Polybenzyl bromide or iodide type monomolecular resin photoresist, preparation method and application thereof

Abstract

The application provides a series of monomolecular resin photoresists based on polybenzyl bromide or polybenzyl iodine and a preparation method and application thereof, and the monomolecular resin can be used as a main body material of the photoresist. Raw materials are cheap and easy to obtain, and the synthesis process is simple. The compound provided by the application takes adamantane as a core unit, is externally connected with multiple benzyl bromide or benzyl iodine groups, and the core structure of adamantane and benzene ring and the introduction of bromine atoms or iodine atoms can maximize the sensitivity and etching resistance of the photoresist.

Description

Technical Field

[0001] This invention belongs to the field of photolithography materials technology, specifically relating to a class of adamantane-based polybenzyl bromide or polybenzyl iodide monomolecular resin photoresists, their preparation methods, and applications. Background Technology

[0002] Photoresist, also known as photoresist, is a key material in the manufacture of integrated circuits. Its performance directly affects the integration density, operating speed, and power consumption of integrated circuit chips. With the rapid development of the semiconductor industry, the integration density of semiconductor devices is increasing, and the resolution requirements for photolithography technology are also increasing. According to Rayleigh's law, reducing the wavelength of the exposure light source is beneficial for forming higher resolution patterns. Currently, photolithography technology has evolved from early ultraviolet lithography and deep ultraviolet lithography to the current extreme ultraviolet lithography. The most advanced extreme ultraviolet lithography technology places more stringent requirements on the resolution, sensitivity, line edge roughness, and etching resistance of photoresists. Based on different molecular structures, extreme ultraviolet photoresists are mainly divided into polymeric photoresists, organic-inorganic hybrid photoresists, and monomolecular resin-based photoresists. Polymeric photoresists, due to their large molecular volume, uneven molecular weight distribution, and entanglement between molecular chains, are difficult to meet the requirements of low line edge roughness and high resolution. Although organic-inorganic hybrid photoresists improve resolution to some extent, their preparation process is complex and costly. Monomolecular resin-type photoresists have a well-defined molecular structure and small molecular size, which ensures their uniform dispersion in the photoresist system and is expected to achieve higher resolution and LER.

[0003] Based on their different solubility transformation mechanisms, photoresists can be divided into chemically amplified photoresists (CAR) and non-chemically amplified photoresists (n-CAR). Chemically amplified photoresists primarily achieve solubility changes before and after exposure through their peripherally modified acid-sensitive groups. This type of photoresist contains multiple components such as the host material, acid-generating agent, and acid-diffusion inhibitor, which can easily lead to uneven component distribution and acid diffusion, reducing the resolution of the lithographic pattern. Non-chemically amplified photoresists mainly rely on peripherally modified photosensitive groups to achieve solubility changes; their "single-component" characteristic helps them achieve higher resolution.

[0004] Therefore, non-chemically amplified monomolecular resin-based photoresists have advantages in high-resolution lithography. Currently, the reaction mechanisms of non-chemically amplified photoresists mainly include chain breakage, decomposition, and cross-linking mechanisms. Compared to chain breakage and decomposition mechanisms, photoresists based on cross-linking mechanisms generate less gas during exposure, resulting in less contamination and damage to the exposure system components. Simultaneously, the formation of a dense network structure after exposure ensures higher film thickness retention and mechanical strength of the lithographic pattern, thus achieving higher resolution. However, there are currently few reports on monomolecular resin photoresists based on cross-linking mechanisms.

[0005] The inventor's prior patent 202410023407X uses compound I-1 as the host material of a single-component negative photoresist. This compound, as a monomolecular resin photoresist based on a cross-linking mechanism, can achieve good photolithography results. However, when performing high-precision electron beam lithography, such as with a period of less than 50 nm, defects appear in the resulting photolithographic patterns, especially the generally low exposure sensitivity of the photoresist, which is still far from practical applications and needs further improvement.

[0006] The structure of compound I-1 in 202410023407X is shown below:

[0007] . Summary of the Invention

[0008] To address the aforementioned technical problems, this invention provides a benzyl bromide and benzyl iodide-based monomeric resin based on adamantane, and uses it as the host material for non-chemically amplified photoresists.

[0009] The technical solution of the present invention is as follows:

[0010] Compounds represented by formula (I), (II), (III), or (IV) as follows:

[0011]

[0012]

[0013] In equations (I) and (III), R is selected from Z, -CH2Br, or -OC. 1-15 Alkyl-C 6-20 Aryl-CH2Br;

[0014] In formulas (II) and (IV), R is selected from Z, -CH2I, or -OC. 1-15 Alkyl-C 6-20 Aryl-CH2I;

[0015] The group Z is H, unsubstituted, or optionally surrounded by one, two, or more R groups. S The following groups are substituted: C 1-15 Alkyl or C 1-15 Alkoxy;

[0016] The Rs is selected from OH, NO2, and C. 1-15 Alkyl, C 1-15 Alkoxy, C 3-20 cycloalkyl, C 6-20 Aryl or 5-20 heteroaryl compounds.

[0017] In some embodiments of the present invention, -CH2Br or -CH2I in formula (I), formula (II), formula (III) or formula (IV) is located at the ortho, meta or para position of the benzene ring it substituted.

[0018] In some embodiments of the present invention, formula (I), formula (II), formula (III) or formula (IV) is a symmetrical structure; that is, -CH2Br or -CH2I is simultaneously located in the ortho position of the benzene ring it substituted.

[0019] Alternatively, it may be located at the meta position of the benzene ring it substituted;

[0020] Alternatively, it may be located at the para position of the benzene ring it substituted.

[0021] In some embodiments of the present invention, R is H or -C. 1-6 Alkyl groups (e.g., methoxy groups).

