalenedimide (1.1 g) and triethylamine (1 mL) were dissolved in 80 mL of dichloromethane, which had been pre-placed in a reaction flask. The reaction flask was placed in an ice-water bath, and p-vinylbenzenesulfonyl chloride (0.86 mL) was added dropwise. The reaction was then carried out at room temperature for 8 h. The product precipitated after the reaction, and a relatively pure product was obtained by filtration. Recrystallization yielded white crystals, which, according to NMR (Bruker AVANCE III HD500 Spectrometer), had the following structure:

[0093] Examples 1-2 Preparation of phthalimide p-vinylbenzenesulfonate

[0094] N-hydroxyphthalimide (0.82 g) and triethylamine (1 mL) were dissolved in 60 mL of dichloromethane that had been pre-placed in a reaction flask. The reaction flask was placed in an ice-water bath, and p-vinylbenzenesulfonyl chloride (0.86 mL) prepared according to the method described in Example 1-1 was added dropwise. The reaction was then carried out at room temperature for 10 h. After acid washing, water washing, and washing with saturated brine, the reaction solution was dried, and the organic solvent was removed by rotary evaporation. Recrystallization yielded white crystals, which had the following structure as determined by NMR (Bruker AVANCE III HD500 Spectrometer):

[0095] Examples 1-3 Preparation of succinimide p-vinylbenzenesulfonate

[0096] N-hydroxysuccinimide (0.58 g) and triethylamine (1 mL) were dissolved in 60 mL of dichloromethane, which had been pre-placed in a reaction flask. The reaction flask was placed in an ice-water bath, and p-vinylbenzenesulfonyl chloride (0.86 mL) prepared according to the method described in Example 1-1 was added dropwise. The reaction was then carried out at room temperature for 6 h. After acid washing, water washing, and washing with saturated brine, the reaction solution was dried, and the organic solvent was removed by rotary evaporation. Recrystallization yielded white crystals, which had the following structure as determined by NMR (Bruker AVANCE III HD500 Spectrometer):

[0097] (II) Example of polymer preparation

[0098] Example 2-1

[0099] The monomer 1,8-naphthalimide p-vinylbenzenesulfonate (0.19 g), the chain transfer agent 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]valeric acid (Adamas, 99%) (4.0 mg), and the free radical initiator azobisisobutyronitrile (Adamas, 99%) (0.1 mg) were dissolved in 0.5 mL of tetrahydrofuran. The reaction mixture was subjected to a three-cycle freeze-evacuation-thawing process in a Shrek tube and reacted at 70°C for 17 hours under a nitrogen atmosphere. After the reaction solution cooled, the cap was opened, and the solution was diluted with dimethyl sulfoxide. The precipitate was added dropwise to diethyl ether, filtered, and dried under vacuum to obtain 0.15 g of a yellow solid. The solid was determined by NMR to have the structure of Formula 1 (Bruker AVANCE III HD500 Spectrometer), where n = 57.

[0100] ( )

[0101] Formula 1

[0102] Example 2-2

[0103] The monomer 1,8-naphthalimide p-vinylbenzenesulfonate (0.19 g), the chain transfer agent 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]valeric acid (Adamas, 99%) (10.1 mg), and the free radical initiator azobisisobutyronitrile (Adamas, 99%) (0.16 mg) were dissolved in 1 mL of N,N-dimethylformamide. The reaction mixture was subjected to a three-cycle freeze-evacuation-thawing process in a Shrek tube and reacted at 70°C for 15 hours under a nitrogen atmosphere. After the reaction solution cooled, the cap was opened, and the reaction solution was added dropwise to methanol to precipitate the solid. The precipitate was filtered, dried under vacuum, and 0.17 g of a yellow solid was obtained. The solid was determined by NMR to have the structure of Formula 1 (BrukerAVANCE III HD500 Spectrometer), where n = 25.

[0104] ( )

[0105] Formula 1

[0106] Example 2-3

[0107] The monomer phthalimide p-vinylbenzenesulfonate (0.16 g), the chain transfer agent 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]valeric acid (Adamas, 99%) (10.1 mg), and the free radical initiator azobisisobutyronitrile (Adamas, 99%) (0.4 mg) were dissolved in 1 mL of tetrahydrofuran. The reaction mixture was subjected to a three-cycle freeze-evacuation-thawing process in a Shrek tube and reacted at 70°C for 17 hours under a nitrogen atmosphere. After the reaction solution cooled, the cap was opened, and the reaction solution was added dropwise to methanol to precipitate the solid. The precipitate was filtered, dried under vacuum, and yielded 0.13 g of a yellow solid. The solid was determined by NMR to have the structure of Formula 2 (Bruker AVANCE III HD500 Spectrometer), where n = 54.

