Photoresist composition and pattern formation method

Abstract

A photoresist composition comprising one or more non-solvent alkali-insoluble substrates present in a total amount exceeding 50% by weight based on the total solids content of the photoresist composition, and a nonpolymeric ionic photoacid generator compound comprising an anion and an iodonium or sulfonium cation, wherein the anion is defined by formula (1) as defined herein. [Formula 1] A photoresist composition comprising a nonpolymeric ionic photoacid generator compound, represented by TIFF2026530380000098.tif50166, and a solvent, wherein the photoacid generator does not produce a photoacid having a higher acidity than the photoacid produced by the nonpolymeric ionic photoacid generator compound.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority and benefits of U.S. Provisional Patent Application No. 65 / 533,270, filed on 17 August 2023, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a photoresist composition and a patterning method using such a photoresist composition. The present invention is particularly applicable to lithography applications in the semiconductor manufacturing industry. [Background technology]

[0003] Photoresist compositions are photosensitive materials used to transfer patterns onto one or more underlying layers, such as metal, semiconductor, or dielectric layers, placed on a substrate. Positive-type chemically amplified photoresist compositions have traditionally been used for high-resolution processing. Such resist compositions typically comprise a polymer having acid-unstable groups and a photoacid generator (PAG). A layer of the photoresist composition is pattern-exposed to activating radiation, and the PAG generates acid in the exposed areas. During post-exposure baking, the acid causes cleavage of the acid-unstable groups of the polymer, resulting in a polarity reversal of the polymer within the exposed areas. This results in a difference in solubility between the exposed and unexposed areas of the photoresist layer in the developer solution. In a positive-type development (PTD) process, the exposed areas of the photoresist layer become soluble in the developer, typically an aqueous-based developer, and are removed from the substrate surface, while the unexposed areas remain on the substrate, forming a positive-type relief image. Alternatively, in the negative development (NTD) process, the unexposed areas of the photoresist layer can be removed with an organic solvent developer, typically n-butyl acetate, while the exposed areas remain on the substrate, forming a negative relief image. The resulting relief image allows for selective processing of the substrate.

[0004] A property of photoresist compositions that can directly impact semiconductor manufacturing costs is photosensitivity, i.e., sensitivity to activation radiation generated by exposure tools, with higher sensitivity corresponding to higher process throughput for a given feature size. To enhance photosensitivity, it is desirable that PAGs generate acids strong enough to cleave acid-unstable groups on the polymer. For this purpose, typical examples are ionic PAG compounds having a photoactive cation and an anion with a fluorinated sulfonate group, where the fluorine atom and / or fluoroalkyl group are adjacent to the sulfonate group and typically bonded as substituents to one or more alkylene carbon atoms bonded to the sulfonate anion group. Upon exposure to activation radiation, the photoactive cation undergoes a cascade of photochemical and chemical processes resulting in the formation of fluorinated sulfonic acids. Certain fluorinated PAGs in this class of compounds enable highly acidic photoacids, but there is growing interest from the semiconductor manufacturing industry and government regulatory bodies in replacing them with more sustainable alternatives.

[0005] Examples of existing fluorine-free PAGs include the p-toluenesulfonate anion and the camphorsulfonate anion. However, these anions have relatively low acid dissociation constants (e.g., about 18 orders of magnitude smaller than tris(trifluoromethylsulfonyl)methane), which limits their usefulness in photoresists requiring higher photoacid strength. Therefore, it is desirable to have a photoresist composition containing an ionic photoacid generator compound that produces a sulfonic acid of sufficient strength that does not depend on specific fluorine substitutions for increasing acidity. [Overview of the project] [Problems that the invention aims to solve]

[0006] There is an ongoing need for photoresist compositions that address one or more problems related to the prior art, and for patterning methods using such photoresist compositions. [Means for solving the problem]

[0007] One aspect is a photoresist composition, comprising: one or more non-solvent alkali-insoluble substrates present in a total amount exceeding 50% by weight based on the total solid content of the photoresist composition; and a non-polymeric ionic photoacid generator compound comprising an anion and an iodonium or sulfonium cation, wherein the anion has formula (I):

Chemical Formula

[0008] Another embodiment provides a patterning method comprising: coating a layer of photoresist composition onto a substrate to provide a photoresist composition layer; pattern-exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer to provide a resist relief image. [Modes for carrying out the invention]

[0009] Here, exemplary embodiments are described in detail, and examples thereof are illustrated in this description. In this regard, these exemplary embodiments may take different forms and should not be construed as being limited to the descriptions expressed herein. Accordingly, exemplary embodiments are described below only by reference to the figures in order to illustrate aspects of this description. As used herein, the terms “and / or” encompass any and all combinations of one or more of the enumerated items relating thereto. Expressions such as “at least one” qualify the entire list of elements, when preceding a list of elements, and do not qualify the individual elements of the list.