[0022] In some embodiments of the present invention, the two R's on the left and right sides of formula (I), (II), (III), or (IV) are identical in structure and are selected from H or -C. 1-6 Alkyl groups (e.g., methoxy groups).

[0023] As an example, the compound shown in formula (I) has the following structure:

[0024] .

[0025] As an example, the compound shown in formula (II) has the following structure:

[0026] .

[0027] As an example, the compound shown in formula (III) has the following structure:

[0028] .

[0029] As an example, the compound represented by formula (Ⅳ) has the following structure:

[0030] .

[0031] The present invention also provides a method for preparing compounds of formula (I), formula (II), formula (III) or formula (IV), comprising:

[0032] The compound (P1) was reacted with trimethylbromosilane to give the compound shown in formula (I);

[0033]

[0034] Alternatively, reacting compound (P1) with trimethyliodosilane yields the compound shown in formula (II);

[0035]

[0036] Alternatively, reacting compound (P2) with trimethylbromosilane yields the compound shown in formula (III);

[0037]

[0038] Alternatively, reacting compound (P2) with trimethyliodosilane yields the compound shown in formula (Ⅳ);

[0039]

[0040] Wherein, in the compound shown in formula (I), R is -CH2Br, -OC 1-15 Alkyl-C 6-20 When aryl-CH2Br, R in compound (P1) is defined the same as R in the compound shown in formula (I); or, R in compound (P1) is selected from -CH2OH, -OC 1-15 Alkyl-C 6-20 Aryl-CH2OH;

[0041] When R is -CH2I or -OC in the compound shown in formula (II) 1-15 Alkyl-C 6-20 When aryl-CH2I, R in compound (P1) is defined the same as R in the compound shown in formula (II); or, R in compound (P1) is selected from -CH2OH, -OC 1-15 Alkyl-C 6-20 Aryl-CH2OH;

[0042] When R is -CH2Br or -OC in the compound shown in formula (III) 1-15 Alkyl-C 6-20 When aryl-CH2Br, R in compound (P2) is defined the same as R in the compound shown in formula (III); or, R in compound (P2) is selected from -CH2OH, -OC 1-15 Alkyl-C 6-20 Aryl-CH2OH;

[0043] When R is -CH2I or -OC in the compound represented by formula (IV) 1-15 Alkyl-C 6-20 When aryl-CH2I, R in compound (P2) is defined the same as R in the compound shown in formula (II); or, R in compound (P2) is selected from -CH2OH, -OC 1-15 Alkyl-C 6-20Aryl-CH2OH.

[0044] According to an embodiment of the present invention, the reaction is carried out at room temperature.

[0045] The present invention also provides the use of the compounds shown in formula (I), formula (II), formula (III) or formula (IV) for the preparation of photoresists.

[0046] The present invention also provides a photoresist composition comprising one or more compounds represented by formula (I), formula (II), formula (III) or formula (IV).

[0047] According to embodiments of the present invention, the compounds represented by formula (I), formula (II), formula (III) or formula (IV) are used as the host material of the photoresist composition.

[0048] According to an embodiment of the present invention, the photoresist composition further includes a photoresist solvent.

[0049] According to an embodiment of the present invention, the photoresist solvent is selected from one, two or more of the following substances: propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), N,N-dimethylformamide (DMF), cyclohexanone, ethyl n-pentanone, ethyl isopentanone, ethanol, acetonitrile, isopropanol, acetone, methyl n-pentanone, and methyl isopentanone.

[0050] According to an embodiment of the present invention, the photoresist composition is a positive or negative photoresist composition comprising the compounds shown in formula (I) and / or (II) and / or (III) and / or (IV) as well as a photoresist solvent.

[0051] In one embodiment of the present invention, the photoresist is a single-component photoresist, which is composed of compounds shown in formula (I) and / or (II) and / or (III) and / or (IV) and a photoresist solvent, that is, the photoresist composition includes only compounds shown in formula (I) and / or (II) and / or (III) and / or (IV) except for the photoresist solvent.

[0052] The present invention also provides a photoresist coating comprising one or more compounds of formula (I), formula (II), formula (III) or formula (IV).

[0053] The present invention also provides a method for preparing the above-mentioned photoresist coating, comprising: applying the above-mentioned photoresist composition onto a substrate to obtain the coating.

[0054] Preferably, the application method is spin coating.

[0055] Preferably, the photoresist coating is a thin film.

[0056] The present invention also provides the application of the photoresist coating in photolithography.

[0057] The compounds described in this invention possess high thermal stability and photosensitivity due to their unique polybenzyl bromide and polybenzyl iodide structures, and can be used in photolithography.

[0058] According to the present invention, the photoresist coating can be used in modern photolithography technologies such as 365nm photolithography, 254nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet (EUV) photolithography, nanoimprint lithography or electron beam lithography, and is preferably used in extreme ultraviolet and electron beam lithography technologies.

[0059] The beneficial effects of this invention are as follows:

[0060] (1) This invention provides a series of benzyl bromide and benzyl iodide type monomeric resins based on the adamantane structure, namely the compounds shown in formula (I), formula (II), formula (III) and formula (IV), which can be used as the host material of photoresist. The raw materials are cheap and readily available, and the synthesis process is simple;

[0061] (2) The benzyl bromide or benzyl iodide monomolecular resin based on the adamantane structure provided by the present invention has good solubility in a variety of polar solvents and can be used to prepare good thin films by spin coating. The thermal decomposition temperature of the main material is greater than 110°C, which is suitable for the requirements of photolithography. The compounds shown in formula (I), (II), (III) or (IV) can be used as single-component non-chemical amplification photoresists, avoiding the problems of uneven distribution of acid-generating agents and anti-acid diffusion agents and uneven acid diffusion in chemical amplification photoresists. The resulting pattern has high resolution and low line edge roughness.

