Electron beam photoresist composition containing self-crosslinking resin as well as preparation method and application of electron beam photoresist composition

Abstract

The invention provides an electron beam photoresist composition containing cross-linked resin as well as a preparation method and application of the electron beam photoresist composition. The electron beam photoresist composition comprises a blend of two different systems of resins, a self-crosslinking resin material is doped on the basis of electron beam photoresist substrate resin, and the problem that lines are prone to collapse is solved under the condition that a later electron beam photoetching basic process is not affected.

Description

[0001] This application is a divisional application of application number 202411374332.6, filed on September 29, 2024, entitled "An electron beam photoresist composition containing self-crosslinking resin and its preparation method and application". Technical Field

[0002] This invention relates to the field of photoresist technology, and in particular to an electron beam photoresist composition containing a self-crosslinking resin polymer material, its preparation method, and its application. Background Technology

[0003] Photoresist, also known as photoresist, is a crucial core material in the photolithography process. It refers to an etch-resistant material whose solubility changes upon exposure to electromagnetic waves such as ultraviolet light, X-rays, and electron beams. It plays a role in transferring patterns and is widely used in the processing of fine patterns in displays, integrated circuits, microelectromechanical systems (MEMS), and optoelectronic devices. In recent years, the rapid development of large-scale integrated circuits and the display industry has placed higher demands on photolithography processes, requiring the acquisition of more refined and higher-resolution replicated patterns. The development of photolithography technology and continuous innovation in photolithography materials have jointly propelled Moore's Law forward. As predicted by Moore's Law, the critical dimension (CD), representing the level of chip manufacturing, continues to decrease, leading to the need to improve photoresist parameters such as line edge roughness and sensitivity. The size of the CD is typically determined by the Rayleigh criterion, and a common strategy for achieving a smaller CD is to reduce the wavelength of the exposure light source. Therefore, the exposure wavelength of lithography machines has been continuously developing from ultraviolet g-line (436nm) → i-line (365nm) → 248nm → 193nm → extreme ultraviolet (EUV) → X-ray, and even non-optical lithography (electron beam exposure, ion beam exposure) has been adopted. The overall performance of photoresist products must also be improved accordingly to meet the requirements of integrated circuit manufacturing processes.

[0004] Electron beam photoresists are widely used in micro / nano pattern fabrication, chip design, mask manufacturing, second / third-generation compound semiconductor chip manufacturing, and optical communication chip manufacturing. Electron beam photoresists are photolithographic materials coated on a substrate surface and used to transfer patterns through electron beam exposure. Electron beam photoresists are synthesized by combining the advantages of benzene ring structures and acrylate resins to create resin molecules with special structures, resulting in photoresist resins with excellent performance. Simultaneously, process parameters are controlled to obtain resin products with stable molecular weight and molecular weight distribution, ensuring product quality and performance stability. Finally, using resins and various additives, electron beam photoresists with different superior properties are prepared. Currently, the most commonly used electron beam photoresist in the large-scale integrated circuit industry is polymethyl methacrylate (PMMA) positive photoresist, which has high resolution. However, due to its relatively low sensitivity, the required exposure time and production cycle are long, resulting in higher production costs. Modified electron beam lithography (EPR) resists, such as ZEP520, are high-resolution, non-chemically amplified, positive chain-breaking EPRens. Their resolution can reach 10 nanometers, and under favorable process conditions, they can achieve pattern structures of 10–50 nanometers. They exhibit high sensitivity and excellent resistance to dry etching. ZEP520 is composed of a copolymer of α-chloromethyl methacrylate and α-methylstyrene, a modified PMMA polymer with added benzene rings, significantly improving its resistance to plasma etching. Like PMMA, ZEP520 offers high contrast, ease of use, and good repeatability. Compared to PMMA, ZEP520 requires a smaller dosage, resulting in higher sensitivity. Its disadvantage is poor adhesion to the substrate, which can lead to pattern collapse. Therefore, heat treatment of the substrate or the use of an HMDS adhesion promoter underlayer may be necessary before coating. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides an electron beam photoresist composition containing a crosslinked resin, its preparation method, and its applications. The electron beam photoresist composition of this invention comprises a blend of two different resin systems, in which a self-crosslinking resin material is doped onto the electron beam photoresist base resin, thereby improving the problem of line collapse without affecting the subsequent basic electron beam lithography process.

[0006] The technical solution of the present invention is as follows: An electron beam photoresist composition comprising: an electron beam photoresist substrate resin material and a self-crosslinking resin; The self-crosslinking resin is obtained by reacting a chain polymer with a crosslinking agent; the chain polymer includes aromatic groups and nitrogen-containing heterocyclic groups. The self-crosslinking resin is a crosslinking polymer.

[0007] According to an embodiment of the present invention, both the aromatic group and the nitrogen-containing heterocyclic group are located on the main chain of the chain polymer.

[0008] According to an embodiment of the present invention, the chain polymer is a polyester-based polymer.

[0009] According to an embodiment of the present invention, the chain polymer is formed by polymerizing at least one compound containing an aromatic group with at least one compound containing a nitrogen-containing heterocycle. For example, the chain polymer is formed by polymerizing one compound containing an aromatic group with two compounds containing nitrogen-containing heterocycles. According to an embodiment of the present invention, in a chain polymer, the polymeric units are linked by ester bonds to form a polymer.

[0010] According to embodiments of the present invention, the aromatic group can be a monocyclic or polycyclic aryl or heteroaryl, for example, C 6-20 Aryl, 5-20 quinone heteroaryl; preferably C 6-14 Aryl, 5-14 heteroaryl, such as phenyl, naphthyl, anthracene or biphenyl.

[0011] According to embodiments of the present invention, the compound containing aromatic groups further includes carboxyl groups and carboxylic acid ester groups (such as COOC). 1-12 Alkyl), carboxylic anhydride, or hydroxyl groups.