[0010] As used herein, the terms “one (a),” “one (an),” and “it” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically indicated herein or the context clearly contradicts this. “Or” means “and / or” unless otherwise specified. The modifier “about” used in relation to quantity includes the expressed value and has meaning determined by the context (e.g., including the degree of error associated with the measurement of a particular quantity). All scopes disclosed herein include endpoints, which can be independently combined with each other. The suffix “(s)” includes both singular and plural forms of the term it modifies and is intended to include at least one of those terms. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes both the cases in which the event occurs and the cases in which the event does not occur. The terms “first,” “second,” etc., used herein do not imply order, quantity, or importance, but rather are used to distinguish one element from another. When an element is said to be “on top of” another element, it may be in direct contact with the other element, or an intervening element may exist between them. In contrast, when an element is said to be “directly on top of” another element, no intervening element is present. It should be understood that the components, elements, limitations, and / or features described in the embodiments may be combined in any suitable manner in various embodiments.

[0011] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which the invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning as those defined in the relevant art and in relation to this disclosure, and it will be further understood that they should not be interpreted in an ideal or overly formal sense unless explicitly defined herein.

[0012] As used herein, "chemical beam" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, or particle beams such as electron beams and ion beams. Furthermore, in this invention, "light" means chemical beam or radiation. A krypton fluoride laser (KrF laser) is a specific type of excimer laser and is sometimes called an exciplex laser. "Excimer" is an abbreviation for "excitation dimer," while "exciplex" is an abbreviation for "excitation complex." An excimer laser uses a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine) and emits coherent stimulating radiation (laser light) in the ultraviolet range under appropriate conditions of electrical stimulation and high pressure. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using mercury lamps, excimer lasers, or other far-ultraviolet, X-ray, or extreme ultraviolet (EUV) light, but also writing using particle beams such as electron beams and ion beams.

[0013] As used herein, the terms “hydrocarbon” means an organic compound or group having at least one carbon atom and at least one hydrogen atom; “alkyl” means a linear or branched saturated hydrocarbon group having the specified number of carbon atoms and a valency of 1; “alkylene” means an alkyl group having a valency of 2; “hydroxyalkyl” means an alkyl group substituted with at least one hydroxyl group (-OH); “alkoxy” means “alkyl-O-”; “carboxyl” and “carboxy "Roubonic acid group" refers to a group having the formula "-C(=O)-OH", "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon, "cycloalkylene" refers to a cycloalkyl group having a valency of 2, "alkenyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon double bond in a straight or branched chain, "alkenoxy" refers to "alkenyl-O-", "alkenylene" refers to an alkenyl group having a valency of 2, and "cycloalkenyl" refers to a group having at least one carbon "Alkynyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms and a sub-carbon double bond; "Alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; "Aromatic group" refers to a monocyclic or polycyclic aromatic ring system that satisfies Huckel's rule (4n + 2π electrons) and contains carbon atoms in the ring; "Heteroaromatic group" refers to an aromatic group that contains one or more heteroatoms (e.g., 1 to 4 heteroatoms) selected from N, O, and S instead of carbon atoms in the ring; "Aryl" refers to a monovalent monocyclic or polycyclic aromatic ring system in which all ring members are carbon and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "Arylene" refers to an aryl group with a valency of 2; "Alkylaryl" refers to an aryl group substituted with an alkyl group; "Arylalkyl" refers to an alkyl group substituted with an aryl group; "Aryloxy" refers to "aryl-O-"; and "Arylthio" refers to "aryl-S-".