[0108] ( )

[0109] Formula 2

[0110] Examples 2-4

[0111] The monomer phthalimide p-vinylbenzenesulfonate (0.14 g), the chain transfer agent 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]valerate (Adamas, 99%) (7.9 mg), and the free radical initiator azobisisobutyronitrile (Adamas, 99%) (0.4 mg) were dissolved in 1 mL of tetrahydrofuran. The reaction mixture was subjected to a three-cycle freeze-evacuation-thawing process in a Shrek tube and reacted at 70 °C for 19 hours under a nitrogen atmosphere. After the reaction solution cooled, the cap was opened, and the reaction solution was added dropwise to methanol to precipitate the solid. The precipitate was filtered, dried under vacuum, and a yellow solid was obtained. The solid was determined by NMR to have the structure of Formula 2 (Bruker AVANCE III HD500 spectrometer), where n = 74.

[0112] ( )

[0113] Formula 2

[0114] Examples 2-5

[0115] The monomer succinimide p-vinylbenzenesulfonate (0.16 g), the chain transfer agent 2-cyano-2-propyldodecyl trithiocarbonate (Adamas, 99%) (8.6 mg), and the free radical initiator azobisisobutyronitrile (Adamas, 99%) (0.4 mg) were dissolved in 1 mL of tetrahydrofuran (Sinopharm, 99.8%). The reaction mixture was subjected to a three-cycle freeze-evacuation-thawing process in a Shrek tube and reacted at 70 °C for 15 hours under a nitrogen atmosphere. After the reaction solution cooled, the cap was opened, and the reaction solution was added dropwise to methanol to precipitate the solid. The precipitate was filtered, dried under vacuum, and a yellow solid was obtained. The solid was determined by NMR to have the structure of Formula 3 (Bruker AVANCE III HD500 spectrometer), where n=31.

[0116] ( )

[0117] Formula 3

[0118] Examples 2-6

[0119] The monomers phthalimide p-vinylbenzenesulfonate (0.18 g), cyanomethyl dodecyl trithiocarbonate (Adamas, 99%) (10.3 mg), and the free radical initiator azobisisobutyronitrile (Adamas, 99%) (0.5 mg) were dissolved in 1 mL of tetrahydrofuran. The reaction mixture was subjected to a three-cycle freeze-evacuation-thawing process in a Shrek tube and reacted at 70 °C for 15 hours under a nitrogen atmosphere. After the reaction solution cooled, the cap was opened, and the solution was added dropwise to methanol to precipitate the solid. The precipitate was filtered, dried under vacuum, and a yellow solid was obtained. The solid exhibited the structure of Formula 4 (Bruker AVANCE III HD500 spectrometer) as determined by NMR, where n = 69.

[0120] ( )

[0121] Formula 4

[0122] (III) Polymer performance testing

[0123] To verify the controllability of molecular weight and molecular weight distribution of the preparation method disclosed herein, the products of Examples 2-1 to 2-4 were designated as Sample 1, Sample 2, Sample 3, and Sample 4, respectively. Under the same conditions, size exclusion chromatography was performed on the four samples (the injector and unit pump were an Agilent 1260 Infinity II Autosampler & Quaternary Pump; the chromatographic column was a combination of Shodex KD-803 and KD 805 Tandem Columns; the detectors were a Wyatt Optilab Differential Refractive Index (dRI) and a DAWN Multi-angle Light Scattering (MALS); the mobile phase was DMF (dimethylformamide) containing 10 mM / L; and all data were processed by Wyatt Astra software). The test results showed that the number-average molecular weight of sample 1 was 22 kDa (kilodaltons), with a molecular weight distribution of 1.04; the number-average molecular weight of sample 2 was 9.7 kDa, with a molecular weight distribution of 1.03; the number-average molecular weight of sample 3 was 8.9 kDa, with a molecular weight distribution of 1.03; and the number-average molecular weight of sample 4 was 12 kDa, with a molecular weight distribution of 1.08. These results indicate that this method provides good control over the molecular weight and molecular weight distribution of this type of styrene sulfonate polymer.

[0124] To verify the good thermal stability of the polymer prepared in this disclosure, thermogravimetric analysis (TGA, Thermo Fisher ISQ 7610) and differential scanning calorimetry (DSC, TA Instruments DSC250) were performed on samples 2 and 3. The test results are as follows. Figure 1 and Figure 2 As shown in the figure. Thermogravimetric analysis showed that the 5% weight loss of samples 2 and 3 was at 271 °C and 265 °C, respectively, indicating that this type of polymer has good thermal stability. DSC thermal analysis showed that the glass transition temperatures (Tg) of samples 2 and 3 were 129 °C and 132 °C, respectively, indicating that they have good hot processability and can cope with high-temperature application scenarios.