[0012] According to embodiments of the present invention, the compound containing aromatic groups further includes at least two groups selected from carboxylic acids, carboxylic esters, carboxylic anhydrides, and / or at least two hydroxyl groups.

[0013] In some embodiments of the present invention, the compound containing an aromatic group has the structure shown in M1' below: ROOC-A-COOR M1' Wherein, A is selected from the following groups that are unsubstituted or optionally substituted by one, two or more Rs: C 6-20 Aryl, 5-20 heteroaryl, C 6-20 Aryl-C 6-20 aryl or 5-20 heteroaryl; Rs is selected from oxo, halogen, cyano, nitro, C 1-12 Alkyl, C 1-12 Alkoxy, C 3-12 Cycloalkyl or 3-12 membered heterocyclic groups; R is selected from C 1-12 alkyl.

[0014] In some embodiments of the present invention, in M1', A is selected from C. 6-14 Aryl, 5-14 heteroaryl, C 6-14 Aryl-C 6-14Aryl or 5-14 heteroaryl-5-14 heteroaryl; R is selected from H and C. 1-6 alkyl.

[0015] In some specific embodiments of the present invention, the compound containing an aromatic group is, for example, the following compound:

[0016] .

[0017] According to embodiments of the present invention, the compound containing a nitrogen-containing heterocycle further includes a carboxyl group and a carboxylic acid ester group (such as COOC). 1-12 Alkyl), carboxylic anhydride, or hydroxyl groups.

[0018] According to embodiments of the present invention, the compound containing a nitrogen-containing heterocycle further includes at least two groups selected from carboxylic acids, carboxylic esters, carboxylic anhydrides, and / or at least two hydroxyl groups.

[0019] According to an embodiment of the present invention, the compound containing a nitrogen-containing heterocycle is a compound of general formula I: I Where R1 and R2 are the same or different, they are selected from -C 1-12 Alkyl-OR4, -C 1-12 Alkyl-COOR5, -C 1-12 Alkyl-OCOR5; R3 is selected from -C 1-12 Alkyl-OR4, -C 1-12 Alkyl-COOR5, -C 1-12 Alkyl-OCOR5, R6; R4, R5, and R6 may be the same or different, selected from H, or arbitrarily selected by one or more R... a The following groups are substituted: C 1-12 Alkyl, C 2-12 alkenyl, C 2-12 alkynyl, aryl, heteroaryl; R a Same or different, selected from oxo, halogen, cyano, nitro, alkyl, cycloalkyl, heterocyclic, aryl, heteroaryl, -NR b R c -OR d -CO-R d -COOR d -SR e -SO-Re -SO2-R e ; R b R c They may be the same or different, independently selected from hydrogen or arbitrarily selected by one, two or more R... a The following groups are substituted: C 1-12 Alkyl, C 3-12 cycloalkyl; R d R e Whether the same or different, independently selected from H, or arbitrarily selected by one, two or more Rs a The following groups are substituted: C 1-12 Alkyl, C 3-12 Cycloalkyl, 3-12 membered heterocyclic groups.

[0020] In some specific embodiments of the present invention, the compound containing a nitrogen-containing heterocycle includes the compounds shown as M2' and M3' below: M2' M3' Among them, R 21 R 22 R 23 Same or different, selected independently from -C 1-12 Alkyl-OH; R 31 R 32 Same or different, selected independently from -C 1-12 Alkyl-COOH or -C 1-12 Alkyl-COOC 1-12 Alkyl; R 33 Selected from H, C 1-12 Alkyl, aryl, heteroaryl, -C 1-12 Alkyl -OH, -C 1-12 Alkyl-OC 1-12 Alkyl, -C 1-12 Alkyl-COOH or -C 1-12 Alkyl-COOC 1-12 alkyl.

[0021] In some embodiments of the present invention, R 21 R 22 R 23 Same or different, selected independently from -C 1-6 Alkyl-OH; R 31 R 32 Same or different, selected independently from -C 1-6 Alkyl-COOH or -C 1-6 Alkyl-COOC 1-6Alkyl; R 33 Selected from H, C 1-6 Alkyl, -C 1-6 Alkyl -OH, -C 1-6 Alkyl-OC 1-6 Alkyl, -C 1-6 Alkyl-COOH or -C 1-6 Alkyl-COOC 1-6 alkyl.

[0022] In some specific embodiments of the present invention, the compound containing a nitrogen-containing heterocycle is, for example, tris(2-hydroxyethyl) isocyanurate or tris(2-carboxyethyl) isocyanurate.

[0023] In some embodiments of the present invention, the chain polymer is a polymer obtained by reacting M1', M2' and M3'.

[0024] Furthermore, when R 31 R 32 R 33 All three groups are -C 1-12 When alkyl-COOH is used, C can be used. 1-12 The fatty alcohol caps the unreacted COOH in monomer M3'.

[0025] The crosslinking agent of the present invention can be a crosslinkable compound having at least two substituents capable of forming crosslinks. The crosslinking agent can be an amino crosslinking agent, such as a glycourea-based crosslinking agent, a melamine-based crosslinking agent, a urea-based crosslinking agent, a benzoguanamine-based crosslinking agent, or a phenolic compound having substituents capable of forming crosslinks, such as hydroxymethyl and methoxymethyl.

[0026] In some embodiments of the present invention, the crosslinking agent may be, for example, methoxymethylated glycourea or methoxymethylated melamine, such as tetramethoxymethylglycourea, tetrabutoxymethylglycourea, or hexamethoxymethylmelamine. The crosslinking agent may be commercially available. For example, glycourea-based crosslinking agents sold by American Cyamine Corporation under the trade names Cymel 1170, 1171, and 1172; melamine-based crosslinking agents sold by American Cyamine Corporation under the trade names Cymel 300, 301, 303, 350, 370, 380, 1116, and 1130; urea-based crosslinking agents sold by American Cyamine Corporation under the trade names Powderlink 1174, 1196, Beetle 60, 65, and 80; and benzoguanamine-based crosslinking agents sold by American Cyamine Corporation under the trade names Cymel 1123 and 1125.

