Sulfonium compound, manufacturing method thereof, polymer comprising the structural unit of the sulfonium compound and composition comprising the same

Abstract

L 1is an alkylene group or none; L 2is a divalent ester group or none; L 3is -C(O)O- or none; L Ais a divalent phenyl group or none; R 1is H or alkyl group; R 2is H, halogen or alkyl group; R 3is a divalent aryl group or none. The advantage of the present invention lies in the application of compound Z, a polymer containing the structural unit of compound Z, and composition thereof in semiconductor processing, which enables the achievement of photoresist patterns with improved resolution.

Description

[Technical Field]

[0001] This invention relates to a thioonium salt compound, particularly to a thioonium salt compound used as a photoresist material, a method for manufacturing the same, its polymers, and compositions comprising the same. [Previous Technology]

[0002] Thionium salt compounds are used in a variety of applications, such as as photoacid generators in chemically amplified photoresist materials. Chemically amplified photoresist materials contain resin, photoacid generators, and solvents. After coating with this chemically amplified photoresist material, the desired area of ​​the coated chemically amplified photoresist pattern is irradiated with DUV or EUV radiation. The photoacid generator senses the irradiated radiation and generates acid. The generated acid alters the solubility of the resin, thus forming a photoresist pattern used to fabricate integrated circuits.

[0003] In recent years, integrated circuits have been trending towards miniaturization. In order to form photoresist patterns with even finer detail, a photoacid-generating agent with excellent resolution is needed. In this regard, prior art, such as Republic of China Patent Publication No. 201427937, discloses a strontium salt compound that can generate acid more effectively, is also well soluble in solvents used in photoresist materials, and can suppress acid diffusion when used with strontium salt compounds that generate stronger acids. The cationic portion of this strontium salt compound has a naphthyl strontium cationic structure, while the anionic portion has an adamantyl or 2-oxo-tyl sulfonic acid anionic or carboxylic acid anionic structure. [Summary of the Invention]

[0004] As mentioned above, in the field of semiconductor manufacturing, there is an urgent need for a photoresist material that can improve the resolution of photoresist patterns. Through research, the inventors have discovered that in the exposure and development process of semiconductor manufacturing, the photoacid-generating agent needs to generate sufficiently strong acidity to effectively destroy the thin film formed by the photoresist, thereby forming fine photoresist patterns. The stronger the acidity generated by the photoacid-generating agent, the higher the resolution of the corresponding photoresist pattern. Furthermore, the inventors have also found that conventional methods for preparing photoresist materials typically include additional purification processes, thereby increasing operational complexity and being quite time-consuming.

[0005] In this regard, the present invention provides a compound Z, which is composed of an anion A and a cation B, wherein the anion A is shown in formula (I) and the cation B is shown in formula (II): Formula (I), Formula (II); wherein, n is 0, 1 or 2; L1 is alkyl or absent; L2 is divalent ester or absent; L3 is -C(O)O- or absent; LA is phenyl or absent; R1 is H or alkyl; R2 is H, halogen or alkyl; R3 is divalent aryl or absent.

[0006] According to some embodiments of the present invention, L1 is methyl or ethyl.

[0007] According to some embodiments of the present invention, R1 is methyl or H.

[0008] According to some embodiments of the present invention, R2 is F, methyl or H.

[0009] Another aspect of the present invention provides a method for manufacturing the aforementioned compound Z, comprising: preparing compound BA' as shown in formula (I-5) when L3 is -C(O)O-, comprising the following steps: in step A1, performing an ion exchange reaction between compound MA1 as shown in formula (I-1) and compound BX as shown in formula (I-2) to form compound BA1 as shown in formula (I-3); and in step 2, performing an esterification reaction between compound BA1 and compound A2 as shown in formula (I-4) to form compound BA', formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5), wherein R4 is Cl, -OC(O)R5, -OH, -OR6 or -NH2; R5 is alkyl; R6 is alkyl or aryl; M is sodium ion, potassium ion, lithium ion or monovalent onium ion.

[0010] According to some embodiments of the present invention, wherein the L2 and LA of the compound A-1 are absent.

[0011] According to some embodiments of the present invention, in step 2, the esterification reaction is carried out in the presence of an acid catalyst, and the acid catalyst is trifluoroacetic acid (TFA), methanesulfonic acid, p-toluenesulfonic acid (PTSA) or pyridinium p-toluenesulfonate (PPTS).

[0012] According to some embodiments of the present invention, in step 2, the esterification reaction is carried out in the presence of a base catalyst, and the base catalyst is pyridine, dimethylaminopyridine (DMAP), triethylamine, dicyclohexylcarbodiimide (DCC), diisopropylmethanediimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (3-[(Ethylimino)methylidene]amino-N,N-dimethylpropan-1-amine (EDCI) or a combination thereof.

[0013] In another aspect, the present invention provides a polymer comprising a structural unit corresponding to compound Z as described above and a structural unit corresponding to comonomer M, wherein the comonomer M is , , or , wherein a is 1 or 2; R7 is an alkyl group having 1 to 6 carbons; R8 is an alkyl group having 1 to 6 carbons or an alkoxy group.

[0014] According to some embodiments of the present invention, the weight average molecular weight (Mw) of the polymer is less than or equal to 4000.

[0015] According to some embodiments of the present invention, in thermogravimetric analysis (TGA), the thermal decomposition temperature Td of the polymer at a weight loss of 5% is greater than or equal to 180°C.

[0016] According to some embodiments of the present invention, the thermal decomposition temperature Td is greater than or equal to 200°C.