[0062] (3) The compound of the present invention uses adamantane as the core unit and is externally attached with multiple benzyl bromide or benzyl iodide groups. The core structure of adamantane and benzene ring maximizes the etching resistance of the main material.

[0063] (4) The benzyl bromide or benzyl iodide monomolecular resin based on the adamantane structure described in this invention has a definite molecular structure and a single molecular size, which can well meet the requirements of high-resolution photolithography.

[0064] (5) Through extensive photolithography experiments and research, the inventors discovered that replacing the chlorine on the benzene ring of the compound disclosed in Patent 202410023407X with bromine or iodine can significantly improve the sensitivity of the compound as a single-component photoresist during photolithography, while obtaining superior photolithographic patterns. This improves upon the problems of excessive pattern defects and poor sensitivity of the compound disclosed in Patent 202410023407X during high-resolution photolithography.

[0065] Terms and Definitions

[0066] Unless otherwise defined, all technical terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains.

[0067] "More than three" means three or more.

[0068] Term "C" 1-15 "Alkyl" should be understood as referring to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 15 carbon atoms. For example, "C 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, 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.

[0069] Term "C" 1-15 "Alkoxy" should be understood as -OC 1-15 Alkyl, wherein C 1-15 Alkyl groups have the above definition.

[0070] Term "C" 3-20 "Cycloalkyl" should be understood as representing a saturated monovalent monocyclic, bicyclic, or polycyclic hydrocarbon ring (also called a fused ring hydrocarbon ring) with 3-20 carbon atoms. Bicyclic or polycyclic cycloalkyl includes fused cycloalkyl, bridged cycloalkyl, and spirocyclic cycloalkyl; fused ring refers to a fused ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing a bond). Bridged ring refers to a fused ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. Spirocyclic refers to a fused ring structure formed by two or more cyclic structures sharing a single ring atom. For example, the C 3-20 Cycloalkyl groups can be C 3-8 Monocyclic cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C 7-12 Circoalkyl, such as decahydronaphthalene ring; or C 7-12 Bridged cycloalkyl groups, such as norbornene, adamantane, and bicyclo[2,2,2]octane.

[0071] The term "3-20 membered heterocyclic group" refers to a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O, and S, preferably a "3-10 membered heterocyclic group". The term "3-10 membered heterocyclic group" also refers to a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3, heteroatoms selected from N, O, and S. The heterocyclic group can be connected to the rest of the molecule via any one of the carbon atoms or a nitrogen atom (if present). Specifically, the heterocyclic group can include, but is not limited to: 4-membered rings, such as azirrobutyl or oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoalkyl, pyrazolyl, or pyrrololinyl; or 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazinyl, or trithiaalkyl; or 7-membered rings, such as diazacycloheptyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, for example, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopenta[c]pyrrole-2(1H)-yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl ring. The nitrogen-containing ring may be partially unsaturated, i.e., it may contain one, two, or more double bonds, for example, but not limited to, 2,5-dihydro-1H-pyrrole, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, or it may be benzo-fused, for example, but not limited to, dihydroisoquinolinyl, 1,3-benzooxazolyl, or 1,3-benzodioxacyclopentenyl. According to the invention, the heterocyclic group is non-aromatic.

[0072] Term "C" 6-20 "Aryl" should be understood as representing a monocyclic, bicyclic, or tricyclic hydrocarbon ring with 6 to 20 carbon atoms, exhibiting monovalent aromaticity or partial aromaticity, preferably "C". 6-14 "Aromatic". 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", such as anthracene. When the C 6-20When 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.

[0073] The term "5-20-membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, such as "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monovalent 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 benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc.

[0074] The term "C" above 1-15 The definition of "alkyl" also applies to other C-containing compounds. 1-15 Alkyl groups, such as -C 1-15 Alkyl-C 6-20 Aryl, -C 1-15 Alkyl-5-20 heteroaryl, -C 1-15 Alkyl-CO-C 6-20 Aryl, -C 1-15 Alkyl-CO-5-20-membered heteroaryl, -C 1-15 Alkyl-CO-C 1-15 Alkyl, -C 1-15 Alkyl-CO-C 3-20 Cycloalkyl groups, etc.

[0075] Similarly, C 6-20 Aryl, 5-20 heteroaryl, C 3-20 The cycloalkyl group has the same definition throughout the text. Attached Figure Description

[0076] Figure 1 This is a thermogravimetric curve of compound I-1 in Example 1 of the present invention.

[0077] Figure 2 This is a thermogravimetric curve of compound I-2 in Example 2 of the present invention.

[0078] Figure 3 This is an atomic force microscope (AFM) image of the thin film of compound I-2 in Example 2 of the present invention.

[0079] Figure 4 This is a scanning electron microscope (SEM) image of the electron beam lithography stripes (exposure period of 60 nm) of the negative photoresist with compound I-2 as the main material in Example 2 of the present invention.

[0080] Figure 5 (a) is a scanning electron microscope (SEM) image of electron beam lithography stripes (exposure period of 50 nm) of negative photoresist with compound I-2 as the main material in Example 2 of the present invention; Figure 5 (b) is a scanning electron microscope (SEM) image of electron beam lithography stripes (exposure period of 50 nm) of negative photoresist with compound I-1 in patent 202410023407X as the main material.

[0081] Figure 6 The image shows a scanning electron microscope (SEM) image of electron beam lithography stripes (exposure period of 44 nm) of a negative photoresist with compound I-2 as the main material in Example 2 of this invention.

[0082] Figure 7 (a) is a scanning electron microscope (SEM) image of the deep ultraviolet (254 nm) lithographic stripes (exposure period of 3 μm) of the negative photoresist with compound IV-1 as the main material in Example 11 of the present invention; Figure 7 (b) is a scanning electron microscope (SEM) image of the deep ultraviolet (254 nm) lithographic stripes (exposure period of 6 μm) of a negative photoresist with compound II-1 in patent 202410023407X as the main material. Detailed Implementation

[0083] 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.