[0027] In some embodiments of the present invention, the crosslinking agent has a structure as shown in formula IC: IC Where s is an integer from 1 to 12; R7 and R8 may be the same or different, and are independently selected from H and C. 1-12 Alkyl, C 6-14 Aryl or 5-14 heteroaryl groups; R9, R 10 R 11 R 12 Same or different, selected independently from C 1-12 alkyl.

[0028] According to an embodiment of the present invention, s is an integer from 1 to 6, such as 1, 2, 3, 4; According to an embodiment of the present invention, R7 and R8 may be the same or different, and are independently selected from H and C. 1-6 Alkyl, phenyl; for example, H, methyl, ethyl, propyl, butyl or phenyl.

[0029] According to an embodiment of the present invention, R9, R 10 R 11 R 12 Same or different, selected independently from C 1-6 Alkyl, such as methyl, ethyl, n-propyl or n-butyl. In some specific embodiments of the present invention, the crosslinking agent is selected from the following structures:

[0030] .

[0031] According to an embodiment of the present invention, the weight-average molecular weight of the self-crosslinking resin is 1000-8000, such as 2000-7000, 3000-6000, or 4000-5000.

[0032] According to an embodiment of the present invention, the molecular weight distribution coefficient of the self-crosslinking resin is <2.5, such as 1.10-1.25, 1.25-1.50, 1.50-2.00, 2.00-2.04, 2.04-2.08 or 2.08-2.14.

[0033] In some specific embodiments of the present invention, the self-crosslinking resin has the following structural units:

[0034] .

[0035] According to an embodiment of the present invention, the electron beam photoresist substrate resin material is a copolymer of aromatic vinyl monomers and α-haloacrylate monomers; According to an embodiment of the present invention, the aromatic vinyl monomer is selected from at least one of α-methylstyrene monomer and 4-fluoro-α-methylstyrene monomer.

[0036] According to an embodiment of the present invention, the α-haloacrylate monomer is selected from at least one of α-chloroacrylate methyl ester monomer, α-chloroacrylate ethyl ester monomer, α-chloroacrylate benzyl ester monomer, α-chloroacrylate-1-adamantyl ester monomer, α-chloroacrylate-2,2,3,3,3-pentafluoropropyl ester monomer, α-chloroacrylate-2,2,3,3,4,4,4-heptafluorobutyl ester monomer, α-fluoroacrylate methyl ester monomer, α-fluoroacrylate ethyl ester monomer, α-fluoroacrylate benzyl ester monomer, α-fluoroacrylate-1-adamantyl ester monomer, α-fluoroacrylate-2,2,3,3,3-pentafluoropropyl ester monomer, and α-chloroacrylate-2,2,3,3,4,4,4-heptafluorobutyl ester monomer.

[0037] In some specific embodiments of the present invention, the base resin material is a resin material obtained by copolymerization of α-methylstyrene and methyl 2-chloroacrylate:

[0038] α-Methylstyrene-2-chloroacrylate.

[0039] According to an embodiment of the present invention, the weight-average molecular weight of the photoresist substrate resin material is 20,000 to 100,000, such as 20,000 to 50,000, 50,000 to 56,300, 56,300 to 58,000, 58,000 to 68,300, 68,300 to 69,900, 69,900 to 75,000, or 75,000 to 100,000.

[0040] According to an embodiment of the present invention, the molecular weight distribution coefficient of the photoresist substrate resin material is <2.5, such as 1.10-1.25, 1.25-1.50, 1.50-2.00, 2.00-2.04, 2.04-2.08 or 2.08-2.14.

[0041] According to an embodiment of the present invention, the electron beam photoresist composition further includes a solvent; the solvent is selected from at least one of anisole, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, butyl acetate, neopentyl acetate, γ-butyrolactone, and ethyl lactate, preferably anisole.

[0042] According to an embodiment of the present invention, the electron beam photoresist composition may further include an additive selected from at least one of surfactants, photoacid generators, thermoacid generators, viscosity control agents, and stabilizers.

[0043] According to embodiments of the present invention, the surfactant comprises: nonionic surfactants, such as polyoxyethylene alkyl ethers like polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers like polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters like sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmitate fluorinated surfactants. Examples include EF301, EF303, EF352, F171, F173, R-30, R-40, R-30-N, FC430, FC431, AG710, S-382, SC101, SC102 and organosilicon polymer KP341.

[0044] According to an embodiment of the present invention, the surfactant may be a single type or a mixture of multiple surfactants in the photoresist composition.

[0045] According to an embodiment of the present invention, the photoacid generator is selected from N-hydroxynaphthalimide trifluoromethanesulfonate, (4,8-dihydroxy-1-naphthyl)dimethylsulfonium trifluoromethanesulfonate, (4,7-dihydroxy-1-naphthyl)dimethylsulfonium trifluoromethanesulfonate, (4-methoxynaphthyl)diphenylsulfonium trifluoromethanesulfonate, (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate, 2-(benzo[d][1,3]dioxolane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4 At least one of (dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-[4-(4-methoxyphenyl)phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0046] According to an embodiment of the present invention, the viscosity control agent is selected from at least one of butanol, chloroform, ethanol, water, acetonitrile, hexane, and isopropanol.

[0047] According to an embodiment of the present invention, the stabilizer is selected from at least one of p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone.

[0048] According to an embodiment of the present invention, the mass percentages of each component in the electron beam photoresist composition are as follows: photoresist base resin material and self-crosslinking resin 3-15%, such as 3-7.5% or 7.5-15%; solvent 84.95-96.998%, such as 84.95-92.488% or 92.488-96.998%; additives 0.002-0.05%, such as 0.003-0.01%.

[0049] According to an embodiment of the present invention, the electron beam photoresist composition comprises the following components in weight percentages: 3-15% substrate resin material and self-crosslinking resin, 0.003-0.008% surfactant and 84.95-96.998% solvent.