[0017] In another aspect, the present invention provides a composition comprising: a polymer as described above; and a resin component.

[0018] According to some embodiments of the present invention, the resin component is a photosensitive resin component.

[0019] According to some embodiments of the present invention, the composition further comprises a metal, and the metal is sodium, potassium, magnesium, aluminum, calcium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, lead or a combination thereof.

[0020] According to some embodiments of the present invention, the content of each metal in the composition is less than or equal to 10 ppb.

[0021] The advantage of this invention lies in that, by employing the manufacturing method of compound Z of this invention, no additional and complex purification methods are required, thereby reducing costs such as time and operational complexity, while obtaining compound Z with high yield and high purity. Thus, this invention provides a highly efficient manufacturing method, which can be directly applied to industrial-scale production compared to existing technologies. Furthermore, by applying compound Z of this invention, polymers containing structural units of compound Z, and their compositions to semiconductor manufacturing processes, photoresist materials with higher sensitivity can be obtained, thereby achieving the technical benefits of photoresist patterns with improved resolution and linewidth roughness.

Implementation Method

[0022] The following embodiments should not be considered as unduly limiting the present invention. Those skilled in the art to which this invention pertains may modify and vary the embodiments discussed herein without departing from the spirit or scope of the present invention, and such modifications and variations shall still fall within the scope of the present invention.

[0023] In this document, the terms “a” and “a kind” mean that there is one or more grammatical objects in this document (i.e., at least one).

[0024] [Compound Z]

[0025] This invention provides a compound Z, which is suitable as a photoresist material in semiconductor manufacturing processes. The photoresist material contains a photoacid generator (also known as a photoacid producing agent), and compound Z is a monomer for preparing the photoacid generator. Compound Z is composed of an anion A and a cation B, wherein the anion A is shown in formula (I) and the cation B is shown in formula (II): Formula (I), Formula (II).

[0026] According to some embodiments of the present invention, n is 0, 1, or 2; not limited by a specific theory, the inventors have found that when n is larger, the photoacid-generating agent containing the structural unit of the corresponding compound Z produces stronger acidity in the exposure and development process of semiconductor manufacturing, and vice versa; in addition, the strong acid property can improve the sensitivity of photoresist materials, thereby improving the resolution, line width roughness, and line edge sharpness of photoresist patterns in subsequent applications. Specifically, the strong acid property can more effectively catalyze the chemical reaction of photoresist, enabling the photoresist to produce sufficient chemical changes at lower exposure doses, which is particularly suitable for EUV and DUV lithography technologies, and also helps to reduce exposure time and thus improve exposure efficiency. Furthermore, the strong acid property makes the acid catalytic ability stronger, making the reaction inside the photoresist more uniform, thereby reducing the variability of local chemical reactions, thus reducing the non-uniformity of line boundaries and reducing line width roughness, making the pattern more refined, so the strong acid property can support the fabrication of smaller line widths. Photocatalytic chemical changes can improve the edge sharpness of photoresist patterns, reduce blurring effects, and make the patterns more refined, thereby improving resolution. Considering cost and acidity, the raw material cost for preparing anion A with n=1 is higher, and the resulting anion A produces weaker acidity in subsequent applications; therefore, anion A with n=2 is preferred. Furthermore, when the value of n is too large, in addition to the increased preparation cost, the structure is not easily biodegradable, which does not meet the industry's environmental protection trends.

[0027] According to some embodiments of the present invention, L1 is an alkyl group or none; the alkyl group may be, for example, a linear, branched, or cyclic alkyl group, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc., preferably methyl or ethyl. According to other embodiments of the present invention, L2 is a divalent ester group or none; the divalent ester group is preferably -C(O)O-. According to other embodiments of the present invention, L3 is -C(O)O- or none; preferably -C(O)O-. According to other embodiments of the present invention, LA is a phenyl group or none; the phenyl group may be, for example, an unsubstituted phenyl group or a substituted phenyl group, preferably an unsubstituted phenyl group, more preferably a p-phenyl group, an o-phenyl group, or a meta-phenyl group, particularly preferably a p-phenyl group.

[0028] According to some embodiments of the present invention, R1 is H or an alkyl group; the alkyl group may be, for example, a straight-chain, branched, or cyclic alkyl group, specifically, for example, methyl, ethyl, n-propyl, isopropyl, or n-butyl, etc., preferably methyl; preferably, R1 is H. According to other embodiments of the present invention, R2 is H, a halogen, or an alkyl group; the halogen is F, Cl, Br, or I, preferably F; the alkyl group may be, for example, a straight-chain, branched, or cyclic alkyl group, specifically, for example, methyl, ethyl, n-propyl, isopropyl, or n-butyl, etc.; preferably, R2 is H, F, or methyl. According to other embodiments of the present invention, R3 is a divalent aryl group or none; the divalent aryl group may be, for example, an ester-containing divalent aryl group, or an enylphenyl or a divalent carboxyphenyl; the enylphenyl group may be, for example, an unsubstituted enylphenyl or a substituted enylphenyl, preferably an unsubstituted enylphenyl, more preferably an enyl-p-phenyl, an o-phenyl, or an meta-phenyl, and especially preferably an enyl-p-phenyl.