[0084] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0085] Example 1

[0086] The synthetic route for preparing compound VI-1 is as follows:

[0087]

[0088] Specific steps: Add 1,3-dibromoadamantane (1 g, 3.4 mmol, 1 eq), 1,3-dibromobenzene (2.4 g, 10.3 mmol, 3 eq), and 15 mL of dry 1,2-dichloroethane sequentially to a 100 mL two-necked flask. Stir the reaction mixture at a constant speed and place it in an ice-water bath. Grind anhydrous aluminum trichloride (150 mg, 1.1 mmol, 0.33 eq) finely and add it to the reaction mixture in three portions, 5 min apart, under a nitrogen atmosphere. React the mixture in an ice-water bath for 1 h, then stir vigorously for 20 min. Filter the reaction solution to obtain a white solid, wash three times with water and petroleum ether to obtain the crude product. Precipitate the crude product three times in n-hexane to obtain 1.8 g of a white solid. 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.51 (s, 2H), 7.42 (s, 4H), 2.34 (s, 2H), 1.90 (m, 10H), 1.77 (s, 2H); MS (EI): m / z = 604.02, calculated C 22 H 20 Br4 + m / z = 604.02 ([M]) + ).

[0089] The synthetic route for preparing compound V-1 is as follows:

[0090]

[0091] Specific steps: Add compound VI-1 (2.5 g, 4.1 mmol, 1.0 eq), 2-(hydroxymethyl)phenylboronic acid (3.77 g, 24.8 mmol, 6.0 eq), and 20 ml of 1,4-dioxane to a 250 ml Schlenk flask. Heat to 60°C; the reactants cannot completely dissolve. Dissolve anhydrous potassium carbonate (4.09 g, 24.8 mmol, 6.0 eq) in 5 ml of deionized water and add it to the reaction flask. Repeat the process three times under vacuum and nitrogen purging. Add the catalyst tetratetraphenylphosphine palladium (143 mg, 0.2 mmol, 0.06 eq) under nitrogen protection, and slowly heat to reflux temperature (set at 100°C). After 1 hour, the reaction solution becomes pale yellow and transparent. After 12 hours, stop heating and stirring, cool to room temperature, and then distill under reduced pressure to remove most of the solvent. The crude product was extracted with ethyl acetate / water, and the organic phase was washed twice with water and once with saturated brine. The organic phases were combined. The mixture was dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure to give a yellow foamy solid, which was dissolved in a small amount of ethyl acetate. After separation and purification by column chromatography (eluent: ethyl acetate: petroleum ether = 2:1), 2.4 g of a white foamy solid was obtained. 1 ¹H NMR (600MHz, deuterated chloroform) δ 7.64 (m, 10⁻⁶ H), 7.61 (d, J = 1.6Hz, 4⁻⁶ H), 7.46 (m, 8⁻⁶ H), 4.76 (s, 8⁻⁶ H), 2.42 (s, 2⁻⁶ H), 2.25 (s, 2⁻⁶ H), 2.14 (m, 8⁻⁶ H), 1.87 (s, 2⁻⁶ H). MS (ESI): m / z = 735.36, calculated C 50 H 48 O4Na + m / z = 735.35([M+Na] + ).

[0092] The synthetic route for preparing compound I-1 is as follows:

[0093] Specific steps: Compound V-1 (1 g, 1.4 mmol, 1.0 eq) and 10 ml of dichloromethane were added to a 100 ml Schlenk reaction flask. Trimethylbromosilane (0.43 g, 2.8 mmol, 2.0 eq) was dissolved in 5 ml of dichloromethane and added dropwise to the reaction flask. The reaction solution was white and turbid, and stirred at room temperature. After stirring for 1 hour, the reaction solution became yellow and transparent. After stirring for 10 hours, stirring was stopped and the solution was distilled under reduced pressure. After removing most of the solvent, the crude product was extracted with dichloromethane / saturated brine, the organic phases were combined, and the organic phase was washed with water until neutral. The organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove the solvent, yielding the crude product. The crude product was purified by column chromatography (DCM:PE = 1:2) to obtain 0.9 g of a white foamy solid. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.62 (m, ¹⁴ H), 7.42 (m, ⁸ H), 4.68 (s, ⁸ H), 2.40 (m, ² H), 2.24 (s, ² H), 2.15 (m, ⁸ H), 1.88 (s, ² H). MS (MALDI): m / z = 964.15, calculated C 50 H 44 Br4m / z = 964.16 [M] + .

[0094] Example 2

[0095] The synthetic route for preparing compound V-2 is as follows:

[0096] The specific steps are the same as the preparation process of V-1 in Example 1, except that 2-(hydroxymethyl)phenylboronic acid is replaced with 3-(hydroxymethyl)phenylboronic acid, and the reaction yield is 73%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.64 (m, 10⁻⁶ H) 7.58 (dt, J=7.7, 1.5 Hz, 4 H), 7.45 (t, J=7.6 Hz, 4 H), 7.36 (m, 4 H), 4.78 (s, 8 H), 2.42 (m, 2 H), 2.27 (s, 2 H), 2.12 (m, 8 H), 1.88 (d, J=3.3 Hz, 2 H). MS (ESI): m / z = 735.36, calculated C 50 H 48 O4Na + m / z = 735.35([M+Na]) + ).

[0097] The synthetic route for preparing compound I-2 is as follows:

[0098] The specific steps are the same as the preparation process of I-1 in Example 1, and the reaction yield is 82%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.65 (m, 14 H), 7.50 (m, 8 H), 4.66 (s, 8 H), 2.45 (p, J=3.1 Hz, 2 H), 2.20 (s, 2 H), 2.12 (m, 8 H), 1.88 (d, J=3.2 Hz, 2 H). MS (MALDI): m / z = 964.15, calculated C 50 H 44 Br4m / z = 964.16 [M] + .

