Sulfonate homopolymer-based photoresist, method for preparing the same, and use thereof

Abstract

The present application provides sulfonate photoresist polymers of formula I or II, and their preparation and use. The polymers can be used as single-component photoresists without the need for additional acid generators, avoiding the problem of uneven distribution of components in multi-component photoresists. The resulting photoresist patterns have excellent resolution, contrast, and low line edge roughness.

Description

Technical Field

[0001] This invention belongs to the field of photolithography materials technology, specifically relating to a type of sulfonate homopolymer, photoresist containing the homopolymer, photoresist coating, and its applications. Background Technology

[0002] Photoresist, also known as photoresist, is a type of etch-resistant thin film material whose solubility changes after being irradiated by energy sources such as light beams, electron beams, ion beams, or X-rays. It is an indispensable core material in the microelectronics industry for manufacturing large-scale and very large-scale integrated circuits. As the integration density of integrated circuits increases, the required resolution of photolithography technology also increases, and higher demands are placed on the quality of high-resolution photolithographic patterns, especially the increasingly stringent requirements for linewidth roughness (LWR) and line edge roughness (LER).

[0003] Currently, conventional high-resolution photoresists still employ chemically amplified photoresists, which are generally mixtures. Their main components are a resin matrix containing acid-sensitive groups, a photoacid generator (PAG), and corresponding additives. The photoacid generator decomposes upon illumination to produce acid, which triggers the decomposition of the acid-sensitive groups. This significantly alters the solubility of the photoresist material in both illuminated and unilluminated areas, allowing for patterning through development. However, as a mixture, chemically amplified photoresists may suffer from uneven component distribution, leading to high line edge roughness. Furthermore, the chemical amplification mechanism introduces acid diffusion issues, affecting pattern resolution and resulting in higher line edge roughness.

[0004] In contrast, non-chemically amplified photoresists contain photosensitive groups that directly undergo photochemical reactions during exposure, creating a difference in solubility between the exposed and unexposed areas. These non-chemically amplified photoresists do not require the addition of acid-generating agents and can form a "single-component" photoresist, overcoming problems such as uneven acid distribution and acid diffusion in chemically amplified photoresist systems. They have the potential to form high-resolution and low-line-roughness lithographic patterns. Summary of the Invention

[0005] The purpose of this invention is to provide a type of sulfonate photoresist polymer that does not require the addition of an additional acid-generating agent when used for photolithography, can be used as a single-component photoresist, and produces photolithographic patterns with excellent resolution, contrast, and low line edge roughness.

[0006] Another object of the present invention is to provide the above-mentioned sulfonate polymer as a photoresist in deep ultraviolet lithography, electron beam lithography and extreme ultraviolet lithography.

[0007] The technical solution provided by this invention is as follows:

[0008] Polymers as shown in Formula I or Formula II:

[0009]

[0010] Where x represents the number of repeating units in the polymer, which may be the same or different, and each has an independent range as shown below: 2≤x≤5000;

[0011] R a They are identical or different, selected independently of each other without substitution or arbitrarily selected by one, two or more Rs. a1 The following groups are substituted: C 1-15 Alkyl, C 3-15 cycloalkyl, C 6-20 Aryl, -C 1-6 Alkyl-C 6-20 Aryl, -C 6-20 Aryl-C 1-10 Alkyl, C 6-20 aryl 3-20 membered heterocyclic groups;

[0012] R a1 They may be the same or different, and are independently selected from halogens, amino groups, nitro groups, CN groups, and -N(C groups). 1-15 Alkyl group 2, halogenated C 1-15 Alkyl, C 1-15 Alkyl, C 1-15 Alkoxy, C 6-20 Aryl.

[0013] According to an embodiment of the present invention, the R a C 1-10 Alkyl, C 3-12 cycloalkyl, C 6-14 Aryl, -C 1-3 Alkyl-C 6-10 Aryl, -C 6-10 Aryl-C 1-3 Alkyl, C 6-10 Aryl 3-10 membered heterocyclic groups; the C 1-10 Alkyl, C 3-12 cycloalkyl, C 6-14 Aryl, -C 1-3 Alkyl-C 6-10 Aryl, -C 6-10 Aryl-C 1-3 Alkyl, C 6-10 The aryl 3-10 membered heterocyclic group may be further substituted by one, two or more of the following groups: halogen, amino, nitro, cyano, -N(C) 1-10 Alkyl)2, C 1-10 Alkyl, C 1-10 Alkoxy, halogenated C 1-10 Alkyl, C 6-10Aryl.