[0029] [Method for manufacturing compound Z]

[0030] Another aspect of the present invention provides a method for manufacturing compound Z, comprising: preparing compound BA' as shown in formula (I-5) when L3 is -C(O)O-, comprising the following steps: firstly, in step 1, performing an ion exchange reaction between compound MA1 as shown in formula (I-1) and compound BX as shown in formula (I-2) to form compound BA1 as shown in formula (I-3); and then, in step 2, performing an esterification reaction between compound BA1 and compound A2 as shown in formula (I-4) to form compound BA' as shown in formula (I-5), wherein formulas (I-1), (I-2), (I-3), (I-4), and (I-5) are defined as previously stated. According to some preferred embodiments of the present invention, L2 and LA of compound A-1 are absent.

[0031] According to some embodiments of the present invention, M is a monovalent cation, preferably, for example, a sodium ion, a potassium ion, a lithium ion, or a monovalent onium ion. The monovalent onium ion may be, for example, a thionium ion.

[0032] According to some embodiments of the present invention, R4 is Cl, -OC(O)R5, -OH, -OR6, or -NH2; R5 is an alkyl group; R6 is an alkyl or aryl group. According to other embodiments of the present invention, R5 may be, for example, a linear, branched, or cyclic alkyl group, specifically, methyl, ethyl, n-propyl, isopropyl, or n-butyl, etc. According to other embodiments of the present invention, R6 may be, for example, a linear, branched, or cyclic alkyl group, specifically, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, or cyclobutyl, etc.; or, R6 may be, for example, an unsubstituted or substituted aryl group, specifically, phenyl or methylphenyl, etc. Not limited by a specific theory, the chlorohydrin formed when R4 is Cl is highly reactive, but also highly unstable, susceptible to water and oxygen, and difficult to store, thus having a disadvantageous impact on large-scale production. In response, the inventors discovered that the anhydride group formed when R4 is -OC(O)R5 has relatively high reactivity and high stability to water and oxygen, making it a better choice for large-scale production.

[0033] According to some embodiments of the present invention, the esterification reaction can be carried out in the presence of an acid catalyst or a base catalyst. According to some preferred embodiments of the present invention, the esterification reaction is carried out in the presence of an acid catalyst, and the acid catalyst is used to catalyze and promote the condensation reaction of compound BA1 and compound A2, which may be, for example, trifluoroacetic acid (TFA), methanesulfonic acid (MSA), p-toluenesulfonic acid (PTSA), or pyridinium p-toluenesulfonate (PPTS); preferably, the acid catalyst is trifluoroacetic acid.

[0034] According to some other preferred embodiments of the present invention, the esterification reaction is carried out in the presence of a base catalyst, which is used to catalyze and promote the condensation reaction of compound BA1 and compound A2. The base catalyst may be, for example, pyridine, dimethylaminopyridine (DMAP), triethylamine, dicyclohexylcarbodiimide (DCC), diisopropylmethanediimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (3-[(Ethylimino)methylidene]amino-N,N-dimethylpropan-1-amine (EDCI) or a combination thereof; preferably, the base catalyst is DCC and DMAP.

[0035] The inventors have discovered that, theoretically, the preparation of the above-mentioned compound BA' can be divided into two paths as shown below. Path one includes ion exchange followed by esterification, while path two includes esterification followed by ion exchange: <Path one> <Path two>; where X is Cl, Br, or I. The inventors have found that, in actual experiments, when using path one to prepare compound BA', during the ion exchange process, the properties of compound BX (also known as a triaryl sulfide halide compound) are similar to those of the ion exchange product (referring to compound BA1), and their solubility in solvents is also similar. Therefore, it is difficult to clean the product by solvent washing. Accordingly, by using Le Chatelier's principle to increase the amount of anion, which is also a reactant, the reaction can be pushed to the right, thereby reducing the residue of compound BX in the product. Furthermore, since the anion in compound BX is a small, water-soluble substance, excess anions are easily carried away by the aqueous layer, thus allowing for complete reaction and obtaining a high-purity product. Furthermore, selecting a suitable organic solvent can further promote the reaction to proceed to the right. Specifically, for example, a solvent with high solubility for the reactants (i.e., compounds MA1 and BX) but insoluble in the product (i.e., compound BA1) can be selected. However, in actual experiments, the aforementioned advantages are not obvious when using the second route method for ion exchange reactions, resulting in low yields of the final product (i.e., compound BA') or even failure to react. To improve purity, additional purification methods are required (e.g., column separation or ion exchange methods using special ion exchange resins), thus significantly increasing production costs. Accordingly, the present invention preferably employs the first route method.

[0036] [Polymer]

[0037] Another aspect of the present invention provides a polymer comprising a structural unit corresponding to compound Z as described above and a structural unit corresponding to comonomer M, and the polymer is preferably used as a photoresist material. The comonomer M has polymerizable functional groups, such as vinyl or acrylic groups. The comonomer M typically has suitable solubility and rheological properties, for example, good solubility in nonpolar or moderately polar organic solvents, which can improve the solubility of the corresponding polymer, facilitating the formation of a uniform and smooth film of the photoresist material on a silicon wafer or other substrate, thereby further improving the resolution of the photoresist pattern. According to some embodiments of the present invention, the comonomer M is, for example, α, β, or α, where α is 1 or 2; R7 is an alkyl group having 1 to 6 carbon atoms; R8 is an alkyl group having 1 to 6 carbon atoms or an alkoxy group. According to some embodiments of the present invention, the alkyl group having 1 to 6 carbon atoms may specifically be, for example, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, isopentyl, tripentyl, n-hexyl, or isohexyl. According to other embodiments of the present invention, the alkoxy group having 1 to 6 carbon atoms may specifically be, for example, alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, or hexoxy.