[0050] The mass ratio of photoresist base resin material to self-crosslinking resin is 1:(30~160), for example 1:(40~120).

[0051] The present invention also provides a method for preparing the above-mentioned electron beam photoresist composition, comprising the following steps: mixing the photoresist substrate resin material and the self-crosslinking resin to obtain the electron beam photoresist composition.

[0052] According to an embodiment of the present invention, the preparation of the photoresist substrate resin material includes the following steps: copolymerizing the aromatic vinyl monomer and the α-haloacrylate monomer in the presence of an initiator to obtain the photoresist substrate resin material.

[0053] According to an embodiment of the present invention, the copolymerization reaction of aromatic vinyl monomers and α-haloacrylate monomers is carried out in an organic solvent.

[0054] According to an embodiment of the present invention, the copolymerization temperature of the aromatic vinyl monomer and the α-haloacrylate monomer is 65–90°C, such as 65–85°C or 85–90°C.

[0055] According to embodiments of the present invention, the initiator used for the aromatic vinyl monomer and the α-haloacrylate monomer is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile, methyl azobisisobutyrate, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, and tert-butyl peroxide.

[0056] According to an embodiment of the present invention, the method further includes a process for preparing a self-crosslinking resin, comprising: S1. A compound containing an aromatic group is polymerized with a compound containing a nitrogen-containing heterocycle to obtain a chain polymer; S2. React the chain polymer with a crosslinking agent.

[0057] According to an embodiment of the present invention, the reaction temperature in S1 is 120-180°C, for example 140-160°C. The reaction time is 1-12 hours.

[0058] According to an embodiment of the present invention, the amount of crosslinking agent may be 20% to 60% wt% of the polymer intermediate, for example 30% to 50%.

[0059] The present invention also provides a method for using the above-mentioned electron beam photoresist composition, comprising the following steps: coating the electron beam photoresist composition on a substrate, and sequentially performing pre-baking, exposure, post-baking, development and fixing to obtain a photolithographic pattern.

[0060] According to an embodiment of the present invention, the substrate is a silicon wafer.

[0061] According to an embodiment of the present invention, the method of use further includes at least one of the following technical features: 1) The pre-baking temperature is 160-200℃, such as 160-170℃, 170-180℃, 180-190℃ or 190-200℃; 2) The pre-baking time is 120-240 seconds, such as 120-180 seconds or 180-240 seconds; 3) The exposure energy is 75–425 μC / cm. 2 ; 4) The developing solution used for developing is amyl acetate or a mixture including amyl acetate and isopropanol; preferably amyl acetate; 5) The development time is 50-70 seconds, such as 50-60 seconds or 60-70 seconds; 6) The fixing solution used for fixing is isopropanol; 7) The fixing time is 10-50 seconds, such as 10-30 seconds or 30-50 seconds.

[0062] The present invention also provides the use of the above-described electron beam photoresist composition in electron beam lithography.

[0063] Beneficial effects This invention provides an electron beam photoresist composition containing a self-crosslinking resin. The self-crosslinking resin has polar groups that enhance the adhesion of the photoresist to the substrate. The photoresist composition of this invention can significantly improve the problem of line collapse in electron beam lithography without affecting resolution, etching resistance, or process tolerance. The resulting pattern has good line edge roughness.

[0064] Terminology Definitions and Explanations 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.

[0065] "More than three" means three or more.

[0066] The term "halogen" includes F, Cl, Br, or I.

[0067] Term "C" 1-12 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably "C". 1-6 Alkyl group. 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, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers.

[0068] Term "C" 1-12 "Alkoxy" should be understood as -OC 1-12 Alkyl, wherein C 1-12 Alkyl groups have the above definition.

[0069] Term "C" 6-20 "Aryl" should be understood to represent an aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, 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. 6-14Aryl), 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 groups, such as anthracene groups, or rings with 16 carbon atoms (“C”). 16 Aryl), such as pyrene. When the C 6-22 When the base is substituted, it can be a single substitution or multiple substitutions. Furthermore, there are no restrictions on the substitution site; for example, it can be an ortho, para, or meta substitution.

[0070] 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.

[0071] Term "C" 3-12 "Cycloalkyl" should be understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. The C... 3-12 Cycloalkyl groups can be monocyclic hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or bicyclic hydrocarbon groups such as decahydronaphthalene ring.

[0072] The term "3-12 membered heterocyclic group" 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 azirmonobutyl or oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoyl, 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 can be benzofused. The heterocyclic group can be bicyclic, such as, but not limited to, a 5,5-membered ring, like a hexahydrocyclopentano[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 can be partially unsaturated, i.e., it can contain one or more double bonds, such as, but not limited to, 2,5-dihydro-1H-pyrrole, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, or it can be benzofused, such as, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic group is non-aromatic. Attached Figure Description

[0073] Figure 1 The electron beam photoresist sample energy for Example 1 was 175 μC / cm. 2 (Left image) and energy of 250 μC / cm 2 (Right image) is a scanning electron microscope image of electron beam photoresist.

[0074] Figure 2 For Example 2, the electron beam photoresist sample was subjected to an energy of 175 μC / cm. 2 (Left image) and energy of 250 μC / cm 2 (Right image) Electron beam lithography scanning electron microscope image.

[0075] Figure 3 For Example 3, the electron beam photoresist sample was tested at an energy of 175 μC / cm. 2 (Left image) and energy of 250 μC / cm 2 (Right image) Electron beam lithography scanning electron microscope image.

[0076] Figure 4 For Example 4, the electron beam photoresist sample was subjected to an energy of 175 μC / cm. 2 (Left image) and energy of 250 μC / cm 2 (Right image) Electron beam lithography scanning electron microscope image.

[0077] Figure 5For Example 5, the electron beam photoresist sample was subjected to an energy of 175 μC / cm. 2 (Left image) and energy of 250 μC / cm 2 (Right image) Electron beam lithography scanning electron microscope image.