[0099] Example 3

[0100] The synthetic route for preparing compound V-3 is as follows:

[0101]

[0102] The specific steps are the same as the preparation process of V-1 in Example 1, except that 2-(hydroxymethyl)phenylboronic acid is replaced with 4-(hydroxymethyl)phenylboronic acid, and the reaction yield is 75%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.64 (m, 10⁻⁶ H), 7.61 (d, J = 1.6 Hz, 4⁻⁶ H), 7.46 (m, 8⁻⁶ H), 4.76 (s, 8⁻⁶ H), 2.42 (s, 2⁻⁶ H), 2.25 (s, 2⁻⁶ H), 2.14 (m, 8⁻⁶ H), 1.87 (s, 2⁻⁶ H). MS (ESI): m / z = 735.36, calculated C 50 H 48 O4Na + m / z = 735.35 ([M+Na]) + ).

[0103] The synthetic route for preparing compound I-3 is as follows:

[0104]

[0105] The specific steps are the same as the preparation process of I-1 in Example 1, with a reaction yield of 80%. 1¹H NMR (600 MHz, deuterated chloroform) δ 7.64 (m, 14 H), 7.50 (m, 8 H), 4.66 (s, 8 H), 2.45 (s, 2 H), 2.20 (s, 2 H), 2.12 (m, 8 H), 1.88 (d, J = 3.2 Hz, 2 H). MS (MALDI): m / z = 964.15, calculated C 50 H 44 Br4m / z = 964.16 [M] + .

[0106] Example 4

[0107] The synthetic route for preparing compound VI-2 is as follows:

[0108]

[0109] Specific steps: Nitrogen gas was introduced into one end of a 250 mL three-necked reaction flask, and a tail gas absorption device was connected to the other end. 1,3-Dibromoadamantane (8.9 g, 30 mmol, 1.0 eq), 2,6-dibromophenol (19 g, 75 mmol, 2.5 eq), and 30 mL of dry 1,2-dichloroethane were added. The reaction was placed in an ice bath and purged with nitrogen. Under nitrogen atmosphere, aluminum trichloride catalyst (1.3 g, 9.9 mmol, 0.33 eq) was added, and the reaction mixture was kept in an ice bath for 5 hours. After the reaction was complete, the system was a brick-red turbid liquid. The reaction was quenched with 2M hydrochloric acid solution, and the crude product was obtained by filtration. The crude product was extracted with dichloromethane / water, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation. Petroleum ether was added and sonicated to dissolve excess phenol. The product was dried to obtain a white solid with a yield of 81%. 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.42 (s, 4 H), 5.75 (s, 2 H), 2.32 (s, 2 H), 2.17 (s, 2 H), 2.04 (q, J=11.6, 10.9 Hz, 8 H), 1.83 (s, 2 H); MS (ESI): m / z = 636.02, calculated C 22 H 20 Br4O2 + m / z = 636.02 ([M]) + ).

[0110] The synthetic route for preparing compound VI-3 is as follows:

[0111]

[0112] Specific steps: Compound VI-2 (8 g, 12.6 mmol, 1.0 eq) and 80 ml of acetone solvent were added to a 250 ml Schlenk flask. After stirring and heating to 60 °C until completely dissolved, potassium carbonate (6.95 g, 50.3 mmol, 4.0 eq) was added. Iodomethane (8.47 g, 50.3 mmol, 4.0 eq) was added dropwise to the reaction flask using a syringe. After the addition was complete, the reaction was carried out at 60 °C for 22 hours. Heating was stopped, and the solvent was removed by vacuum distillation. The mixture was then extracted with dichloromethane / water. The organic phases were combined, dried over anhydrous magnesium sulfate, and most of the solvent was removed by vacuum distillation. Approximately 20 ml of methanol was added to the crude product, and after sonication, a white precipitate formed. Vacuum distillation yielded a white solid, with a yield of 93%. 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.41 (s, 4 H), 3.87 (s, 6 H), 2.34 (s, 2 H), 2.17 (s, 2 H), 2.04 (q, J=11.6, 10.9 Hz, 8 H), 1.83 (s, 2 H). MS (ESI): m / z = 663.85, calculated C 24 H 24 Br4O2 + m / z = 663.85 ([M]) + ).

[0113] The synthetic route for preparing compound V-4 is as follows:

[0114]

[0115] The specific steps are the same as the preparation process of V-3 in Example 3, except that compound VI-1 is replaced with compound VI-3, and the reaction yield is 79%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.64 (m, 10 H), 7.61 (d, J=1.6Hz, 4 H), 7.46 (m, 8 H), 4.76 (s, 8 H), 3.90 (s, 6 H), 2.42 (s, 2 H), 2.25 (s, 2 H), 2.14 (m, 8 H), 1.87 (s, 2 H). MS (ESI): m / z = 795.97, calculated C 52 H 52 O6Na + m / z = 795.97([M+Na]) + ).

[0116] The synthetic route for preparing compound I-4 is as follows:

[0117]

[0118] The specific steps are the same as the preparation process of I-3 in Example 3, except that compound V-3 is replaced with compound V-4, and the reaction yield is 89%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.64 (m, 8 H), 7.61 (d, J=1.6 Hz, 4 H), 7.42 (m, 8 H), 4.91 (s, 8 H), 3.92 (s, 6 H), 2.41 (s, 2 H), 2.22 (s, 2 H), 2.14 (m, 8 H), 1.87 (s, 2 H). MS (MALDI): m / z = 1024.56, calculated C 52 H 48 O2Br4 + m / z = 1024.57 [M] + .