[0038] According to some embodiments of the present invention, the weight-average molecular weight (Mw) of the polymer is less than or equal to 4000, specifically, for example, less than or equal to 4000, less than or equal to 3500, less than or equal to 3000, less than or equal to 2500, less than or equal to 2000, less than or equal to 1500, less than or equal to 1000; preferably, it is between 2500 and 4000, specifically, for example: 2500, 2616, 2750, 2780, 3000, 3006, 3250, 3500, 3750, 4000, or a range between any two of the aforementioned values. Not limited by any particular theory, controlling the weight-average molecular weight of the polymer to less than or equal to 4000 can further improve the solubility and diffusivity of the polymer, thereby enhancing the resolution of the photoresist pattern formed when subsequently applied to photoresist materials.

[0039] According to some embodiments of the present invention, in thermogravimetric analysis (TGA), the thermal decomposition temperature Td of the polymer at a weight loss of 5% is greater than or equal to 180°C, specifically, for example, greater than or equal to 180°C, greater than or equal to 185°C, greater than or equal to 190°C, greater than or equal to 195°C, greater than or equal to 200°C, or greater than or equal to 205°C; preferably, the thermal decomposition temperature Td is greater than or equal to 200°C.

[0040] [Composition]

[0041] In another aspect, the present invention provides a composition comprising the polymer as described above and a resin component. According to some preferred embodiments of the present invention, the resin component is a photosensitive resin component. The photocondensation resin component may specifically be, for example, polycarboxylate resins such as poly(methyl methacrylate) (PMMA) or polystyrene-maleic anhydride copolymer (PSMA); polyester resins such as polylactic acid (PLA) or photosensitive polyester; phenolic resins such as epoxy novolac resin (ENR); polyimide (PI) such as photosensitive polyimide (PSPI) or polybenzoxazole (PBO); polyether resins such as polyethylene glycol (PEG) or epoxy resin, or combinations thereof.

[0042] According to some embodiments of the present invention, the composition further comprises a metal; preferably, the metal may be, for example, sodium, potassium, magnesium, aluminum, calcium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, lead, or a combination thereof. According to other embodiments of the present invention, the content of each metal in the composition is less than or equal to 10 ppb, specifically, for example, less than or equal to 10 ppb, less than or equal to 9 ppb, less than or equal to 8 ppb, less than or equal to 7 ppb, less than or equal to 6 ppb, or less than or equal to 5 ppb. Not limited by any particular theory, if the content of each metal is too high, it can easily contaminate the wafer in subsequent applications and reduce yield. Examples

[0043] The present invention will be further described below with detailed description and specific embodiments. However, it should be understood that these specific embodiments are only for the purpose of helping to more readily understand the present invention and are not intended to limit the scope of the present invention.

[0044] 1. Preparation of compound Z and its precursor

[0045] [Synthesis Example 1]

[0046] Add 30 mL of MEK, 5.92 g of sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonate (SFO2), and 6.25 g of Ph3SCl (triphenylsulfonyl chloride, TPSC) to a 50-mL three-necked flask. Stir until a suspension is formed, and continue stirring for 16 hours. Filter to remove salts, and concentrate the filtrate. Add 35 mL of dichloroethane and 20 mL of RO water to the concentrate and stir for 30 minutes to dissolve, forming a two-phase mixture. Collect the dichloroethane layer separately, and extract the aqueous layer twice with 10 mL of dichloroethane. Combine the dichloroethane layers and concentrate. Wash the concentrate twice with 40 mL of diisopropyl ether. Recrystallize with isopropanol / isopropyl ether, crush the resulting solid, add 40 mL of isopropyl ether, stir and wash, filter, and vacuum dry to obtain 7.9 g of powder (78.2% yield). See Figure 1 for the 1H-NMR spectrum. 1H-NMR (400 MHz, DMSO-d6) δ7.83(15H, m), 4.70(-OH, 1 H, t,J=5.6 Hz), 3.64(2H, m), 2.42(2H, m). 19F-NMR: δ-111.3(2F), -118.4(2F).

[0047] [Synthesis Example 2]

[0048] A nitrogen stream was passed through a 250-mL three-necked flask. 15.89 g (40 mmol) of tris(4-fluorophenyl)-strontium bromide (FTPSB) was added, along with 11.41 g (46 mmol) of SFO2 (sodium 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonate) and 180 mL of MEK. The mixture was stirred at room temperature for 6 hours. The solids were removed by filtration through filter paper, and the filtrate was concentrated. 70 mL of dichloroethane, 2.5 g of SFO2, and 25 mL of RO water were added to the concentrate, and the mixture was stirred for 1 hour. The resulting oil and liquid layers were collected, and the aqueous layer was discarded. The collected oil and liquid layers were combined and concentrated. 70 mL of isopropyl ether was added to the concentrate, and the mixture was stirred for 3 hours. The isopropyl ether layer was discarded, and the mixture was stirred for another 3 hours. The isopropyl ether layer was discarded, and the mixture was concentrated and dried. The resulting oily substance was added to 70 mL of isopropanol and heated at 48°C for 25 minutes until completely dissolved. The solution was then concentrated to remove approximately 20 mL of IPA. After cooling, 100 L of isopropyl ether was added while stirring overnight. A granular precipitate formed; the liquid layer was decanted, and 70 mL of isopropyl ether was added and stirred for 3 hours. The isopropyl ether layer was decanted, and another 70 mL of isopropyl ether was added and stirred for 3 hours. After solidification, the isopropyl ether layer was decanted, and the solidified product was scraped with a spatula. Another 70 mL of isopropyl ether was added and stirred for 3 hours. The product was filtered and vacuum dried to obtain 17.98 g (82.9% yield). The 1H-NMR spectrum is shown in Figure 2. 1H-NMR (400 MHz, DMSO-d6) δ7.94(6H, m), 7.67(6H, m), 4.71(-OH, 1 H, t, J=5.5 Hz), 3.63(2H, m), 2.39(2H, m). 19F-NMR: δ-103.5(3F), -111.4(2F), -118.4(2F).