[0078] Figure 6 The electron beam photoresist samples of Examples 1-5 were subjected to an energy of 175 μC / cm. 2 (Left image) and energy of 250 μC / cm 2 The LER statistics of the electron beam lithography pattern shown in the right figure. Detailed Implementation

[0079] 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.

[0080] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0081] Synthesis Example 1

[0082]

[0083] Synthesis steps of self-crosslinking resin TJ-1: 9g of dimethyl 2,6-naphthalenedicarboxylate (M1), 13.0g of tris(2-hydroxyethyl)isocyanurate (M2), 8.6g of tris(2-carboxyethyl)isocyanurate (M3), 0.24g of p-toluenesulfonic acid monohydrate, 5.16g of n-butanol, and 14.6g of anisole were added to a reaction flask in no specific order. The reaction flask was heated to 140-160℃ and stirred vigorously for 6 hours. After complete reaction, the anisole and n-butanol in the reaction flask were removed by distillation. Subsequently, the obtained reactants were diluted with 67.8g of methyl 2-hydroxyisobutyrate and neutralized with triethylamine. 4.09 g of methyl-2-hydroxyisobutyrate and 10.9 g of 1,3,4,6-tetra(methoxymethyl)glycourea (C1) were added to the obtained 19.2 g polymer solution. The mixture was stirred at 50 °C for 3 hours, cooled to room temperature, and neutralized with triethylamine. The resulting reactants were then precipitated. The precipitate was washed, filtered, and dried to obtain 16 g of polymer TJ-1 resin solid powder (M). W =3514、M W / Mn=1.888).

[0084] Synthesis Example 2

[0085]

[0086] Synthesis steps of self-crosslinking resin TJ-2: 9g of dimethyl 2,6-naphthalenedicarboxylate, 13.0g of tris(2-hydroxyethyl) isocyanurate, 8.6g of tris(2-carboxyethyl) isocyanurate, 0.24g of p-toluenesulfonic acid monohydrate, 5.16g of n-butanol, and 14.6g of anisole were added to a reaction flask in no specific order. The reaction flask was heated to 140-160℃ and stirred vigorously for 6 hours. After complete reaction, the anisole and n-butanol in the reaction flask were removed by distillation. Subsequently, the obtained reactants were diluted with 66.8g of methyl 2-hydroxyisobutyrate and neutralized with triethylamine. 4.19g of methyl-2-hydroxyisobutyrate and 9.92g of crosslinking agent C2 were added to the resulting 20.2g polymer solution, and the mixture was stirred at 50℃ for 3 hours. After cooling to room temperature, it was neutralized with triethylamine. The resulting reactants were then precipitated, and the precipitate was washed, filtered, and dried to obtain 16g of polymer TJ-2 resin solid powder (M). W =4375、M W / Mn=2.010).

[0087] Synthesis Example 3

[0088]

[0089] Synthesis steps of self-crosslinking resin TJ-3: 9g of dimethyl 2,6-naphthalenedicarboxylate, 13.0g of tris(2-hydroxyethyl) isocyanurate, 8.6g of tris(2-carboxyethyl) isocyanurate, 0.24g of p-toluenesulfonic acid monohydrate, 5.16g of n-butanol, and 14.6g of anisole were added to a reaction flask in no specific order. The reaction flask was heated to 140-160℃ and stirred vigorously for 6 hours. After complete reaction, the anisole and n-butanol in the reaction flask were removed by distillation. Subsequently, the obtained reactants were diluted with 68.2g of methyl 2-hydroxyisobutyrate and neutralized with triethylamine. 4.31g of methyl-2-hydroxyisobutyrate and 12.89g of crosslinking agent C3 were added to the resulting 18.3g polymer solution, and the mixture was stirred at 50℃ for 3 hours. After cooling to room temperature, it was neutralized with triethylamine. The resulting reactants were then precipitated, and the precipitate was washed, filtered, and dried to obtain 14g of polymer TJ-3 resin solid powder (M). W =3345、M W / Mn=1.740).

[0090] Synthesis Example 4 Preparation method of electron beam matrix polymer resin: 891.60 g (4.0 mol) of α-methylstyrene monomer and 606.00 g (5.2 mol) of 2-chloroacrylate monomer were dissolved in 400 g of anisole. After the temperature inside the reactor stabilized at 35 ± 1 °C, the monomer solution was added to the reactor. After the monomer solution was added, the external temperature was set to 40 °C. After the temperature of the solution inside the reactor rose to 40 ± 1 °C, the initiator solution (an anisole solution containing 1.29 g of azobisisobutyronitrile) was added to the reactor. The container was rinsed twice with 25 g of anisole, and the rinsing solution was added to the reactor. After the initiator solution was added, the external temperature was set to 60 °C. The temperature was then raised to 85 °C. Then, a dioxane solution containing 0.50 g of azobisisobutyronitrile was added, and the reaction was continued for 24 hours. After cooling to room temperature, the reaction solution was precipitated, washed, and dried to obtain 400 g of resin solid powder. GPC test data: weight average molecular weight 58687, molecular weight distribution 1.91.

[0091] Preparation of electron beam matrix resin photoresist solution TJ-4: Weigh 23g of the above-mentioned resin solid powder and 180g of anisole, add them to a 500mL brown glass bottle, and place them on a shaker for 1h to dissolve completely; after dissolution, circulate the mixed solution through a 40nm Nenz filter for 24h to finally obtain electron beam matrix resin photoresist solution TJ-4 with a solid content of 11.06%.

[0092] Stripping experiment in developer As shown in Table 1, the samples prepared in Examples 1-5 were spin-coated on a 2-inch silicon wafer at 3000 rpm for 60 seconds and then baked on a hot plate at 180°C for 1 minute to form a thin film. The film thickness was measured using a film thickness gauge and recorded as T1. The films formed by the samples of each example were immersed in amyl acetate and kept for 30 seconds. They were then spin-dried on a spin coater for 1 minute and then baked on a hot plate at 100°C for 30 seconds. Finally, the film thickness was measured using a film thickness gauge and recorded as T2. The peeling rate S was calculated as (T1-T2) / T1*100%. As can be seen from the data in Table 1, the peeling rate of the films formed in the examples is all <2%, which shows good anti-peeling effect, indicating that these materials meet the compatibility requirements of electron beam photoresist.