[0014] The prefix "hetero" means that a compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) instead of a carbon atom, and each heteroatom can be independently N, O, S, Si, or P. "Heteroatom-containing group" refers to a substituent containing at least one heteroatom, "heteroalkyl" refers to an alkyl group having at least one heteroatom instead of carbon, and "heterocycloalkyl" refers to a cycloalkyl group having 1 to 4 heteroatoms as ring members instead of carbon. The terms "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of 2, and "heteroaryl" refers to an aromatic 4-8 member monocyclic, 8-12 member bicyclic, or 11-14 member tricyclic group having 1-4 heteroatoms (in the case of a monocyclic), 1-6 heteroatoms (in the case of a bicyclic), or 1-9 heteroatoms (in the case of a tricyclic) (for example, in the case of a monocyclic, bicyclic, or tricyclic, respectively, carbon atoms and 1-3, 1-6, or 1-9 heteroatoms of N, O, or S). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl, etc., and "heteroarylene" refers to a heteroaryl group having a valence of 2.

[0015] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one or more fluoro, chloro, bromo, or iodo substituents instead of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or a fluoro group alone may exist. For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C 1~8 "Haloalkyl" refers to C substituted with at least one halogen. 1~8This refers to an alkyl group that is further substituted with one or more other non-halogen substituents. It should be understood that because halogen atoms do not replace carbon atoms, substitution of a group at a halogen atom is not considered a heteroatom-containing group.

[0016] Unless explicitly specified otherwise, each of the aforementioned substituents may be optionally substituted. The term “optionally substituted” means substituted or unsubstituted. “Substituted” means that at least one hydrogen atom of the chemical structure or group is replaced by another terminal substituent, which is typically monovalent, provided that the valency does not exceed the normal valency of the specified atom. When the substituent is oxo (i.e., O), two geminal hydrogen atoms on the carbon atom are replaced by a terminal oxo group. It is further noted that the oxo group is bonded to the carbon atom via a double bond to form a carbonyl (C=O), and the carbonyl group is represented herein as -C(O)-. Combinations of substituents or variables are permitted. Exemplary substituents that may be present in the “substituted” position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di-(C) 1~6 ) Alkylamino, alkanoyl (e.g., C 2~6 Alkanoyl groups (e.g., acyl), formyl (-C(O)H), carboxylic acids or their alkali metal or ammonium salts, esters (including acrylates, methacrylates and lactones), for example, C 2~6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl) and C 7~13 Aryl esters (-C(O)O-aryl or -OC(O)-aryl), amides (-C(O)NR2 (wherein R is hydrogen or C 1~6 Alkyl carboxamide (-CH2C(O)NR2 (wherein R is hydrogen or C) 1~6 Alkyl, halogen, thiol (-SH), C 1~6 Alkylthio(-S-alkyl), thiocyano(-SCN), C 1~6 Alkyl, C 2~6 Alkenil, C 2~6 Alkinyl, C 1~6Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, a C2 molecule having at least one aromatic ring. 6~12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is substituted or unsubstituted aromatic), having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms. 7~19 Arylalkyls, arylalkoxys having 1-3 separate or condensed rings and 6-18 carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(O)2-alkyl), C 6~12 Examples include, but are not limited to, arylsulfonyl (-S(O)2-aryl) or tosyl (CH3C6H4SO2-).

[0017] In this specification, unless otherwise defined, “divalent linking group” refers to -O-, -S-, -Te-, -Se-, -C(O)-, -C(O)O-, -N(R ’ )-,-C(O)N(R ’ )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 This refers to a divalent group containing one or more heteroarylenes or combinations thereof, where each R ’ These are, independently, hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30is heteroaryl. Typically, the divalent linking group is -O-, -S-, -C(O)-, -C(O)O-, -N(R’)-, -C(O)N(R ’ )-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 alkylene, substituted or unsubstituted C 3~30 cycloalkylene, substituted or unsubstituted C 3~30 heterocycloalkylene, substituted or unsubstituted C 6~30 arylene, substituted or unsubstituted C 3~30 heteroarylene, or one or more combinations thereof, wherein R' is hydrogen, substituted or unsubstituted C 1~20 alkyl, substituted or unsubstituted C 1~20 heteroalkyl, substituted or unsubstituted C 6~30 aryl, or substituted or unsubstituted C 3~30 heteroaryl. More typically, the divalent linking group is -O-, -C(O)-, -C(O)O-, -N(R ’ )-, -C(O)N(R')-, substituted or unsubstituted C 1~10 alkylene, substituted or unsubstituted C 3~10 cycloalkylene, substituted or unsubstituted C 3~10 heterocycloalkylene, substituted or unsubstituted C 6~10 arylene, substituted or unsubstituted C 3~10 heteroarylene, or at least one combination thereof, wherein R is hydrogen, substituted or unsubstituted C 1~10 alkyl, substituted or unsubstituted C 1~10 heteroalkyl, substituted or unsubstituted C 6~10 aryl, or substituted or unsubstituted C 3~10 heteroaryl.