[0049] [Synthesis Example 3]

[0050] 25 mL of dichloroethane and 1.503 g of SFO3 were added to a 50 mL three-necked flask and stirred until dissolved. 0.925 g of methacrylic anhydride and 0.18 g of methanesulfonic acid were added, and the mixture was heated to 48 °C for 6 hours. The reaction endpoint was confirmed by thin-layer silica gel chromatography (TLC) (developing solvent: methanol / dichloroethane = 1:3). The reaction solution was washed twice with 20 mL of water, transferred to a new flask to remove water droplets, and concentrated to obtain an oily substance. The initial oily product was washed seven times with 6 mL of diisopropyl ether, stirred for 30 minutes, and TLC confirmed complete removal of methacrylic acid. The solution was concentrated and vacuum dried to obtain 1.584 g of the oily substance (92.7% yield). See Figure 3 for the 1H-NMR spectrum. 1H-NMR (400 MHz, DMSO-d6) δ7.82(15H, m), 6.03(1H, s), 5.69(1H, s), 4.33(2H, t, J=6.4 Hz), 2.55(2H, m), 1.87(3H, s). 19F-NMR: δ-111.5(2F), -118.5(2F).

[0051] [Synthesis Example 4]

[0052] Add 15 mL of dichloromethane and 1.085 g of FSF03 to a 50 mL three-necked flask and stir. Add 0.617 g of methacrylic anhydride and 0.12 g of methanesulfonic acid, and heat to 41 °C for 5 hours. The reaction endpoint was confirmed by thin-layer silica gel chromatography (TLC). The reaction solution was washed twice with 10 mL of water, transferred to a different flask to remove water droplets, and concentrated to obtain an oily initial product. The oily initial product was washed seven times with 5 mL of isopropyl ether and stirred for 30 minutes, and the complete removal of methacrylic acid was confirmed by TLC. Concentrate and vacuum dry to obtain 1.14 g of oil (93.9% yield). Please refer to Figure 4 for the 1H-NMR spectrum. 1H-NMR (400 MHz, DMSO-d6) δ7.95(6H, m), 7.65(6H, m), 6.04(1H, s), 5.69(1H, s), 4.33(2H, t, J=6.4 Hz), 2.61 (2H, m), 1.88(3H, s). 19F-NMR: δ-103.5(3F), -111.5(2F), -118.5(2F).

[0053] [Synthetic Example 5]

[0054] 45 mL of dichloroethane and 10.15 g of SFO3 were added to a 100-mL three-necked flask and stirred. The flask was cooled in an ice-water bath to maintain the internal temperature at 10°C. 3.39 g of vinylbenzoic acid, 5.36 g of DCC (dicyclohexylcarbodiimide), and 0.50 g of DMAP (4-dimethylaminopyridine) were added sequentially. The mixture was slowly warmed to room temperature and reacted for 4 hours. The reaction endpoint was confirmed by TLC. The reaction solution was filtered to remove solid byproducts. 28 mg of BHT (2,6-dibutyl-p-cresol) was added to the filtrate as a polymerization inhibitor, followed by 30 mL of water. The mixture was stirred for 30 minutes and filtered again to remove solid byproducts. The resulting two-phase liquid was separated, the aqueous layer was removed, and the organic layer was concentrated to obtain an oily crude product. Add 40 mL of dichloroethane to dissolve the product, then add 80 mL of toluene and stir. Filter to remove insoluble matter, concentrate the filtrate to obtain an oily primary product. Wash the oily primary product with 35 mL of toluene / 50 mL of isopropyl ether for 60 minutes, and discard the solvent layer. Repeat the washing process three times, confirming cleanliness by TLC. Dissolve the product in 65 mL of dichloroethane, add 28 mg of BHT as a polymerization inhibitor, filter to remove insoluble matter, concentrate the filtrate to obtain 12.72 g of the oily product (94.9% yield). See Figure 5 for the 1H-NMR spectrum. 1H-NMR(400 MHz, DMSO-d6) δ7.93(2H, d, J=8.3 Hz), 7.78(15H, m), 7.63(2H, d, J=8.3 Hz), 6.82(1H, dd, J1=17.7 Hz, J2=11.0 Hz), 6.01(1H, d, J=17.7 Hz), 5.44(1H, d, J=11.0 Hz), 4.51(2H, t, J=6.3 Hz), 2.73(2H, m). 19F-NMR: δ -111.3(2F), -118.4(2F).