[0014] According to an embodiment of the present invention, the R a Same or different, selected independently from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 6-12 cycloalkyl (e.g.) ), phenyl, phenyl-5-membered heterocyclic group (e.g. ), halogenated naphthyl, halogenated phenyl, halogenated C 1-6 Alkyl-substituted phenyl, C 1-6 Alkoxy-substituted phenyl, amino-substituted phenyl, nitro-substituted phenyl, cyano-substituted phenyl, naphthyl, phenyl-substituted phenyl.

[0015] According to an embodiment of the present invention, the x may be the same or different, and independently have the following ranges: 5≤x≤2000, 5≤x≤1000, 10≤x≤900, such as 50≤x≤800, 100≤x≤600.

[0016] According to the present invention, the polymer represented by Formula I has the following structure:

[0017]

[0018]

[0019] According to the present invention, the polymer represented by Formula II has the following structure:

[0020]

[0021] Where x has the definition described above.

[0022] According to an embodiment of the present invention, the polymer has a molecular weight of 2,000-200,000 Daltons, for example 3,000-100,000 Daltons, such as 4,000-50,000 Daltons.

[0023] According to an embodiment of the present invention, the polydispersity index (PDI) of the polymer resin is less than or about equal to 1.5, for example, 1.00-1.40, such as 1.00-1.20.

[0024] The present invention also provides a method for preparing the polymer as described above, comprising the following steps:

[0025] The monomers shown in Formula III or Formula IV undergo polymerization reactions;

[0026]

[0027] Among them, R a It has the definition described above.

[0028] According to an embodiment of the present invention, the method includes:

[0029] The monomers shown in Formula III or Formula IV are subjected to a reversible addition-fracture transfer (RAFT) reaction in the presence of the chain transfer agent (CTA) shown in Formula V:

[0030]

[0031] Among them, R a It has the definition as described above;

[0032] In the chain transfer agent shown in Formula V, Z is selected from the following groups: C 6-12 Aryl, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, 5-12 heteroaryl, -OC 6-12 Aryl, -N(C 1-6 Alkyl)C 6-20 Aryl or -N(C) 1-6 Alkyl)2;

[0033] R is selected from CN replacing C. 1-6 Alkyl, phenyl substituted C 1-6 Alkyl, phenyl and COOH-substituted C 1-6 Alkyl, -COOC 1-6 Alkyl-substituted C 1-6 Alkyl or C 1-6 alkyl.

[0034] In one embodiment, Z is selected from the following groups: Or other groups that can activate the C=S bond to undergo radical addition, among which This indicates the bond between the substituent and the carbon atom in the C=S bond;

[0035] In one implementation, R is selected from the following groups: Other groups that readily form reactive free radicals, among which This indicates the bond between the substituent and sulfur.

[0036] In one embodiment, the chain transfer agent shown in Formula V is isopropylphenyl dithiobenzoate.

[0037] In one embodiment, the monomer represented by Formula III can be prepared by the following method:

[0038] Reaction of Formula 4-vinylbenzenesulfonyl chloride with the alcohol shown in Formula VI in the presence of pyridine yields the monomer shown in Formula III:

[0039]

[0040] Among them, R a It has the characteristics defined above.

[0041] In one embodiment, the monomer shown in Formula IV can be prepared by the following method:

[0042] Reaction of formula 4-vinylphenol with sulfonyl chloride shown in formula VII in the presence of pyridine yields the monomer shown in formula IV:

[0043]

[0044] Among them, R a It has the characteristics defined above.

[0045] The present invention also provides a photoresist composition comprising at least one of the polymers shown in Formula I or Formula II as described above.

[0046] Furthermore, the polymer represented by Formula I or Formula II accounts for 1%-10% of the total mass of the photoresist composition, for example, 2%-8%.

[0047] According to an embodiment of the present invention, the photoresist composition further comprises a solvent, the solvent being selected, for example, from one or more of the following substances: propylene glycol methyl ether, ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, ethylene glycol monomethyl ether, cyclohexanone, methyl n-pentanone, methyl isopentanone, cyclopentanone, ethanol, acetonitrile, isopropanol, and acetone.

[0048] According to an embodiment of the present invention, the photoresist composition comprises at least one of the polymers shown in Formula I or Formula II as described above and a solvent.

[0049] According to an embodiment of the present invention, the photoresist composition is a non-chemically amplified photoresist.

[0050] According to an embodiment of the present invention, the photoresist composition is a negative photoresist.