[0093] Table 1. Peel strength test results in amyl acetate

[0094] Example 1 An electron beam photoresist, without self-crosslinking resin, is prepared as follows: 2g of photoresist solution TJ-4 obtained in Synthesis Example 4 is mixed with 0.022g of surfactant R-40 (1% solid content) and 6g of anisole to obtain a solution. After shaking for 12 hours, the solution is filtered through a 0.22-micron polyethylene microporous filter to obtain a clear filtrate, which is the electron beam photoresist composition. The prepared electron beam photoresist composition is used as follows: the electron beam photoresist is spin-coated onto a 2-inch silicon wafer at a spin speed of 3000 rpm, and the coating thickness is 50 nm; pre-baking is performed at 180°C for 180 seconds; exposure is performed in an electron beam lithography machine with an electron beam lithography voltage of 100 kV, a current of 100 pA, and an exposure energy of 75-425 μC / cm. 2 Then, bake at 90℃ for 2 minutes; develop in amyl acetate for 60 seconds, fix with isopropanol for 10 seconds, and observe the morphology of the pattern under a scanning electron microscope. Figure 1 At an exposure energy of 250 μC / cm 2 The graph at that time is shown Figure 1 As can be seen from the image, there is a clear collapse at the edge of the line.

[0095] Example 2 An electron beam photoresist, doped with 10% self-crosslinking resin (crosslinking agent C1), is prepared as follows: 2g of photoresist solution TJ-4 obtained in Synthesis Example 4 is mixed with 0.0221g of polymer TJ-1 obtained in Synthesis Example 1, 0.022g of surfactant R-40 with a solid content of 1wt%, and 6g of anisole to obtain a solution. After shaking for 12 hours, the solution is filtered through a 0.22-micron polyethylene microporous filter to obtain a clear filtrate, which is the electron beam photoresist composition. The prepared electron beam photoresist composition is used as follows: The electron beam photoresist is spin-coated onto a 2-inch silicon wafer at a spin speed of 3000 rpm, and the coating thickness is 50 nm; pre-baking is performed at 180°C for 180 seconds; exposure is performed in an electron beam lithography machine with an electron beam lithography voltage of 100 kV, a current of 100 pA, and an exposure energy of 75-425 μC / cm. 2 Then, it was post-baked at 90℃ for 2 minutes; development was performed in a developer solution (amyl acetate) for 60 seconds, followed by fixing with isopropanol for 10 seconds. The morphology of the pattern was observed using a scanning electron microscope. The exposure energy was 250 μC / cm². 2 The graph at that time is shown Figure 2 As can be seen from the picture, the lines are basically intact.

[0096] Example 3 An electron beam photoresist, doped with 20% self-crosslinking resin (crosslinking agent C1), is prepared as follows: 2g of photoresist solution TJ-4 obtained in Synthesis Example 4 is mixed with 0.0442g of polymer TJ-1 obtained in Synthesis Example 1, 0.022g of surfactant R-40 with a solid content of 1wt%, and 6g of anisole to obtain a solution. After shaking for 12 hours, the solution is filtered through a 0.22-micron polyethylene microporous filter to obtain a clear filtrate, which is the electron beam photoresist composition. The prepared electron beam photoresist is used as follows: the electron beam photoresist is spin-coated onto a 2-inch silicon wafer at a spin speed of 3000 rpm, and the coating thickness is 50 nm; pre-baking is performed at 180°C for 180 seconds; exposure is performed in an electron beam lithography machine with an electron beam lithography voltage of 100 kV, a current of 100 pA, and an exposure energy of 75-425 μC / cm. 2 Then, it was post-baked at 90℃ for 2 minutes; development was performed in a developer solution (amyl acetate) for 60 seconds, followed by fixing with isopropanol for 10 seconds. The morphology of the pattern was observed using a scanning electron microscope. The exposure energy was 250 μC / cm². 2 The graph at that time is shown Figure 3 As can be seen from the picture, the lines have not collapsed at all.

[0097] Example 4 An electron beam photoresist, doped with 20% self-crosslinking resin TJ-2 (crosslinking agent C2), is prepared as follows: 2g of photoresist solution TJ-4 obtained in Synthesis Example 4 is mixed with 0.0442g of polymer TJ-2 obtained in Synthesis Example 2, 0.022g of surfactant R-40 with a solid content of 1wt%, and 6g of anisole to obtain a solution. After shaking for 12 hours, the solution is filtered through a 0.22-micron polyethylene microporous filter to obtain a clear filtrate, which is the electron beam photoresist composition. The prepared electron beam photoresist is used as follows: the electron beam photoresist is spin-coated onto a 2-inch silicon wafer at a spin speed of 3000 rpm, and the coating thickness is 50 nm; pre-baking is performed at 180°C for 180 seconds; exposure is performed in an electron beam lithography machine with an electron beam lithography voltage of 100 kV, a current of 100 pA, and an exposure energy of 75-425 μC / cm. 2 Then, it was post-baked at 90℃ for 2 minutes; development was performed in a developer solution (amyl acetate) for 60 seconds, followed by fixing with isopropanol for 10 seconds. The morphology of the pattern was observed using a scanning electron microscope. The exposure energy was 250 μC / cm². 2 The graph at that time is shown Figure 4 As can be seen from the picture, the lines have not collapsed at all.