[0018] As used herein, “acid-unstable group” refers to a group whose bonds are selectively and typically cleaved by the action of an acid during heat treatment, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group. In some cases, the acid-unstable group may be formed on a polymer, and selectively and typically, the portion bound to the cleaved bond is detached from the polymer. In other systems, a nonpolymeric compound may contain an acid-unstable group that can be cleaved by the action of an acid, and a polar group such as a carboxylic acid group or an alcohol group is formed on the cleaved portion of the nonpolymeric compound. Such acids are typically photocatalytic acids in which bond cleavage occurs during post-exposure baking (PEB). However, embodiments are not limited thereto, and for example, such acids may be thermally produced. Suitable acid-unstable groups include, for example, tertiary alkyl ester groups, secondary or tertiary ester groups having an aryl group, secondary or tertiary ester groups having a combination of an alkyl group and an aryl group, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-unstable groups are also commonly referred to in this technical field as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-unstable protecting groups," "acid-leaving groups," "acid-degradable groups," and "acid-sensitive groups."

[0019] The sensitivity of photoresist performance often correlates with the final device manufacturing throughput. In particular, high-resolution lithography technologies such as 193nm lithography (ArF) tend to struggle with photoresists that have optimal sensitivity. To achieve good sensitivity, many photoresists use photoacid generators (PAGs) containing anions belonging to the sulfonate class bonded to polymers containing low-activation-energy leaving groups (e.g., ester acetals or acetal-esters). Over the past decade, many sulfonate derivatives have been developed for this purpose, with fluorinated sulfonates being one example. Compounds in this class excel in lithography thanks to their very high acidity and are expected to be replaced worldwide with more sustainable alternatives. However, there is still a need for PAG anions with good acidity and higher persistence.

[0020] The present inventors have discovered a photoacid generator comprising an anionic core containing an aromatic group substituted with a sulfonate anionic group and an anionic stabilizing group that stabilizes the sulfonate anionic group by an intramolecular non-covalent bond. That is, the anionic stabilizing group is configured to form an intramolecular non-covalent bond with the sulfonate anionic group. For example, although we do not wish to be bound by theory, the anionic stabilizing group can form an intramolecular non-covalent bond with the sulfonate anionic group, or for example, the anionic stabilizing group can form an intramolecular non-covalent bond with the sulfonate anionic group. In some embodiments, the intramolecular non-covalent bond can be formed in situ, for example, when a nonpolymeric ionic photoacid generator compound is included in a photoresist composition. When used in a photoresist composition, the PAG according to the present invention has a sizing energy (E size This can result in appropriate lithography characteristics such as exposure freedom % (EL%) and / or line width roughness.

[0021] A nonpolymeric ionic photoacid generator compound comprising one or more non-solvent alkali-insoluble substrates present in a total amount exceeding 50% by weight (wt%) based on the total solids content of the photoresist composition, and an anion, iodonium, or sulfonium cation, wherein the anion is of formula (1): [ka] A photoresist composition is provided comprising a nonpolymeric ionic photoacid generator compound and a solvent, wherein the photoresist composition does not contain a photoacid generator that produces a photoacid having a higher acidity than the photoacid produced by the ionic photoacid generator compound. It will be understood that the total solids consist of one or more non-solvent alkali-insoluble substrates, a nonpolymeric ionic photoacid generator compound and other non-solvent components.

[0022] In equation (1), Ar 1 C is either monocyclic or polycyclic. 3~60 It is an aromatic group. For example, monocyclic or polycyclic carbon atoms. 3~60 Aromatic groups are monocyclic C 3~60 Aromatic group or polycyclic carbon 6~60It may be an aromatic group. In one embodiment, it may be a monocyclic or polycyclic carbon. 3~60 Aromatic groups are monocyclic or polycyclic carbon groups. 6~60 Arylene group or monocyclic or polycyclic C 3~60 Heteroarylene groups, typically monocyclic or polycyclic C 6~30 Arylene group or monocyclic or polycyclic C 3~30 It may be a heteroarylene group.