[0051] The present invention also provides a photoresist coating comprising at least one of the polymers shown in Formula I or Formula II as described above.

[0052] The present invention also provides a method for preparing the photoresist coating, comprising: spin-coating the photoresist composition onto a substrate to form a film, thereby obtaining a photoresist coating.

[0053] In some embodiments of the present invention, the substrate is a silicon wafer or the like.

[0054] In some embodiments of the present invention, the photoresist coating is a thin film of 20nm-150nm.

[0055] The present invention also provides the application of the photoresist coating as described above in photolithography.

[0056] In some embodiments of the present invention, the photoresist coating is used in modern photolithography technologies such as 248nm photolithography, 254nm photolithography, 193nm photolithography, extreme ultraviolet photolithography, nanoimprint lithography or electron beam lithography; it is especially suitable for high-resolution photolithography technologies such as 254nm photolithography, electron beam lithography and extreme ultraviolet (EUV).

[0057] Beneficial effects

[0058] (1) This invention provides a series of sulfonate homopolymers as shown in Formula I or Formula II. The raw materials for the sulfonate homopolymers are readily available, the synthesis process is simple, and the final product can be separated from the system by precipitation, making them suitable for industrial production;

[0059] (2) The sulfonate homopolymer of the present invention can be used as the main material of photoresist. The sulfonate groups in the polymer can decompose under light, causing a change in solubility, thereby achieving photolithography. In the photoresist composition formed by the polymer of the present invention, no additional acid-generating agent is required, and there are no problems such as uneven acid distribution and acid diffusion, which helps to achieve high resolution and low edge roughness. Furthermore, the photoresist composition of the present invention can contain only the polymer and solvent of the present invention, without any other additives, and there is no problem of uneven component distribution;

[0060] (3) The sulfonate polymer described in this invention can be polymerized using the RAFT method. The polymer has a small molecular weight distribution index, the polymerization is controllable, and the polymerization results are reproducible.

[0061] (4) The photoresist containing the sulfonate homopolymer described above has a wide range of applications and can be used in various photolithography technologies such as deep ultraviolet lithography, electron beam lithography, and extreme ultraviolet lithography. The resulting photolithographic pattern has excellent resolution, contrast, and low line edge roughness.

[0062] Terminology Definitions and Explanations

[0063] 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.

[0064] Some functional groups in this application The location indicates the connection point.

[0065] All polymer molecular weights mentioned in this article refer to weight-average molecular weights.

[0066] The term "homogeneous polymer" refers to a polymer composed of monomer molecules linked together by covalent bonds.

[0067] The term "polydispersity index (PDI) of polymer resins" refers to the ratio of the polymer's weight-average molecular weight to its number-average molecular weight.

[0068] "More than three" means three or more.

[0069] The term "halogen" includes F, Cl, Br, or I.

[0070] Term "C" 1-15 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 15 carbon atoms, preferably "C". 1-6 Alkyl group. "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.

[0071] Term "C" 1-15 "Alkoxy" should be understood as -OC 1-15 Alkyl, wherein C 1-15 Alkyl groups have the above definition.

[0072] Term "C" 6-20 "Aryl" should be understood to represent an aromatic monocyclic, bicyclic, or polycyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C". 6-14 Aryl. The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20When 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] Term "C" 3-15 "Cycloalkyl" should be understood to refer to a saturated monocyclic or bicyclic hydrocarbon ring having 3 to 15 carbon atoms, preferably "C". 3-12 cycloalkyl. The 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.

[0074] The term "3-20 membered heterocyclic group" refers to a saturated or partially unsaturated monocyclic or bicyclic hydrocarbon ring comprising 3 to 20 ring atoms, wherein one or more ring atoms are heteroatoms or groups selected from N, O, NH, S, S(O) or S(O)2, but excluding ring portions of -OO-, -OS- or -SS-, and the remaining ring atoms are carbon. Preferably, it comprises 3 to 12 ring atoms, wherein 1 to 4 are heteroatoms (e.g., 1, 2, 3, and 4). More preferably, it comprises 3 to 6 ring atoms (e.g., 3, 4, 5, and 6). 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), or an oxygen or sulfur atom (especially in the case of forming ononium salts). The heterocyclic group can include fused or bridged rings and / or spirocyclic rings. Non-limiting examples of monocyclic heterocyclic groups include azirrobutyl, oxacyclobutyl, pyrrolyl, imidazoalkyl, tetrahydrofuranyl, tetrahydrothiophenyl, dihydroimidazoyl, dihydrofuranyl, dihydropyrazolyl, dihydropyrrolyl, dioxacyclopentenyl, tetrahydropyranyl, pyrrolinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dithiaalkyl, trithiaalkyl, homopiperazinyl, diazacycloheptyl, etc., preferably piperidinyl or pyrrolyl. Polycyclic heterocyclic groups include spirocyclic, fused-ring, and bridged-ring heterocyclic groups, and may also be benzofused heterocyclic groups such as dihydroisoquinolinyl. The heterocyclic group may be bicyclic, and non-limiting examples include hexahydrocyclopenta[c]pyrrolo-2(1H)-yl and hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl. Heterocyclic groups can also be partially unsaturated, meaning they can contain one or more double bonds. Non-limiting examples include dihydrofuranyl, dihydropyranyl, 2,5-dihydro-1H-pyrroleyl, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl.