[0125] The polymer prepared in this disclosure also exhibits extremely strong ultraviolet absorption. Sample 3 was dissolved in tetrahydrofuran and subjected to ultraviolet absorption testing of the solution (Shimadzu, UV-2600), and the results are as follows... Figure 3 As shown, the ultraviolet absorption spectrum indicates that this type of polymer exhibits strong absorption in the ultraviolet band of 200 to 300 nm. A series of photoresponsive applications can be implemented using ultraviolet light, such as antibacterial materials under ultraviolet light and patterned materials under ultraviolet light.

[0126] (iv) Example of photoresist preparation

[0127] Example 3-1

[0128] A polymer (12 mg) of formula 2 with a number-average molecular weight of 8900 was dissolved in tetrahydrofuran (1 mL), sonicated for 5 min, and the liquid was filtered once through a 0.22 μm filter membrane (ASONE, PTFE). 80 μL of the resulting photoresist liquid was spin-coated at 6000 rpm onto a 20 μm thick film. A 20 mm silicon wafer was baked at 80°C for 1 minute (Laurell WS-650MZ-23NPPB). The silicon wafer was placed on a hot plate (WIGGENS WH500D-3K) and baked at 80°C for 1 minute, resulting in a photoresist film with a thickness of approximately 40 nm on the silicon wafer surface.

[0129] Example 3-2

[0130] A polymer (10 mg) of formula 2 with a number-average molecular weight of 12000 was dissolved in acetonitrile (1 mL), sonicated for 10 min, and the liquid was filtered once through a 0.22 μm filter membrane (ASONE, PTFE) and once through a 0.10 μm filter membrane (JINVILL, PTFE). 60 μL of the resulting photoresist liquid was spin-coated onto a 15-layer substrate at 7000 rpm. 1 min on a 15 mm silicon wafer (Laurell WS-650MZ-23NPPB). The silicon wafer was placed on a hot plate (WIGGENS WH500D-3K) and baked at 100 °C for 1 min, resulting in a photoresist film with a thickness of approximately 30 nm on the silicon wafer surface.

[0131] (v) Electron beam exposure experiment

[0132] The photoresists from Examples 3-1 and 3-2 were subjected to electron beam exposure experiments (Elionix / ELS-F125G8, Germany) under an accelerating voltage of 125 kV, with different exposure doses and patterns. After exposure, the samples were developed in acetonitrile for 30 seconds and dried under a nitrogen flow to obtain clear patterned structures. These were subsequently characterized using a scanning electron microscope (Carl Zeiss / Sigma300, UK). The results are as follows: Figure 4 As shown, the photoresist of Example 3-1 can achieve a resolution of 50 nm HP and a line edge roughness of 5.9 nm (top image). The photoresist of Example 3-2, under L / S 1 / 1 conditions, can easily achieve a critical size of 21 nm and a line edge roughness of 2.5 nm, forming a well-formed and stable pattern (bottom image).

[0133] By exposing the photoresist to different doses and then scanning and analyzing the pattern using a high-resolution fast atomic force microscope (BRUKER / USA / Dimension Fastscan), the relationship curve between dose and film thickness can be obtained, such as... Figure 5 As shown. A tangent line is drawn at y=0.5 on the fitted S-curve. The x-value at y=0 is set to D0, and the x-value at y=1 is set to D. 100 (y represents the ordinate), calculate the contrast of the photoresist in Examples 3-1 and 3-2. The contrast calculation formula is: As shown in Table 1 below.

[0134] Table 1 Photoresist contrast

[0135] The specific embodiments of the present invention have been described above through examples. The scope of protection of the present invention is not limited to the exemplary embodiments described above. 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 scope of protection of the present invention.

Claims

1. A vinylbenzene sulfonate imide compound, characterized in that, The compound has the structure shown in Formula I: Equation I Wherein R is a divalent organic group selected from substituted or unsubstituted C1-C4 alkylene, substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C4-C6 cycloalkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted norbornyl, substituted or unsubstituted oxanorbornyl, wherein in the structure shown in Formula I, at least one carbon atom in R is connected to two carbon atoms in the imide group to form a four- to seven-membered heterocycle.

2. The compound according to claim 1, characterized in that, The substituents of the substituted C1-C4 alkylene, substituted C2-C4 alkenyl, substituted C4-C6 cycloalkenyl, substituted C6-C30 aryl, substituted C6-C30 heteroaryl, substituted norbornyl, and substituted oxanorbornyl are selected from halogens, C1-C6 alkyl, and C1-C6 alkoxy groups.