[0055] [Synthesis Example 6]

[0056] Add 40 mL of dichloroethane and 2.17 g of FSF03 to a 100-mL three-necked flask and stir until dissolved. Cool the reaction flask in an ice-water bath to maintain the internal temperature at 10°C. Add 0.752 g of ethylene benzoic acid, 1.22 g of DCC, and 33 mg of DMAP sequentially. Slowly warm to room temperature and react for 16 hours. Confirm the reaction endpoint by TLC. Filter the reaction solution to remove solid byproducts. Add 10 mg of BHT as a polymerization inhibitor to the filtrate, then add 30 mL of water and stir for 60 minutes. Filter again to remove solid byproducts. Separate the aqueous layer from the resulting two-phase liquid, concentrate the organic layer to obtain an oily crude product. Add 10 mL of dichloroethane to dissolve the crude product, then add 10 mL of toluene and stir. Filter to remove insoluble matter, concentrate the filtrate to obtain an oily primary product. Add 15 mL of toluene / 18 mL of isopropyl ether to the oily primary product, stir for 60 minutes, wash, and discard the solvent layer. The washing process was repeated four times, and the washing was confirmed by TLC. The solution was dissolved in 35 mL of dichloroethane, and 10 mg of BHT was added again as a polymerization inhibitor. The mixture was filtered to remove insoluble matter, and the filtrate was concentrated to give 2.452 g of the oily product (79.9% yield). The 1H-NMR spectrum is shown in Figure 6. 1H-NMR(400 MHz, DMSO-d6) δ7.94(8H, m), 7.64(8H, m), 6.82(1H, dd, J1=17.6 Hz, J2=11.0 Hz), 6.01(1H, d, J=17.6 Hz), 5.44(1H, d, J=11.0 Hz), 4.51(2H, t, J=6.3 Hz), 2.72(2H, m). 19F-NMR: δ -103.4(3F), -111.4(2F), -118.4(2F).

[0057] [Synthetic Example 7]

[0058] Please refer to Table 1 for the dosage ratio and reaction temperature of FSF03, BMA, DCC, DMAP and DCM.

[0059] [Table 1] FSF03 (mmol) BMA (eq.) Reagent (eq.) solvent Reaction temperature (°C) 1.0 1.2 DCC / DMAP (1.2 / 1.2%) dichloromethane (DCM) 0

[0060] Add BMA and dichloromethane to the reaction flask, cool the reaction vessel to 0°C under a nitrogen gas flow, add DMAP and FSF03, and wait until the internal temperature is < 0°C. Then, add DCC and dichloromethane dropwise to prepare the reaction (the process is exothermic). After the addition is complete, stir overnight at 0°C. Add BHT and stir for 5 minutes. Filter the solid through a 5µm Nylone membrane. Wash the filtrate three times with H2O. Dry the organic layer. Add dichloromethane:toluene = 1:4, and a solid will precipitate. Filter the solid through a 5µm Nylone membrane, and dry the organic layer. The oily substance was then washed with a mixture of 10 ml toluene and 25 ml (0.259 g BHT + 500 ml isopropyl ether). The oily substance was insoluble. The mixture was stirred for 1 hour, the supernatant was discarded, and the above steps were repeated until the impurities were removed. The washing was confirmed by TLC. The product was then completely dissolved in dichloromethane, and 0.2% BHT (w / w) was added. The mixture was mixed thoroughly and dried to obtain a maltose viscous substance with a yield of 50-80%. Please refer to Figure 7 for the 1H-NMR spectrum. 1H-NMR(400 MHz, DMSO-d6) δ7.94(7H, m), 7.67(7H, m), 7.46(1H, m), 7.29(1H, m), 6.29(1H, s), 5.90(1H, s), 4.42(2H, t, J=6.7 Hz), 2.65(2H, m), 2.10(3H, s). 19F-NMR: δ -103.5, -111.4, -118.5.

[0061] [Synthesis Example 8]

[0062] Synthetic Example 8 was prepared using a similar procedure to that of Synthetic Example 2. The 1H-NMR spectrum is shown in Figure 8. 1H-NMR (400 MHz, DMSO-d6) δ 7.94 (6H, m), 7.67 (6H, m), 5.48 (1H, m, OH), 3.91 (2H, m). 19F-NMR: δ -103.5, -117.6, -121.3.

[0063] [Synthesis Example 9]

[0064] Please refer to Table 2 for the dosage ratio and reaction temperature of FSF03, BMA, DCC, DMAP and DCM.

[0065] [Table 2] FSF03-3C (mmol) BMA (eq.) Reagent (eq.) solvent Reaction temperature (°C) 1.0 1.2 DCC / DMAP (1.2 / 1.2%) dichloromethane (DCM) 0

[0066] Synthetic Example 9 was prepared using a similar procedure to that of Synthetic Example 7. The 1H-NMR spectrum is shown in Figure 9. 1H-NMR (400 MHz, DMSO-d6) δ 8.01 (1H, m), 7.92 (6H, m), 7.74 (1H, m), 7.68 (6H, m), 7.47 (1H, m), 7.34 (1H, d, J=8.0 Hz), 6.28 (1H, s), 5.90 (1H, s), 4.84 (2H, t, J=15.8 Hz), 2.00 (3H, s). 19F-NMR: δ -103.5, -118.2, -119.2.

[0067] [Synthesis Example 10]

[0068] Add 4.12 g of A2, 5.96 g of Ph3SCl (TPSC), and 17 mL of RO water to a 100-mL three-necked flask and stir until dissolved. Continue stirring for 30 minutes, then add 35 mL of dichloromethane and stir for 30 minutes to dissolve, forming a two-phase mixture. Collect the dichloromethane layer separately, then extract the aqueous layer with 10 mL of dichloromethane. Combine the dichloromethane layers, dry with magnesium sulfate, and concentrate to obtain an oily product. Please refer to Figure 10 for the 1H-NMR spectrum. 1H NMR (500 MHz, d-DMSO) δ 7.76-7.87 (m, 15H), 7.55 (2H, d, J=8.2 Hz), 7.41 (2H, d, J=8.2 Hz), 6.71 (1H, dd, J=18 Hz, 11 Hz), 5.83 (1H, d, J=18 Hz), 5.26 (1H, d, J=11 Hz).