[0098] Example 5 An electron beam photoresist, doped with 20% self-crosslinking resin TJ-3 (crosslinking agent C3), is prepared as follows: 2g of photoresist solution TJ-4 obtained in Synthesis Example 4 is mixed with 0.0442g of polymer TJ-3 obtained in Synthesis Example 3, 0.022g of surfactant R-40 with a solid content of 1%wt, and 6g of anisole to obtain a solution. After shaking for 12 hours, the solution is filtered through a 0.22-micron polyethylene microporous filter to obtain a clear filtrate, which is the electron beam photoresist composition. The prepared electron beam photoresist is used as follows: the electron beam photoresist is spin-coated onto a 2-inch silicon wafer at a spin speed of 3000 rpm, and the coating thickness is 50nm; pre-baking is performed at 180°C for 180s; exposure is performed in an electron beam lithography machine with an electron beam lithography voltage of 100KV, a current of 100pA, and an exposure energy of 75-425μC / cm. 2 Then, it was post-baked at 90℃ for 2 minutes; development was performed in a developer solution (amyl acetate) for 60 seconds, followed by fixing with isopropanol for 10 seconds. The morphology of the pattern was observed using a scanning electron microscope. The exposure energy was 250 μC / cm². 2 The graph at that time is shown Figure 5 As can be seen from the picture, the lines have not collapsed at all.

[0099] Comparing the electron micrographs and line edge roughness (LER) test results of Examples 2, 3, 4, and 5 with Example 1, it can be seen that when designing dense line / groove patterns with a period of 100 nm at a thickness of 50 nm, the introduction of self-crosslinking resin into the electron beam photoresist of Examples 2-5 not only increases the adhesion of the polymer resin to the substrate, but also maintains the original photolithography process of the main polymer, improves the problem of line collapse when using ZEP520 electron beam photoresist, and the line pattern can also be significantly improved by doping with self-crosslinking resin at lower exposure energies.

[0100] The LER of the photolithographic patterns obtained in Examples 1-5 is as follows Figure 6 As shown. By Figure 6 It can be seen that the photolithographic patterns of Examples 2-5 significantly improved the line edge roughness compared to Example 1.

[0101] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An electron beam photoresist composition, characterized in that, include: Electron beam photoresist substrate resin materials and self-crosslinking resins; The self-crosslinking resin is obtained by reacting a chain polymer with a crosslinking agent; the chain polymer includes aromatic groups and nitrogen-containing heterocyclic groups.

2. The electron beam photoresist composition according to claim 1, characterized in that, Both the aromatic groups and nitrogen-containing heterocyclic groups are located on the main chain of the chain polymer. Preferably, the chain polymer is a polyester-based polymer. Preferably, the chain polymer is formed by polymerizing at least one compound containing an aromatic group with at least one compound containing a nitrogen-containing heterocycle. For example, the chain polymer is formed by polymerizing one compound containing an aromatic group with two compounds containing nitrogen-containing heterocycles. Preferably, in the chain polymer, the polymeric units are linked by ester bonds to form the polymer. Preferably, the aromatic group is a monocyclic or polycyclic aryl or heteroaryl group, for example, C1. 6-20 Aryl, 5-20 quinone heteroaryl; preferably C 6-14 Aryl, 5-14 heteroaryl, such as phenyl, naphthyl, anthracene or biphenyl. Preferably, the compound containing aromatic groups further includes carboxyl groups and carboxylic acid ester groups (such as COOC). 1-12 Alkyl), carboxylic anhydride, or hydroxyl groups. Preferably, the compound containing an aromatic group further includes at least two groups selected from carboxylic acids, carboxylic esters, carboxylic anhydrides, and / or at least two hydroxyl groups. Preferably, the compound containing a nitrogen-containing heterocycle further includes a carboxyl group, a carboxylic acid ester group, a carboxylic acid anhydride group, or a hydroxyl group. Preferably, the compound containing a nitrogen-containing heterocycle further includes at least two groups selected from carboxylic acids, carboxylic esters, carboxylic anhydrides, and / or at least two hydroxyl groups.

3. The electron beam photoresist composition according to claim 1 or 2, characterized in that, The compound containing aromatic groups has the structure shown in M1' below: ROOC-A-COOR M1’ Wherein, A is selected from the following groups that are unsubstituted or optionally substituted by one, two or more Rs: C 6-20 Aryl, 5-20 heteroaryl, C 6-20 Aryl-C 6-20 aryl or 5-20 heteroaryl; Rs is selected from oxo, halogen, cyano, nitro, C 1-12 Alkyl, C 1-12 Alkoxy, C 3-12 Cycloalkyl or 3-12 membered heterocyclic groups; R is selected from C 1-12 alkyl. Preferably, in M1', A is selected from C. 6-14 Aryl, 5-14 heteroaryl, C 6-14 Aryl-C 6-14 Aryl or 5-14 heteroaryl-5-14 heteroaryl; R is selected from H and C. 1-6 alkyl. Preferably, the compound containing an aromatic group is, for example, one of the following compounds: 。 Preferably, the compound containing a nitrogen-containing heterocycle is a compound of general formula I: I Where R1 and R2 are the same or different, they are selected from -C 1-12 Alkyl-OR4, -C 1-12 Alkyl-COOR5, -C 1-12 Alkyl-OCOR5; R3 is selected from -C 1-12 Alkyl-OR4, -C 1-12 Alkyl-COOR5, -C 1-12 Alkyl-OCOR5, R6; R4, R5, and R6 may be the same or different, selected from H, or arbitrarily selected by one or more R... a The following groups are substituted: C 1-12 Alkyl, C 2-12 alkenyl, C 2-12 alkynyl, aryl, heteroaryl; R a Same or different, selected from oxo, halogen, cyano, nitro, alkyl, cycloalkyl, heterocyclic, aryl, heteroaryl, -NR b R c -OR d -CO-R d -COOR d -SR e -SO-R e -SO2-R e ; R b R c They may be the same or different, independently selected from hydrogen or arbitrarily selected by one, two or more R... a The following groups are substituted: C 1-12 Alkyl, C 3-12 cycloalkyl; R d R e Whether the same or different, independently selected from H, or arbitrarily selected by one, two or more Rs a The following groups are substituted: C 1-12 Alkyl, C 3-12 Cycloalkyl, 3-12 membered heterocyclic groups. Preferably, the compound containing a nitrogen-containing heterocycle includes the compounds shown in M2' and M3' below: M2’ M3’ Among them, R 21 R 22 R 23 Same or different, selected independently from -C 1-12 Alkyl-OH; R 31 R 32 Same or different, selected independently from -C 1-12 Alkyl-COOH or -C 1-12 Alkyl-COOC 1-12 Alkyl; R 33 Selected from H, C 1-12 Alkyl, aryl, heteroaryl, -C 1-12 Alkyl -OH, -C 1-12 Alkyl-OC 1-12 Alkyl, -C 1-12 Alkyl-COOH or -C 1-12 Alkyl-COOC 1-12 alkyl. Preferably, R 21 R 22 R 23 Same or different, selected independently from -C 1-6 Alkyl-OH; R 31 R 32 Same or different, selected independently from -C 1-6 Alkyl-COOH or -C 1-6 Alkyl-COOC 1-6 Alkyl; R 33 Selected from H, C 1-6 Alkyl, -C 1-6 Alkyl -OH, -C 1-6 Alkyl-OC 1-6 Alkyl, -C 1-6 Alkyl-COOH or -C 1-6 Alkyl-COOC 1-6 alkyl. Preferably, the compound containing a nitrogen-containing heterocycle is: tris(2-hydroxyethyl) isocyanurate or tris(2-carboxyethyl) isocyanurate. Preferably, the chain polymer is a polymer obtained by reacting M1', M2' and M3'.