[0075] Term "C" 6-20 In the aryl 3-20 membered heterocyclic group, C6-20 Aryl groups and 3-20 membered heterocyclic groups have the definitions described above. Preferably, "C" 6-10 Aryl 3-10 membered heterocyclic group. Attached Figure Description

[0076] Figure 1 The GPC test curves for polymers I-4 and II-4 in Example 9 of this invention are shown.

[0077] Figure 2 This is an AFM image of the polymer I-4 film in Example 10 of the present invention.

[0078] Figure 3 This is an AFM image of the polymer I-9 film in Example 10 of the present invention.

[0079] Figure 4 This is an AFM image of the polymer I-10 film in Example 10 of the present invention.

[0080] Figure 5 The thermogravimetric curves of polymers I-4 and II-4 in Example 11 of this invention are shown.

[0081] Figure 6 The differential scanning calorimetry (DSC) curves of polymers I-4 and II-4 in Example 11 of this invention are shown.

[0082] Figure 7 This is the ultraviolet exposure pattern of the photoresist of polymer I-4 in Example 12 of the present invention.

[0083] Figure 8 This is the electron beam exposure pattern of the photoresist of polymer I-4 in Example 12 of the present invention.

[0084] Figure 9 This is the ultraviolet exposure pattern of the photoresist of polymer I-8 in Example 12 of the present invention.

[0085] Figure 10 This is the electron beam exposure pattern of the photoresist of polymer I-9 in Example 12 of the present invention.

[0086] Figure 11 This is the electron beam exposure pattern of the photoresist of polymer I-10 in Example 12 of the present invention.

[0087] Figure 12 This is the ultraviolet exposure pattern of the photoresist of polymer I-11 in Example 12 of the present invention.

[0088] Figure 13 This is the ultraviolet exposure pattern of the photoresist of polymer I-12 in Example 12 of the present invention.

[0089] Figure 14This is the ultraviolet exposure pattern of the photoresist of polymer II-4 in Example 12 of the present invention. Detailed Implementation

[0090] 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.

[0091] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0092] Example 1

[0093] The synthetic route for preparing compound III-4 is as follows:

[0094]

[0095] Specific steps: In a 100ml round-bottom flask, add methanol (8ml, 4eq) and pyridine (20ml, 5eq), mix thoroughly, and cool to -20℃. Add 10g of 4-vinylsulfonyl chloride (1eq) dropwise to the mixture and react at -20℃ for 1 hour. Wash the reaction solution with 1N hydrochloric acid, extract with dichloromethane, and then perform column chromatography with dichloromethane to obtain a white solid product with a yield of 61%. 1 ¹H NMR (600 MHz, deuterated chloroform) δ 7.78 (s, 2H), 7.49 (s, 2H), 6.68 (s, 1H), 5.85 (s, 1H), 5.40 (s, 1H), 3.68 (s, 3H). MS (ESI): m / z = 198.03, calculated C9H 10 O3S + m / z = 198.03 ([M]) + ).

[0096] The synthetic route for preparing polymer I-4 is as follows:

[0097]

[0098] Specific steps: Compound III-1 (3g, 50 eq), isopropylphenyl dithiobenzoate (CDB, 82.5mg, 1 eq), and azobisisobutyronitrile (AIBN, 24.9mg, 0.5 eq) were added to a 25ml Shrek flask. 3.1ml of ultra-dry tetrahydrofuran was added, and the mixture was deoxygenated three times under freeze-drying conditions. The mixture was then refluxed in an oil bath at 70°C. After 24 hours, the reaction was stopped, quenched with liquid nitrogen, diluted with 15ml of tetrahydrofuran, and then added dropwise to 200ml of petroleum ether to precipitate. The precipitate was dried, weighed, and yielded 2.82g of a pink solid, with a yield of 93%.1 HNMR (600MHz, DMSO-d6) δ7.78 -7.49 (s, 4H), 3.68 (s, 3H), 1.80-1.20 (s, 3H). GPC: Mn=9210, Mw=9670, PDI=1.05.