[0069] As can be seen from the above synthesis examples 1 to 10, by using the manufacturing method of the present invention to prepare compound Z, high yield of compound Z can be obtained without additional and complex purification methods. Specifically, the present invention has the advantage of obtaining high yield of compound Z without additional purification methods (such as column separation), thereby significantly reducing time costs and operational complexity. In addition, the 1H-NMR spectra corresponding to synthesis examples 1 to 10 (see Figures 1 to 10) are clear and do not have abnormal peaks and / or peak shapes, indicating that the products of synthesis examples 1 to 10 have high purity. Accordingly, the present invention provides a highly efficient manufacturing method, which can be directly applied to industrial-scale production compared to the prior art.

[0070] 2. Polymer Preparation

[0071] [Synthesis Example 11]

[0072] In a three-necked reaction flask, add 0.259 g of photopolymer monomer FSF04B, 4.0 g of acetonitrile, 0.181 g of comonomer CP1 (2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate), and 8.0 g of tetrahydrofuran. After stirring and mixing thoroughly, insert the flask bottom and purge with nitrogen gas for 3 minutes. Heat the flask in an oil bath to an internal temperature of 60°C and maintain the internal temperature at 60°C. Add AIBN / THF (5 mg / 12 g) solution dropwise and maintain the temperature overnight. After the reaction is complete, concentrate the resulting reaction solution to obtain a viscous substance. Add 15 times the volume (v / w) of methanol (6.6 mL), stir at room temperature for 30 minutes until a powdery solid suspension is obtained, and filter through a 5 μm nylon membrane. Add another 6.6 mL of methanol to the obtained solid, stir at room temperature for 30 minutes, and filter again through a 5 μm nylon membrane. A white solid is obtained, which weighs 0.079 g after vacuum drying, with a yield of 18%.

[0073] The polymer was analyzed by gel permeation chromatography (GPC), yielding a peak molecular weight (Mp) of 3076 and a weight-average molecular weight (Mw) of 2062. ¹H-NMR analysis revealed a molar ratio of CP1 to FSF04B structural units of 1:0.23. The molar ratio of FSF04B and CP1, and the molar ratio of FSF04B to CP1 structural units in the polymer, can be found in Table 3 below.

[0074] [Table 3] Photonic acid monomer Dosage in mole Various structures in polymers Mohrbi of the building unit FSF04B CP1 FSF04B CP1 FSF04B 0.33 1 0.23 1

[0075] [Synthesis Example 12]

[0076] Synthesis Example 12 was prepared using a similar procedure to that of Synthesis Example 11. ¹H-NMR analysis of the polymer revealed a molar ratio of CP1 to FSF04 structural units of 1:0.26. The molar ratio of FSF04 and CP1, and the molar ratio of FSF04B to CP1 structural units in the polymer, can be found in Table 4 below.

[0077] [Table 4] Photonic acid monomer Dosage in mole Various structures in polymers Mohrbi of the building unit FSF04 CP1 FSF04 CP1 FSF04 0.66 1 0.26 1

[0078] [Synthesis Example 13]

[0079] Synthesis Example 13 was prepared using a similar procedure to that of Synthesis Example 11. ¹H-NMR analysis of the polymer revealed a molar ratio of CP1 to FSF04B3C of 1:0.23. The molar ratio of FSF04B3C and CP1, and the molar ratio of FSF04B to CP1 in the polymer, can be found in Table 5 below.

[0080] [Table 5] Photonic acid monomer Dosage in mole Various structures in polymers Mohrbi of the building unit FSF04B3C CP1 FSF04B3C CP1 FSF04B3C 0.33 1 0.23 1

[0081] [Synthesis Example 14]

[0082] Synthesis Example 14 was prepared using a similar procedure to that of Synthesis Example 11. Analysis of the polymer by 1H-NMR revealed a molar ratio of 1:1.42 between the structural unit corresponding to M1 (1-ethylcyclohexyl methacrylate) and the structural unit corresponding to A2B2. The molar ratio of A2B2 and M1, and the molar ratio of the structural unit corresponding to A2B2 to the structural unit corresponding to M1 in the polymer, can be found in Table 6 below.

[0083] [Table 6] Photonic acid monomer Dosage in mole Various structures in polymers Mohrbi of the building unit A2B2 M1 A2B2 M1 A2B2 1 0.91 1.42 1

[0084] [Synthesis Example 15]

[0085] The polymer of Synthesis Example 15 was prepared by using photopolymer monomer A2B2 and comonomer M1 in a manner similar to that of Synthesis Example 14. UV-Vis absorption spectroscopy analysis of the polymer revealed a maximum UV absorption peak of 241 nm. GPC analysis of the polymer showed a number average molecular weight (Mn) of 2181, a weight average molecular weight (Mw) of 2780, a peak molecular weight (Mp) of 2072, a Z-average molecular weight (Mz) of 3580, an Mz+1 value of 4580, and a polydispersity index of 1.27.

[0086] The metal content of the product of Synthesis Example 16 was analyzed by ICP-MS, and it was found that it contained magnesium, calcium, zinc, sodium, aluminum, potassium, titanium, chromium, manganese, iron, cobalt, nickel, copper, silver and lead, and the content of each metal was less than 10 ppb. The polymer was analyzed by TGA, and its thermal decomposition temperature Td at 5% weight loss was 203°C.