[0119] Example 5

[0120] The synthetic route for preparing compound II-1 is as follows:

[0121]

[0122] The specific steps are the same as the preparation process of I-1 in Example 1, except that the compound trimethylbromosilane is replaced with the compound trimethyliodosilane, and the reaction yield is 60%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.63 (m, ¹⁴ H), 7.42 (m, ⁸ H), 4.66 (s, ⁸ H), 2.39 (m, ² H), 2.21 (s, ² H), 2.10 (m, ⁸ H), 1.82 (s, ² H). MS (MALDI): m / z = 1152.51, calculated C 50 H 44 I₄m / z = 1152.52 [M] + .

[0123] Example 6

[0124] The synthetic route for preparing compound II-2 is as follows:

[0125]

[0126] The specific steps are the same as the preparation process of I-2 in Example 2, except that the compound trimethylbromosilane is replaced with the compound trimethyliodosilane, and the reaction yield is 61%. 1¹H NMR (600 MHz, deuterated chloroform) δ 7.66 (m, 14 H), 7.50 (m, 8 H), 4.67 (s, 8 H), 2.45 (p, J=3.1 Hz, 2 H), 2.20 (s, 2 H), 2.11 (m, 8 H), 1.88 (d, J=3.2 Hz, 2 H). MS (MALDI): m / z = 1152.52, calculated C 50 H 44 I₄m / z = 1152.52 [M] + .

[0127] Example 7

[0128] The synthetic route for preparing compound II-3 is as follows:

[0129]

[0130] The specific steps are the same as the preparation process of I-3 in Example 3, except that the compound trimethylbromosilane is replaced with the compound trimethyliodosilane, and the reaction yield is 70%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.64 (m, ¹⁴ H), 7.49 (m, ⁸ H), 4.67 (s, ⁸ H), 2.45 (s, ⁻² H), 2.20 (s, ⁻² H), 2.12 (m, ⁻² H), 1.88 (s, ⁻² H). MS (MALDI): m / z = 1152.52, calculated C 50 H 44 I₄m / z = 1152.52 [M] + .

[0131] Example 8

[0132] The synthetic route for preparing compound II-4 is as follows:

[0133]

[0134] The specific steps are the same as the preparation process of I-4 in Example 4, except that the compound trimethylbromosilane is replaced with the compound trimethyliodosilane, and the reaction yield is 69%. 1¹H NMR (600 MHz, deuterated chloroform) δ 7.64 (m, 8 H), 7.62 (d, J=1.6 Hz, 4 H), 7.44 (m, 8 H), 4.90 (s, 8 H), 3.98 (s, 6 H), 2.41 (s, 2 H), 2.22 (s, 2 H), 2.14 (m, 8 H), 1.89 (s, 2 H). MS (MALDI): m / z = 1212.57, calculated C 52 H 48 O2I4 + m / z = 1212.57 [M] + .

[0135] Example 9

[0136] The synthetic route for preparing compound VI-4 is as follows:

[0137]

[0138] The specific steps are the same as the preparation process of VI-1 in Example 1, except that compound 1,3-dibromoadamantane is replaced with compound 1,3,5-tribromoadamantane, with a yield of 80%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 9.71 (s, 3H), 7.62 (s, 6H), 2.40 (s, 1H), 2.03 (d, J = 11.8 Hz, 3H), 1.83 (m, 9H). MS (EI): m / z = 837.68, calculated C 28 H 22 Br6 + m / z = 837.68 ([M]) + ).

[0139] The synthetic route for preparing compound V-5 is as follows:

[0140]

[0141] The specific steps are the same as the preparation process of V-2 in Example 2, except that compound VI-1 is replaced with compound VI-4, and the reaction yield is 70%. 1¹H NMR (600 MHz, deuterated chloroform) δ 7.69 (dt, J=12.4, 1.5Hz, 9H), 7.55 (dt, J=7.5, 1.2Hz, 6H), 7.47 (m, 12H), 7.36 (m, 6H), 4.79 (s, 12H), 2.40 (s, 1H), 2.03 (d, J = 11.8 Hz, 3H), 1.83 (m, 9H). MS (ESI): m / z = 1023.46, calculated C 70 H 64 O6Na + m / z = 1023.46 ([M+Na]) + ).

[0142] The synthetic route for preparing compound III-1 is as follows:

[0143] The specific steps are the same as the preparation process of I-2 in Example 2, except that compound V-2 is replaced with compound V-5, and the reaction yield is 87%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.70 (dt, J=12.4, 1.5 Hz, 9H), 7.55 (dt, J=7.5, 1.2 Hz, 6H), 7.48 (m, 12H), 7.37 (m, 6H), 4.91 (s, 12H), 2.41 (s, 1H), 2.00 (d, J = 11.8 Hz, 3H), 1.83 (m, 9H). MS (MALDI): m / z = 1378.66, calculated C 70 H 58 Br6 + m / z = 1378.66 ([M]) + ).

[0144] Example 10

[0145] The synthetic route for preparing compound V-6 is as follows:

[0146]

[0147] The specific steps are the same as the preparation process of V-3 in Example 3, except that compound VI-1 is replaced with compound VI-4, and the reaction yield is 82%. 1¹H NMR (600 MHz, deuterated chloroform) δ 8.00 (s, 3H), δ 7.83 (s, 6H), 7.42 (m, 24H), 4.81 (s, 12H), 2.40 (s, 1H), 2.03 (d, J = 11.3 Hz, 3H), 1.73 (m, 9H). MS (ESI): m / z = 1023.46, calculated C 70 H 64 O6Na + m / z = 1023.46 ([M+Na]) + ).

[0148] The synthetic route for preparing compound III-2 is as follows:

[0149]

[0150] The specific steps are the same as the preparation process of I-3 in Example 3, except that compound V-3 is replaced with compound V-6, and the reaction yield is 79%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 8.02 (s, 3H), δ 7.84 (s, 6H), 7.45 (m, 24H), 4.92 (s, 12H), 2.30 (s, 1H), 2.03 (d, J = 11.3 Hz, 3H), 1.78 (m, 9H). MS (MALDI): m / z = 1378.65, calculated C 70 H 58 Br6 + m / z = 1378.66 ([M]) + ).