[0099] Example 2

[0100] The synthetic route for preparing compound III-4 is as follows:

[0101]

[0102] The specific steps are the same as the first step of the preparation process in Example 1, except that methanol is replaced with phenol, and the reaction conditions are changed from -20℃ to room temperature. The reaction yield is 56%. 1 ¹H NMR (600MHz, deuterated chloroform) δ 7.87 (d, J = 6.6 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H), 7.39 (s, 2H), 7.35 (s, 1H), 7.10 (s, 2H), 6.85 (dd, J = 17.6, 10.9 Hz, 1H), 6.02 (d, J = 17.6 Hz, 1H), 5.59 (s, 1H). MS (ESI): m / z = 260.05, calculated C 14 H 12 O3S + m / z = 260.05 ([M]) + ).

[0103] The synthetic route for preparing polymer I-4 is as follows:

[0104]

[0105] The specific steps are the same as the second step of the preparation process in Example 1, except that compound III-1 is replaced with compound III-4, and the reaction yield is 93%. 1 H NMR (600MHz, DMSO-d6) δ7.90 -7.08 (s, 9H), 1.80-1.20 (s, 3H). GPC: Mn=6220, Mw=6470, PDI=1.04.

[0106] Example 3

[0107] The synthetic route for preparing compound III-8 is as follows:

[0108]

[0109] The specific steps are the same as the first step of the preparation process in Example 1, except that methanol is replaced with 4-trifluoromethylphenol, and the reaction conditions are changed from -20°C to room temperature. The reaction yield is 60%.1 ¹H NMR (600MHz, deuterated chloroform) δ 7.79 (d, J = 8.5Hz, 2H), 7.56 (dd, J = 19.0, 8.5Hz, 4H), 7.13 (d, J = 8.5Hz, 2H), 6.74 (s, 1H), 5.93 (d, J = 17.6Hz, 1H), 5.50 (d, J = 10.9Hz, 1H). MS (ESI): m / z = 328.31, calculated C 15 H 11 F3O3S + m / z = 328.31 ([M]) + ).

[0110] The synthetic route for preparing polymer I-4 is as follows:

[0111]

[0112] The specific steps are the same as the second step of the preparation process in Example 1, except that compound III-1 is replaced with compound III-8, and the reaction yield is 93%. 1 H NMR (600MHz, DMSO-d6) δ7.91 -7.08 (s, 8H), 1.80-1.20 (s, 3H). GPC: Mn=4420, Mw=5220, PDI=1.18.

[0113] Example 4

[0114] The synthetic route for preparing compound III-9 is as follows:

[0115]

[0116] The specific steps are the same as the first step of the preparation process in Example 1, except that methanol is replaced with 4-methoxyphenol, and the reaction conditions are changed from -20℃ to room temperature. The reaction yield is 56%. 1 ¹H NMR (600MHz, deuterated chloroform) δ 7.75 (s, 2H), 7.52 (s, 2H), 6.88 (s, 2H), 6.77 (s, 3H), 5.91 (d, J = 17.6 Hz, 1H), 5.47 (d, J = 12.0 Hz, 1H), 3.77 (s, 3H). MS (ESI): m / z = 290.06, calculated C 15 H 14 O4S + m / z = 290.06 ([M]) + ).

[0117] The synthetic route for preparing polymer I-9 is as follows:

[0118]

[0119] The specific steps are the same as the second step of the preparation process in Example 1, except that compound III-1 is replaced with compound III-9, and the reaction yield is 90%. 1 H NMR (600MHz, DMSO-d6) δ7.80 -6.49 (s, 8H), 3.64 (s, 1H), 1.80-1.20 (s, 3H). GPC: Mn=6710, Mw=7000, PDI=1.04.

[0120] Example 5

[0121] The synthetic route for preparing compound III-10 is as follows:

[0122]

[0123] The specific steps are the same as the first step of the preparation process in Example 1, except that methanol is replaced with 4-aminophenol, and the reaction conditions are changed from -20℃ to room temperature. The reaction yield is 52%. 1 ¹H NMR (600MHz, DMSO-d⁶) δ 9.40 (s, 2H), 7.60 (s, 4H), 6.84 (s, 2H), 6.75 (dd, J = 17.6, 10.9Hz, 1H), 6.60 (s, 2H), 5.96 (d, J = 17.6Hz, 1H), 5.42 (s, 1H). MS (ESI): m / z = 275.06, calculated C 14 H 13 NO3S + m / z = 275.06 ([M]) + ).