[0087] [Synthesis Example 16]

[0088] The polymer of Synthesis Example 16 was prepared by using photopolymer monomer A2B2 and comonomer M1 in a manner similar to that of Synthesis Example 14. UV-Vis absorption spectroscopy analysis of the polymer revealed a maximum UV absorption peak of 241 nm. GPC analysis of the polymer showed a number average molecular weight (Mn) of 2139, a weight average molecular weight (Mw) of 2616, a peak molecular weight (Mp) of 2586, a Z-average molecular weight (Mz) of 3002, an Mz+1 of 3340, and a polydispersity index of 1.22. ICP-MS analysis of the metal content of the product of Synthesis Example 16 revealed that it contained magnesium, calcium, zinc, sodium, aluminum, potassium, titanium, chromium, manganese, iron, cobalt, nickel, copper, silver, and lead, with the content of each metal less than 10 ppb.

[0089] The metal content of the product of Synthesis Example 16 was analyzed by ICP-MS, and it was found that it contained magnesium, calcium, zinc, sodium, aluminum, potassium, titanium, chromium, manganese, iron, cobalt, nickel, copper, silver and lead, and the content of each metal was less than 10 ppb. The polymer was analyzed by TGA, and its thermal decomposition temperature Td at 5% weight loss was 204°C.

[0090] In summary, the advantage of the present invention lies in that, by employing the manufacturing method of compound Z of the present invention, no additional and complex purification methods are required, thereby reducing costs such as time and operational complexity, while obtaining compound Z with high yield and high purity. Thus, the present invention provides a highly efficient manufacturing method, which can be directly applied to industrial-scale production compared to existing technologies. Furthermore, by applying compound Z of the present invention, polymers containing structural units of compound Z, and their compositions to semiconductor manufacturing processes, photoresist materials with higher sensitivity can be obtained, thereby achieving the technical benefits of photoresist patterns with improved resolution and linewidth roughness.

[0091] In this document, all ranges provided are intended to include each specific range within a given range and combinations of subranges between that given range. Furthermore, unless otherwise stated, all ranges provided herein include the endpoints of the range. Thus, ranges 1 to 5 specifically include 1, 2, 3, 4, and 5, and subranges such as 2 to 5, 3 to 5, 2 to 3, 2 to 4, 1 to 4, etc.

[0092] All publications and patent applications cited in this specification are incorporated herein by reference, and for any and all purposes, each individual publication or patent application is expressly and individually identified as incorporated herein by reference. In the event of any inconsistency between this document and any publication or patent application incorporated herein by reference, this document shall prevail. [Simplified Explanation of the Diagram]

[0093] To make the above and other objects, features, advantages and embodiments of this application more readily understood, the accompanying drawings are described below:

[0094] Figures 1 to 10 are 1H-NMR spectra according to some embodiments of the present invention.

Claims

1. A compound Z, comprising an anion A and a cation B, wherein the anion A is represented by formula (I) and the cation B by formula (II): Formula (I), Formula (II); wherein, n is 2; L1 is methyl or ethyl; L2 is divalent ester; L3 is -C(O)O- or none; LA is phenyl; R1 is H or alkyl; R2 is H, halogen or alkyl; R3 is none.

2. The compound as claimed in claim 1, wherein R1 is methyl or H.

3. The compound as claimed in claim 1, wherein R2 is F, methyl or H.

4. A method for manufacturing compound Z as claimed in claim 1, comprising: preparing compound BA' of formula (I-5) when L2 is -C(O)O-, comprising the following steps: in step 1, subjecting compound MA1 of formula (I-1) to ion exchange with compound BX of formula (I-2) to form compound BA1 of formula (I-3); and in step 2, subjecting compound BA1 to esterification with compound A2 of formula (I-4) to form compound BA' of formula (I-5), formulas (I-1), (I-2), (I-3), (I-4), and (I-5), wherein R4 is Cl, -OC(O)R5, -OH, -OR6, or -NH2; R5 is alkyl; R6 is alkyl or aryl; and M is sodium ion, potassium ion, lithium ion, or monovalent onium ion. ion); X is Cl, Br or I.

5. The manufacturing method as described in claim 4, wherein, In step 2, the esterification reaction is carried out in the presence of an acid catalyst, which is trifluoroacetic acid (TFA), methanesulfonic acid (MSA), p-toluenesulfonic acid (PTSA), or pyridinium p-toluenesulfonate (PPTS).

6. The manufacturing method as described in claim 4, wherein, In step 2, the esterification reaction is carried out in the presence of a base catalyst, which is pyridine, dimethylaminopyridine (DMAP), triethylamine, dicyclohexylcarbodiimide (DCC), diisopropylmethanediimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (3-[(Ethylimino)methylidene]amino-N,N-dimethylpropan-1-amine (EDCI)) or a combination thereof.

7. A polymer comprising a structural unit corresponding to compound Z as shown in claim 1 and a structural unit corresponding to comonomer M, wherein the comonomer M is , , or , wherein a is 1 or 2; R7 is an alkyl group having 1 to 6 carbons; and R8 is an alkyl group having 1 to 6 carbons or an alkoxy group.

8. The polymer as described in claim 7 has a weight average molecular weight (Mw) of less than or equal to 4000.

9. A composition comprising: a polymer as described in claim 7; and a resin component.

10. The composition as claimed in claim 9, wherein the resin component is a photosensitive resin component.

11. The composition as claimed in claim 9, further comprising a metal, wherein the metal is sodium, potassium, magnesium, aluminum, calcium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, lead, or a combination thereof.

12. The composition as claimed in claim 11, wherein the content of each metal is less than or equal to 10 ppb.

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