[0023] "Single-ring or poly-ring C" 6~60 When an "arylene group" is polycyclic, it should be understood that the number of carbon atoms is sufficient to make the group chemically feasible. For example, "monocyclic or polycyclic C 6~60 "Arylene group" refers to "monocyclic C6 arylene group or polycyclic C6 group" 10~60 This can refer to an "arylene group," or for example, a "monocyclic C6 arylene group or a polycyclic C6 group." 10~30 It is an "arylene group". Similarly, it is a "monocyclic or polycyclic C 3~60 If the heteroarylene group is polycyclic, the number of carbon atoms is sufficient for the group to be chemically realizable. For example, monocyclic or polycyclic C 3~60 "Heterorialene group" is a "monocyclic C 3~6 Heteroarylene group or polycyclic C 5~60 This could refer to a "heteroarylene group," or, for example, a "monocyclic C group." 3~6 Heteroarylene group or polycyclic C 5~30 It is a "heteroarylene group".

[0024] Exemplary monocyclic or polycyclic C 3~60 Aromatic groups include, but are not limited to, benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, or benz[a]pyrene.

[0025] In equation (1), each L 1 Independently, L is a single bond or one or more divalent linking groups. 1 It does not contain fluorine. In other words, L 1If L is one or more divalent linking groups, 1 It does not contain fluorine.

[0026] Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups are, independently, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R')-, and -C(O)N(R ’ )-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It can be a heteroaryl compound. Typically, L 1 C is a single bond or a substituted or unsubstituted C 1~20 Alkylene, preferably single bond or substituted or unsubstituted C 1~10 It could be alkylene, L 1 It does not contain an α-carbon atom directly covalently bonded to the sulfur atom of a sulfonate anion group substituted with a fluorine atom or a fluoroalkyl group.

[0027] In equation (1), each R 1 These are, independently, halogens, hydroxyls, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 It is a heteroaryloxy. For example, each R 1 These are independently hydroxyl, substituted, or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 It may be a heteroaryloxy. In some embodiments, at least one R 1 is substitution C 6~30 Aryl or substituted C 7~30 It is an arylalkyl.

[0028] In equation (1), each R 1 It optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 You can choose from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It could be a heteroaryl.

[0029] In some embodiments, one or more R 1 Each of these may independently contain an acid-unstable group, a lactone-containing group, a base-solubilizing group, or a combination thereof.

[0030] In equation (1), each Z 1 It independently contains an anion stabilizing group and at least one Z 1 It is configured to form a ring having 5 to 8 atoms by forming an intramolecular non-covalent bond with a sulfonate anion group, Z 1 These are independently -OH, -C(O)OH, -SH, -C(O)SH, and -NHS(O)2R 2 -S(O)2R 2 -S(O)2NHS(O)2R 2 -CH (=NOH) or -B (R 3 ) Selected from 2, R 2 and R 3 These are as defined herein. Typically, each anionic stabilizing group Z 1 The can be independently selected from -OH, C(O)OH, SH, or -B(OH)2, preferably at least one anionic stabilizing group Z. 1 It contains -OH.

[0031] For example, each Z 1 It can be configured to form a ring having 6 or 7 atoms by forming an intramolecular non-covalent bond with a sulfonate anion group. Monocyclic or polycyclic C 3~60 Aromatic group Ar 1 two or more anionic stabilizing groups Z1 If it contains an anionic stabilizing group Z 1 It should be understood that at least one of these is configured to form a ring having 5 to 8 atoms by forming an intramolecular non-covalent bond with at least one sulfonate anion group.

[0032] As used herein, “anion stabilizing group” refers to any suitable group that can stabilize a sulfonate anion group via an intramolecular non-covalent bond provided herein. Thus, the anion stabilizing group is configured to form an intramolecular non-covalent bond with the sulfonate anion group, i.e., the anion stabilizing group can form an intramolecular non-covalent bond with the sulfonate anion group. As used herein, “non-covalent bond” may refer to any non-covalent interaction between the anion stabilizing group and the sulfonate anion group. As described above, the non-covalent interaction is intramolecular, and the anion stabilizing group and the sulfonate anion group are on the same molecule. Exemplary non-covalent bonds include hydrogen bonds or ionic bonds. The anion stabilizing group may include a protic group. For example, the intramolecular non-covalent bond may be an intramolecular hydrogen bond between a suitable hydrogen atom of the anion stabilizing group and the sulfonate anion group. For example, in some embodiments, the anion-stabilizing group may be configured to form an intramolecular hydrogen bond with the sulfonate anion group. In some embodiments, the intramolecular non-covalent bond includes dipole-dipole interactions, ion-dipole interactions, or a combination thereof. As used herein, “non-covalent bond” does not include bonds based solely on van der Waals forces.