[0124] The synthetic route for preparing polymer I-10 is as follows:

[0125]

[0126] The specific steps are the same as the second step of the preparation process in Example 1, except that compound III-1 is replaced with compound III-10, and the reaction yield is 71%. 1 H NMR (600MHz, DMSO-d6) δ9.60 -9.21 (s, 2H), 7.68-6.49 (s, 8H), 1.80-1.20 (s, 3H). GPC: Mn=4430, Mw=5210, PDI=1.20.

[0127] Example 6

[0128] The synthetic route for preparing compound III-11 is as follows:

[0129]

[0130] The specific steps are the same as the first step of the preparation process in Example 1, except that methanol is replaced with 4-nitrophenol, and the reaction conditions are changed from -20℃ to room temperature. The reaction yield is 66%. 1 ¹H NMR (600MHz, deuterated chloroform) δ 8.20 (d, J = 9.1Hz, 2H), 7.80 (d, J = 8.5Hz, 2H), 7.56 (d, J = 8.5Hz, 2H), 7.19 (d, J = 6.9Hz, 2H), 6.76 (dd, J = 17.6, 10.9Hz, 1H), 5.94 (d, J = 17.6Hz, 1H), 5.52 (d, J = 10.9Hz, 1H). MS (ESI): m / z = 305.30, calculated C 14 H 11 NO5S + m / z = 305.31 ([M]) + ).

[0131] The synthetic route for preparing polymer I-11 is as follows:

[0132]

[0133] The specific steps are the same as the second step of the preparation process in Example 1, except that compound III-1 is replaced with compound III-11, and the reaction yield is 93%. 1 H NMR (600MHz, DMSO-d6) δ8.41 -6.88 (s, 8H), 1.80-1.20 (s, 3H). GPC: Mn=4500, Mw=4680, PDI=1.04.

[0134] Example 7

[0135] The synthetic route for preparing compound III-12 is as follows:

[0136]

[0137] The specific steps are the same as the first step of the preparation process in Example 1, except that methanol is replaced with 4-cyanophenol, and the reaction conditions are changed from -20°C to room temperature. The reaction yield is 79%. 1 ¹H NMR (600MHz, deuterated chloroform) δ 7.81–7.74 (m, 2H), 7.65–7.59 (m, 2H), 7.58–7.51 (m, 2H), 7.19–7.07 (m, 2H), 6.76 (dd, J = 17.6, 10.9 Hz, 1H), 5.94 (d, J = 17.6 Hz, 1H), 5.51 (d, J = 10.9 Hz, 1H). MS (ESI): m / z = 285.32, calculated C 15 H 11NO3S + m / z = 285.32 ([M]) + ).

[0138] The synthetic route for preparing polymer I-12 is as follows:

[0139]

[0140] The specific steps are the same as the second step of the preparation process in Example 1, except that compound III-1 is replaced with compound III-12, and the reaction yield is 93%. 1 H NMR (600MHz, DMSO-d6) δ7.91 -6.60 (s, 8H), 1.80-1.20 (s, 3H). GPC: Mn=5300, Mw=6000, PDI=1.13.

[0141] Example 8

[0142] The synthetic route for preparing compound V-4 is as follows:

[0143]

[0144] Specific steps: Add p-hydroxystyrene (15g, 1.5eq) and pyridine (23ml, 5eq) to a 100ml round-bottom flask, mix thoroughly, and cool to 0℃. Add benzenesulfonyl chloride (6.8g, 1eq) dropwise to the mixture and react at room temperature for 22h. Wash the reaction solution with 2N hydrochloric acid, extract with dichloromethane, and then perform column chromatography with a 1:1 mixture of dichloromethane and petroleum ether to obtain a white solid product with a yield of 95%. 1 ¹H NMR (600MHz, DMSO-d⁶) δ 7.86 (s, 2H), 7.83 (s, 1H), 7.67 (s, 2H), 7.47 (s, 2H), 6.98 (s, 2H), 6.69 (s, 1H), 5.79 (s, 1H), 5.28 (s, 1H). MS (ESI): m / z = 260.05, calculated C 14 H 12 O3S + m / z = 260.05 ([M]) + ).