4. The electron beam photoresist composition according to any one of claims 1-3, characterized in that, The crosslinking agent is a crosslinkable compound having at least two substituents capable of forming crosslinks. Preferably, the crosslinking agent is an amino crosslinking agent. For example, glycourel crosslinking agents, melamine crosslinking agents, urea crosslinking agents, benzoguanamine crosslinking agents, or phenolic compounds having substituents such as hydroxymethyl and methoxymethyl that can form crosslinks. Preferably, the crosslinking agent is methoxymethylated glycourea or methoxymethylated melamine, such as tetramethoxymethylglycourea, tetrabutoxymethylglycourea or hexamethoxymethylmelamine. Preferably, the crosslinking agent has the structure shown in formula IC: IC Where s is an integer from 1 to 12; R7 and R8 may be the same or different, and are independently selected from H and C. 1-12 Alkyl, C 6-14 Aryl or 5-14 heteroaryl groups; R9, R 10 R 11 R 12 Same or different, selected independently from C 1-12 alkyl. Preferably, s is an integer from 1 to 6; Preferably, R7 and R8 may be the same or different, and are independently selected from H and C. 1-6 Alkyl, phenyl; for example, H, methyl, ethyl, propyl, butyl or phenyl. Preferably, R9, R 10 R 11 R 12 Same or different, selected independently from C 1-6 Alkyl, such as methyl, ethyl, n-propyl or n-butyl. Preferably, the crosslinking agent is selected from the following structures: 。 5. The electron beam photoresist composition according to any one of claims 1-4, characterized in that, The weight-average molecular weight of the self-crosslinking resin is 1000–8000. Preferably, the molecular weight distribution coefficient of the self-crosslinking resin is <2.

5. Preferably, the self-crosslinking resin has the following structural units: 。 6. The electron beam photoresist composition according to any one of claims 1-5, characterized in that, The electron beam photoresist substrate resin material is a copolymer of aromatic vinyl monomers and α-haloacrylate monomers; Preferably, the aromatic vinyl monomer is selected from at least one of α-methylstyrene monomer and 4-fluoro-α-methylstyrene monomer. Preferably, the α-haloacrylate monomer is selected from at least one of α-chloroacrylate methyl ester monomer, α-chloroacrylate ethyl ester monomer, α-chloroacrylate benzyl ester monomer, α-chloroacrylate-1-adamantyl ester monomer, α-chloroacrylate-2,2,3,3,3-pentafluoropropyl ester monomer, α-chloroacrylate-2,2,3,3,4,4,4-heptafluorobutyl ester monomer, α-fluoroacrylate methyl ester monomer, α-fluoroacrylate ethyl ester monomer, α-fluoroacrylate benzyl ester monomer, α-fluoroacrylate-1-adamantyl ester monomer, α-fluoroacrylate-2,2,3,3,3-pentafluoropropyl ester monomer, and α-chloroacrylate-2,2,3,3,4,4,4-heptafluorobutyl ester monomer. Preferably, the base resin material is a resin material obtained by copolymerization of α-methylstyrene and methyl 2-chloroacrylate: α-Methylstyrene-2-chloroacrylate.

7. The electron beam photoresist composition according to any one of claims 1-6, characterized in that, The electron beam photoresist composition further includes a solvent; the solvent is selected from at least one of anisole, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, butyl acetate, neopentyl acetate, γ-butyrolactone, and ethyl lactate. Preferably, the electron beam photoresist composition further includes an additive selected from at least one of surfactants, photoacid generators, thermal acid generators, viscosity control agents, and stabilizers.

8. A method for preparing the electron beam photoresist composition according to any one of claims 1-7, characterized in that, The process includes the following steps: mixing the photoresist substrate resin material and the self-crosslinking resin to obtain the electron beam photoresist composition. Preferably, the method further includes a process for preparing a self-crosslinking resin, comprising: S1. A compound containing an aromatic group is polymerized with a compound containing a nitrogen-containing heterocycle to obtain a chain polymer; S2. React the chain polymer with a crosslinking agent.

9. A method of using the electron beam photoresist composition according to any one of claims 1-7, characterized in that, The process includes the following steps: coating the electron beam photoresist composition onto a substrate, and sequentially performing pre-baking, exposure, post-baking, development, and fixing to obtain a photolithographic pattern.

10. Use of the electron beam photoresist composition according to any one of claims 1-7 in electron beam lithography.

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