[0151] Example 11

[0152] The synthetic route for preparing compound IV-1 is as follows:

[0153] The specific steps are the same as the preparation process of Ⅲ-1 in Example 9, except that the compound trimethylbromosilane is replaced with the compound trimethyliodosilane, and the reaction yield is 68%. 1¹H NMR (600 MHz, deuterated chloroform) δ 7.71 (dt, J=11.4, 1.4 Hz, 9 Hz), 7.55 (dt, J=7.2, 1.5 Hz, 6 Hz), 7.47 (m, 12 Hz), 7.37 (m, 6 Hz), 4.90 (s, 12 Hz), 2.41 (s, 1 Hz), 2.02 (d, J = 11.8 Hz, 3 Hz), 1.83 (m, 9 Hz). MS (MALDI): m / z=1660.66, calculated C 70 H 58 I6 + m / z = 1660.66 ([M]) + ).

[0154] Example 12

[0155] The synthetic route for preparing compound IV-2 is as follows:

[0156]

[0157] The specific steps are the same as the preparation process of Ⅲ-2 in Example 10, except that the compound trimethylbromosilane is replaced with the compound trimethyliodosilane, and the reaction yield is 69%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 8.00 (s, 3H), δ 7.84 (s, 6H), 7.45 (m, 24H), 4.90 (s, 12H), 2.30 (s, 1H), 2.03 (d, J = 11.3Hz, 3H), 1.81 (m, 9H). MS (MALDI): m / z = 1660.66, calculated C 70 H 58 I6 + m / z = 1660.66 ([M]) + ).

[0158] Example 13

[0159] The thermal stability of compound I-1 prepared in Example 1 and compound I-2 prepared in Example 2 was determined. The thermogravimetric analysis curve of compound I-1 in Example 1 is shown in Figure 1. Figure 1 The thermogravimetric analysis curve of compound I-2 in Example 2 is shown in Figure 2. Figure 2 The results showed that the thermal decomposition temperatures of both compounds were above 110℃, indicating good thermal stability.

[0160] Example 14

[0161] Compound I-2 was dissolved in propylene glycol methyl ether acetate to prepare a solution with a concentration of 30 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate. The uniformity of the film was analyzed using atomic force microscopy (AFM). The test results are shown in the appendix. Figure 3 ,from Figure 3 As can be seen, the obtained film is very uniform and there is no crystallization, which is beneficial for obtaining a smooth photolithographic pattern.

[0162] Example 15

[0163] A negative photoresist formulation and photolithography: Compound I-2 from Example 2 was dissolved in propylene glycol methyl ether acetate to prepare a solution with a mass concentration of 20 mg / ml. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. This solution was then spin-coated onto a silicon substrate, pre-baked at 80°C for 2 minutes, and the film thickness was measured using an ellipsometry. The prepared film was exposed using an electron beam light source at the National Center for Nanoscience and Technology with an exposure period of 60 nm, resulting in very uniform lithographic stripes. The test results are shown in [Figure number missing]. Figure 4 The results show that the obtained pattern has both good resolution and contrast, as well as very low line edge roughness.

[0164] Example 16

[0165] Comparison of photolithographic patterning capabilities between two types of negative photoresists:

[0166] In Example 2 of this invention, compound I-2 was used as the negative photoresist formulation and photolithography for a single-component photoresist substrate: Compound I-2 was dissolved in propylene glycol methyl ether acetate to obtain a solution with a mass concentration of 20 mg / ml. This solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. Spin-coating was performed on a silicon substrate, followed by pre-baking at 80°C for 2 minutes. The film thickness was measured using an ellipsometer. The prepared film was then exposed using an electron beam light source at the National Center for Nanoscience and Technology, using dense lines with a period of 50 nm and a duty cycle of 1:1 as the pattern, and an exposure dose of 1576 μC / cm. 2 Then, hexane was used for development, and the resulting stripes are shown in the figure. Figure 5 In (a), the width of the lithographic stripes is 25 nm. A dense pattern of lines with a period of 44 nm and a duty cycle of 1:1 is used, and the exposure dose is 1658 μC / cm². 2 Then, hexane was used for development, and the resulting stripes are shown in the figure. Figure 6 The width of the photolithographic stripes is 22 nm.

[0167] The negative photoresist formulation and photolithography using compound I-1 from patent 202410023407X as the host material of a single-component photoresist: Compound I-1 from patent 202410023407X was dissolved in propylene glycol methyl ether acetate to prepare a solution with a mass concentration of 20 mg / ml. This solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. Spin-coating was performed on a silicon substrate, followed by pre-baking at 80°C for 2 minutes. The film thickness was measured using an ellipsometer. The prepared film was then exposed using an electron beam light source at the National Center for Nanoscience and Technology, using dense lines with a period of 50 nm and a duty cycle of 1:1 as the pattern, and an exposure dose of 2500 μC / cm. 2 Then, hexane was used for development, and the resulting stripes are shown in the figure. Figure 5 In (b), the width of the photolithographic stripes is 25 nm, and the edge roughness of the stripes is relatively large.

[0168] In summary, the negative photoresist formulation of compound I-1 in patent 202410023407X, used as the host material of a single-component photoresist, requires an exposure dose of 2500 μC / cm² to obtain lithographic stripes with a period of 50 nm (duty cycle 1:1) in electron beam lithography. 2 The negative photoresist formulation using compound I-2 as the host material of this invention to achieve 50 nm period (duty cycle 1:1) lithographic stripes with the same properties as compound I-1 in patent 202410023407X requires an exposure dose of only 1576 μC / cm². 2 The exposure dose is significantly lower than that of compound I-1 in patent 202410023407X, resulting in a significant improvement in photolithography sensitivity.