3. The compound according to claim 1, characterized in that, The compound satisfies at least one of the following: C1-C4 alkylene groups are selected from methylene, ethylene, 1,2-propylene, and 1,3-propylene; C2-C4 alkenyl groups are selected from 1,2-vinylene, 1,2-propenylene, and 1,3-propenylene; C4-C6 cyclohexene groups are selected from cyclobutene-1,2-diyl, cyclobutene-2,3-diyl, cyclobutene-3,4-diyl, cyclopentene-1,2-diyl, cyclopentene-2,3-diyl, cyclopentene-3,4-diyl, cyclohexene-1,2-diyl, cyclohexene-2,3-diyl, cyclohexene-3,4-diyl, and cyclohexene-4,5-diyl. C6-C30 arylene groups are selected from o-phenylene, o-biphenylene, o-terphenylene, 1,2-naphthylene, 2,3-naphthylene, and 1,8-naphthylene; C6-C30 heteroaryl groups are selected from 2,3-pyridinyl, 3,4-pyridinyl, 3,4-pyridazinyl, 5,6-pyridazinyl, 4,5-pyrimidinyl, 5,6-pyrimidinyl, 2,3-pyridazinyl, 2,3-quinolineyl, 3,4-quinolineyl, 5,6-quinolineyl, 6,7-quinolineyl, 7,8-quinolineyl, 3,4-isoquinolineyl, 5,6 -Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 3,4-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 2,3-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline; The norbornyl group is selected from 2,3-norbornyl and 5,6-norbornyl; The oxa-norbornenyl is selected from 7-oxa-2,3-norbornenyl and 7-oxa-5,6-norbornenyl.

4. The compound according to claim 1, characterized in that, The compounds are selected from the group consisting of: 。 5. A vinylbenzene sulfonate imide polymer, characterized in that, This polymer is synthesized from the monomers shown in Formula I: Equation I R is selected from substituted or unsubstituted C1-C4 alkylene, substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C4-C6 cycloalkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted norbornyl, and substituted or unsubstituted oxanorbornyl. In the structure shown in Formula I, at least one carbon atom in R is connected to two carbon atoms in the imide group to form a four- to seven-membered heterocycle.

6. The polymer according to claim 5, characterized in that, The substituents of the substituted C1-C4 alkylene, substituted C2-C4 alkenyl, substituted C4-C6 cycloalkenyl, substituted C6-C30 aryl, substituted C6-C30 heteroaryl, substituted norbornyl, and substituted oxanorbornyl are selected from halogens, C1-C6 alkyl, and C1-C6 alkoxy groups.

7. The polymer according to claim 5, characterized in that, The polymer satisfies at least one of the following: C1-C4 alkylene groups are selected from methylene, ethylene, 1,2-propylene, and 1,3-propylene; C2-C4 alkenyl groups are selected from 1,2-vinylene, 1,2-propenylene, and 1,3-propenylene; C4-C6 cyclohexene groups are selected from cyclobutene-1,2-diyl, cyclobutene-2,3-diyl, cyclobutene-3,4-diyl, cyclopentene-1,2-diyl, cyclopentene-2,3-diyl, cyclopentene-3,4-diyl, cyclohexene-1,2-diyl, cyclohexene-2,3-diyl, cyclohexene-3,4-diyl, and cyclohexene-4,5-diyl. C6-C30 arylene groups are selected from o-phenylene, o-biphenylene, o-terphenylene, 1,2-naphthylene, 2,3-naphthylene, and 1,8-naphthylene; C6-C30 heteroaryl groups are selected from 2,3-pyridinyl, 3,4-pyridinyl, 3,4-pyridazinyl, 5,6-pyridazinyl, 4,5-pyrimidinyl, 5,6-pyrimidinyl, 2,3-pyridazinyl, 2,3-quinolineyl, 3,4-quinolineyl, 5,6-quinolineyl, 6,7-quinolineyl, 7,8-quinolineyl, 3,4-isoquinolineyl, 5,6 -Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 3,4-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline, 2,3-Isoquinoline, 5,6-Isoquinoline, 6,7-Isoquinoline, 7,8-Isoquinoline; The norbornyl group is selected from 2,3-norbornyl and 5,6-norbornyl; The oxa-norbornenyl is selected from 7-oxa-2,3-norbornenyl and 7-oxa-5,6-norbornenyl.

8. The polymer according to claim 5, characterized in that, The polymer is selected from the group consisting of: ， Where n = 10 to 100.

9. A photoresist composition, characterized in that, The photoresist composition comprises the polymer according to any one of claims 5-8.

10. A method for forming a pattern, characterized in that, The method includes forming a photoresist layer using the photoresist composition of claim 9.

Images