[0145] The synthetic route for preparing polymer II-4 is as follows:

[0146]

[0147] The specific steps are the same as the second step of the preparation process in Example 1, except that compound III-1 is replaced with compound V-4, and the reaction yield is 95%. 1H NMR (600MHz, DMSO-d6) δ7.96 -6.88 (s, 9H), 1.80-1.20 (s, 3H). GPC: Mn=5520, Mw=5980, PDI=1.08.

[0148] Example 9

[0149] The molecular weight and molecular weight distribution index of polymers I-4 and II-4 were determined by gel permeation chromatography (GPC) (see Appendix). Figure 1 Among them, the molecular weight of polymer I-4 was measured to be 6470, and the PDI was 1.05; the molecular weight of polymer II-4 was measured to be 5980, and the PDI was 1.08. It can be seen that the polymer molecular weight distribution of the present invention is narrow, therefore it will not affect the resolution and edge roughness of the photolithographic pattern, and can meet the requirements for finer lithography.

[0150] Example 10

[0151] Polymers I-4, I-9, and I-10 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare solutions with a concentration of 30 mg / ml. These solutions were then filtered through a 0.22 μm microporous filter to obtain spin-coating solutions. The spin-coating solutions were then used to spin-coat films on a silicon substrate. The uniformity and flatness of the films were analyzed using atomic force microscopy (AFM), and the results are shown in the appendix. Figure 2 Appendix Figure 3 and appendix Figure 4 As can be seen from the figure, the obtained film is very uniform and shows no crystallization, which is beneficial for obtaining a smooth photolithographic pattern.

[0152] Example 11

[0153] The thermal stability of polymers I-4 and II-4 was determined. Thermogravimetric (TGA) curves of polymers I-4 and II-4 are shown below. Figure 5 Differential scanning calorimetry (DSC) curves and thermogravimetric analyses of polymers I-4 and II-4 are shown in [reference needed]. Figure 6 The results showed that the glass transition temperatures (T0) of the two polymers were... g Above 80℃, the thermal decomposition temperature (T) d All of them are above 300℃ and have excellent thermal stability.

[0154] Example 12

[0155] A negative photoresist formulation and photolithography: Polymer I-4 was dissolved in PGMEA to prepare a solution with a mass concentration of 30 mg / ml. The solution was filtered through a 0.22 μm microporous filter to obtain a spin-coating solution. This solution was then spin-coated onto an untreated silicon substrate. After pre-baking at 100°C for 3 minutes, the film thickness was measured using an ellipsometry. The prepared film was subjected to UV exposure experiments using a 254 nm mercury lamp, yielding a very clear 1 μm stripe pattern. The test results are shown below. Figure 7 The prepared thin films were subjected to electron beam lithography experiments using the electron beam lithography system at the National Center for Nanoscience and Technology. Exposure pattern periods of 80 nm, 60 nm, 50 nm, 44 nm, and 40 nm were designed. The lithographic fringes with periods of 80 nm, 60 nm, 50 nm, and 44 nm achieved complete resolution. The test results are shown in [Figure number missing]. Figure 8 The results show that the obtained pattern has both good resolution and contrast, as well as very low line edge roughness.

[0156] Following the same method described above, a negative photoresist containing polymer I-8 was obtained and spin-coated. The prepared film was then subjected to UV exposure experiments using a 254nm mercury lamp, yielding a very clear 1μm stripe pattern. The test results are shown below. Figure 9 .

[0157] Following the same method described above, a negative photoresist containing polymer I-9 was obtained and spin-coated. Electron beam exposure was performed, with exposure pattern periods of 80nm, 60nm, 50nm, 44nm, and 40nm. The photolithographic stripes with periods of 80nm, 60nm, 50nm, and 44nm achieved complete resolution. Test results are shown below. Figure 10 The results show that the obtained pattern has both good resolution and contrast, as well as very low line edge roughness.

[0158] Following the same method described above, a negative photoresist containing polymer I-10 was obtained and spin-coated. Electron beam exposure was performed, with exposure pattern periods of 80nm, 60nm, 50nm, 44nm, and 40nm. The photolithographic stripes with periods of 80nm, 60nm, 50nm, and 44nm achieved complete resolution. Test results are shown below. Figure 11 The results show that the obtained pattern has both good resolution and contrast, as well as very low line edge roughness.

[0159] Following the same method described above, a negative photoresist containing polymer I-11 was obtained and spin-coated to form a film. The prepared film was then subjected to UV exposure experiments using a 254nm mercury lamp, yielding a very clear 1μm stripe pattern. The test results are shown below. Figure 12 .