[0169] Furthermore, the negative photoresist formulation using compound I-2 of the present invention as the host material of a single-component photoresist requires an exposure dose of only 1658 μC / cm² to obtain lithographic stripes with a period of 44 nm (duty cycle 1:1) in electron beam lithography. 2 As can be seen, compared with the compound with benzyl chloride as the photosensitive group in patent 202410023407X, the compound with benzyl bromide as the photosensitive group in this invention not only requires a lower exposure dose to obtain the same stripes without obvious defects, but also can achieve higher resolution patterns with a lower exposure dose. This shows that the negative photoresist formulation of this invention as a single-component photoresist host material has significant advantages.

[0170] Example 17

[0171] Comparison of photolithographic patterning capabilities between two types of negative photoresists:

[0172] In Example 11 of this invention, compound IV-1 was used as the negative photoresist formulation and photolithography for a single-component photoresist substrate: Compound IV-1 was dissolved in acetonitrile to prepare a solution with a mass concentration of 20 mg / ml. This solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. A spin-coating film was then formed on a silicon substrate, pre-baked at 80°C for 2 minutes, and the film thickness was measured using an ellipsometry. The prepared film was then exposed to a 254 nm mercury lamp via contact exposure for 30 s, resulting in very uniform photolithographic stripes. The test results are shown in [Figure number missing]. Figure 7 (a) Among them, Figure 7 In the middle (a), the photolithographic pattern has an exposure period of 3 μm and a stripe width of about 1.5 μm. The results show that the obtained pattern has both good resolution and contrast and very low line edge roughness.

[0173] The negative photoresist formulation and photolithography using compound II-1 as the host material in patent 202410023407X: Compound II-1 is dissolved in acetonitrile to prepare a solution with a mass concentration of 25 mg / ml. This solution is filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. A film is then spin-coated onto a silicon substrate, pre-baked at 80°C for 2 minutes, and the film thickness is measured using an ellipsometry. The prepared film is then exposed to a 254 nm mercury lamp via contact exposure for 2 minutes, resulting in uniform photolithographic stripes. The test results are shown in […]. Figure 7 (b) Among them, Figure 7 In the middle (b), the photolithography pattern has an exposure period of 6 μm and the width of the photolithography stripes is about 3 μm.

[0174] In summary, the negative photoresist formulation using compound II-1 in patent 202410023407X as the main material of a single-component photoresist requires an exposure time of 2 minutes to obtain 6 μm periodic lithographic stripes in deep ultraviolet lithography. However, the negative photoresist formulation of this invention using compound IV-1 as the main material of a single-component photoresist requires an exposure time of only 30 seconds to obtain 3 μm periodic lithographic stripes with a smaller period than compound II-1 in patent 202410023407X. The exposure dose is significantly lower than that of compound II-1 in patent 202410023407X, resulting in a significant improvement in lithographic sensitivity. As can be seen, the compound of this invention using benzyl iodine as the photosensitive group, compared with the compound of similar structure using benzyl chloride as the photosensitive group in patent 202410023407X, can achieve higher resolution patterns with significantly lower exposure dose while obtaining the same stripes without obvious defects. This indicates that the negative photoresist formulation of this invention as a single-component photoresist host material has significant advantages over the compound in patent 202410023407X.

[0175] The exemplary embodiments of the present invention have been described above. However, the scope of protection 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 scope of protection of the present invention.

Claims

1. Compounds represented by formula (I), (II), (III), or (IV): in, R is H or -C 1-6 Alkoxy; -CH2Br or -CH2I is simultaneously located in the ortho position of the benzene ring it substituted; Alternatively, it may be located at the meta position of the benzene ring it substituted; Alternatively, it may be located at the para position of the benzene ring it substituted.

2. The compound according to claim 1, wherein, In formulas (I), (II), (III), or (IV), the two R's on the left and right sides have the same structure and are both selected from H or -C. 1-6 Alkyl group.

3. The compound according to claim 1, wherein, In formulas (I), (II), (III), or (IV), the two Rs on the left and right sides have the same structure and are selected from H or methoxy groups.

4. The compound according to any one of claims 1-3, wherein, The compound shown in formula (I) has the following structure: ;or, The compound shown in formula (II) has the following structure: ;or, The compound shown in formula (III) has the following structure: ;or, The compound shown in formula (Ⅳ) has the following structure: 。 5. A method for preparing the compound according to any one of claims 1-4, wherein, include: The compound (P1) was reacted with trimethylbromosilane to give the compound shown in formula (I); Alternatively, reacting compound (P1) with trimethyliodosilane yields the compound shown in formula (II); Alternatively, reacting compound (P2) with trimethylbromosilane yields the compound shown in formula (III); Alternatively, reacting compound (P2) with trimethyliodosilane yields the compound shown in formula (Ⅳ); ； Where R is H or -C 1-6 Alkoxy; -CH2OH, -CH2Br, or -CH2I are simultaneously located in the ortho position of the benzene ring they substituted; Alternatively, it may be located at the meta position of the benzene ring it substituted; Alternatively, it may be located at the para position of the benzene ring it substituted.

6. A photoresist composition comprising one or more compounds of formula (I), (II), (III) or (IV) as described in any one of claims 1-4.

7. The photoresist composition according to claim 6, wherein, The compounds shown in formula (I), formula (II), formula (III) or formula (IV) are used as the host material of the photoresist composition.

8. A photoresist coating comprising one or more of the compounds of formula (I), formula (II), formula (III) or formula (IV) as described in any one of claims 1-4.

9. The application of the photoresist composition of claim 6 or 7, or the photoresist coating of claim 8, in photolithography.

10. The application according to claim 9, wherein, The photolithography is 365nm photolithography, 254nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet photolithography, nanoimprint lithography, or electron beam lithography.

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