[0033] In some embodiments, the anionic stabilizing group may have a pKa of 25 or less, typically 20 or less, or 18 or less, preferably 16 or less.

[0034] In some embodiments, each anion stabilizing group includes a protic group. For example, if the anion stabilizing group is protic, each Z 1is -OH, -C(O)OH, -SH, -C(O)SH, -NHS(O)2R 2 -S(O)2R 2a -S(O)2NHS(O)2R 2 -CH (=NOH) or -B (R 3a )2 can be selected independently, and each R 2 C is fluorine, hydroxyl, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 Selected independently from heteroaryls, each R 2a is hydroxyl, and each R 3a C is hydrogen, fluorine, hydroxyl, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 Selected independently from heteroaryls, however, at least one R 3a It is hydrogen or hydroxyl.

[0035] In equation (1), each Z 1 It optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 You can choose from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It can be a heteroaryl compound. Typically, Z 1 -O-, -C(O)-, -C(O)O-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 It may optionally further contain one or more divalent linking groups selected from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It may be a heteroaryl. In some embodiments, the anion stabilizing group is Ar 1 Each Z 1 It does not necessarily have to contain a divalent linking group independently.

[0036] In equation (1), each R 2 C is fluorine, hydroxyl, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It is selected independently of heteroaryl compounds.

[0037] In equation (1), each R 3 C is hydrogen, fluorine, hydroxyl, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It is selected independently of heteroaryl compounds.

[0038] In equation (1), there are two R 1 Together, Ar 1 A fused ring is optionally formed, and this fused ring optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups is substituted or unsubstituted, and the fused ring is substituted or unsubstituted.

[0039] In equation (1), one Z 1 and one R 1 Together, Ar 1 Ar optionally forms a fused ring, the fused ring optionally further containing one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups is substituted or unsubstituted, and the fused ring is substituted or unsubstituted. 1 The fused ring formed can be aliphatic or aromatic.

[0040] In equation (1), each a is independently either 1 or 2.

[0041] In equation (1), b is an integer between 0 and 4. Typically, b is an integer between 0 and 2, and preferably b is 0 or 1.

[0042] In equation (1), c is an integer between 1 and 3. Typically, c is 1 or 2, and preferably c is 1. For example, in some embodiments, a can be 1 or 2, and c can be 1. In some embodiments, c can be 1, and L 1 It is a single bond.

[0043] In some embodiments, the anion may not contain a trifluoromethyl group and a difluoromethylene group. In other words, in some embodiments, the anion of formula (1) may not contain a trifluoromethyl group and a difluoromethylene group. For example, in some embodiments, the anion may not contain fluorine (the anion of formula (1) may not contain fluorine).

[0044] In some embodiments, Ar 1 is a single ring C 3~60 It can be an aromatic group and has at least one Z 1 ha-L 1 -SO3 - It is located in the ortho position relative to the group represented by . For example, Ar 1 is a single ring C 3~6 It can be an aromatic group, and at least one Z1 is -L 1 -SO3 - It can be located in the ortho position relative to the group represented by . In some embodiments, Ar 1 is a single ring C 3~6 It can be a compound group, L 1 It is a single bond, and at least one Z1 is -L 1 -SO3 - It can be located in the ortho position relative to the group represented by [the specified symbol].

[0045] In some embodiments, Ar 1 This is a polycyclic C 6~60 It can be an aromatic group and has at least one Z 1 The base is -L 1 -SO3 - For a group represented by, the Ar located in the ortho position on the same ring 1 It can be bonded to the ring carbon atom. For example, Ar 1 is a polycyclic C 6~60 It can be a compound group, L 1 It is a single bond and has at least one Z 1 The base is -L 1 -SO3 - For a group represented by, the Ar located in the ortho position on the same ring 1 It can be bonded to the ring carbon atom.

[0046] In some embodiments, in formula (1), Ar 1 This is a polycyclic C 6~60 It can be an aromatic group and has at least one Z 1 The base is -L 1 -SO3 - The Ar at the β position relative to the ring carbon atom to which it is bonded. 1 It can be bonded to the ring carbon atom, and at least one Z1 Base and -L 1 -SO3 - These are bonded to different rings of a polycyclic aromatic group. As used herein, the term “beta-position substituent” refers to a substituent bonded to each aromatic ring carbon atom on different rings of a polycyclic ring system, the ring carbon atom being separated by the bonded ring carbon atom.