[0160] Following the same method described above, a negative photoresist containing polymer I-12 was obtained and spin-coated to form a film. The prepared film was then subjected to UV exposure experiments using a 254nm mercury lamp, yielding a very clear 1μm stripe pattern. The test results are shown below. Figure 13 .

[0161] Following the same method described above, a negative photoresist containing polymer II-4 was obtained and spin-coated. The prepared film was then subjected to UV exposure experiments using a 254nm mercury lamp, yielding a very clear 1μm stripe pattern. The test results are shown below. Figure 14 .

[0162] 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. The polymer shown in Formula I or Formula II: in, x represents the number of repeating units in the polymer, which may be the same or different, and each has an independent range as follows: 2 ≤ x ≤ 5000; R a They are identical or different, selected independently of each other without substitution or arbitrarily selected by one, two or more Rs. a1 The following groups are substituted: C 1-15 Alkyl, C 3-15 cycloalkyl, C 6-20 Aryl, -C 1-6 Alkyl-C 6-20 Aryl, -C 6-20 Aryl-C 1-10 Alkyl, C 6-20 aryl 3-20 membered heterocyclic groups; R a1 They may be the same or different, and are independently selected from halogens, amino groups, nitro groups, CN groups, and -N(C groups). 1-15 Alkyl group 2, halogenated C 1-15 Alkyl, C 1-15 Alkyl, C 1-15 Alkoxy, C 6-20 Aryl.

2. The polymer according to claim 1, wherein, The R a C 1-10 Alkyl, C 3-12 cycloalkyl, C 6-14 Aryl, -C 1-3 Alkyl-C 6-10 Aryl, -C 6-10 Aryl-C 1-3 Alkyl, C 6-10 Aryl 3-10 membered heterocyclic groups; the C 1-10 Alkyl, C 3-12 cycloalkyl, C 6-14 Aryl, -C 1-3 Alkyl-C 6-10 Aryl, -C 6-10 Aryl-C 1-3 Alkyl, C 6-10 The aryl 3-10 membered heterocyclic group may be further substituted with one, two or more of the following groups: halogen, amino, nitro, cyano, -N(C) 1-10 Alkyl)2, C 1-10 Alkyl, C 1-10 Alkoxy, halogenated C 1-10 Alkyl, C 6-10 Aryl.

3. The polymer according to claim 1 or 2, wherein, The R a Same or different, selected independently from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 6-12 Cycloalkyl, phenyl, phenyl-5-membered heterocyclic, halogenated naphthyl, halogenated phenyl, halogenated C 1-6 Alkyl-substituted phenyl, C 1-6 Alkoxy-substituted phenyl, amino-substituted phenyl, nitro-substituted phenyl, cyano-substituted phenyl, naphthyl, and phenyl-substituted phenyl.

4. The polymer according to any one of claims 1-3, wherein, The polymer shown in Formula I has the following structure: Preferably, the polymer represented by Formula II has the following structure: Wherein, x has the definition as described in any one of claims 1-3.

5. The polymer according to any one of claims 1-4, wherein, The molecular weight of the polymer is 2,000-200,000 Daltons; Preferably, the polydispersity index (PDI) of the polymer resin is less than or equal to 1.

5.

6. A method for preparing the polymer according to any one of claims 1-5, comprising the following steps: The monomers shown in Formula III or Formula IV undergo polymerization reactions; in, R a It has the definition as described in any one of claims 1-5.

7. A photoresist composition, wherein, The photoresist composition comprises at least one of the polymers represented by Formula I or Formula II as described in any one of claims 1-5 and a photoresist solvent.

8. The photoresist composition according to claim 7, wherein, The polymer represented by Formula I or Formula II accounts for 1%-10% of the total mass of the photoresist composition, with the remainder being photoresist solvent. Preferably, the photoresist solvent is selected from one or more of the following substances: propylene glycol methyl ether, ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, ethylene glycol monomethyl ether, cyclohexanone, methyl n-pentanone, methyl isopentanone, cyclopentanone, ethanol, acetonitrile, isopropanol, and acetone. Preferably, the photoresist composition is a non-chemically amplified photoresist; Preferably, the photoresist composition is a negative photoresist.

9. A photoresist coating comprising the photoresist composition of claim 7 or 8.

10. The photoresist composition of claim 7 or 8, or the application of the photoresist coating of claim 9 in photolithography; Preferably, the photoresist coating is used in modern photolithography technologies such as 248nm photolithography, 254nm photolithography, 193nm photolithography, extreme ultraviolet photolithography, nanoimprint lithography, or electron beam lithography.

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