[0047] In some embodiments, the conjugate acid of the photoacid generator compound may have a pKa of 0 or less. Typically, the conjugate acid of the photoacid generator compound may have a pKa of -2 or less, preferably -5 or less. The conjugate acid of the photoacid generator compound may have a pKa of, for example, -15 to 0 or -15 to -2.

[0048] In some embodiments, the anion of formula (1) is formula (1a): [ka] It can be represented by:

[0049] In equation (1a), Ar 1 This is a monocyclic or polycyclic C defined by equation (1). 3~60 It is an aromatic group.

[0050] In equation (1a), each Z 1 It independently contains an anionic stabilizing group defined by formula (1).

[0051] In equation (1a), each R 1 These are independent, as defined in equation (1).

[0052] In equation (1a), a is either 1 or 2, and b is an integer between 0 and 4.

[0053] In some embodiments, the anion of formula (1) is given by formulas (2a) to (2f): [ka] It can be represented by one of the following.

[0054] In equations (2a) to (2f), each Z 1 It independently contains an anionic stabilizing group defined by formula (1).

[0055] In equations (2a) to (2f), each R 1 This is defined independently for equation (1).

[0056] In equations (2a) to (2f), a is either 1 or 2, and b is an integer between 0 and 4.

[0057] In some embodiments, the anions of formula (1) are given by formulas (3a) to (3n): [ka] It can be represented by one of the following.

[0058] In equations (3a) to (3n), each Z 1 It independently contains an anionic stabilizing group defined by formula (1).

[0059] In equations (3a) to (3n), each R 1 This is defined independently for equation (1).

[0060] In equations (3a) to (3n), b is an integer between 0 and 4.

[0061] At least one Z1 is -L 1 -SO3 - Similar groups located in the ortho position relative to the group represented by include, but are not limited to, the groups represented by formulas (3a), (3b), (3c), (3d), (3f), (3g), (3h), (3j), (3k), and / or (3l).

[0062] Ar 1 is a condensed polycyclic C 6~60 It is an aromatic group and has at least one Z 1 The base is -L 1 -SO3 -The Ar at the β position relative to the ring carbon atom to which it is bonded. 1 It is bonded to the ring carbon atom, and at least one Z 1 Base and -L 1 -SO3 - However, condensed polycyclic C 6~60 Examples of groups bonded to different rings of an aromatic group include, but are not limited to, those represented by formulas (3e), (3i), (3m), and / or (3n).

[0063] In yet another embodiment, Ar 1 is at least one Z 1 The base is -L 1 -SO3 - For a group represented by, the Ar located in the ortho position on the same ring 1 It is bonded to the ring carbon atom, and at least one Z 1 The base is -L 1 -SO3 - The Ar located at the beta position relative to the ring carbon atom to which it is bonded. 1 It is bonded to the ring carbon atom, and at least one Z 1 Base and -L 1 -SO3 - However, condensed polycyclic C 6~60 A fused polycyclic carbon atom with aromatic groups bonded to different rings. 6~60 It can be an aromatic group. -L 1 -SO3 - Located in the ortho position relative to the group represented by, Ar 1 is polycyclic C 6~60 At least one Z1 is an aromatic group, and a second substituent (sulfonate, -L 1 -SO3 - The Ar at the β position relative to the ring carbon atom to which the ) is bonded. 1 At least one Z bonded to the ring carbon atom 1 Structures possessing both the base and the base include, but are not limited to, formulas (3f) and (3h).

[0064] Exemplary anions represented by formula (1) of nonpolymeric ionic photoacid generator compounds include the following: [ka] [ka] [ka] [ka] [ka]

[0065] Anions of nonpolymeric ionic photoacid-generating compounds can be obtained from commercial sources or prepared by any suitable method. For example, such anions can be prepared as described in the examples herein.

[0066] As described above, the anion stabilizing group is configured to form an intramolecular non-covalent bond with the sulfonate anion group. For example, although we do not wish to be constrained by theory, the anion stabilizing group can form an intramolecular non-covalent bond with the sulfonate anion group, or for example, the anion stabilizing group may form an intramolecular non-covalent bond with the sulfonate anion group. In some embodiments, the intramolecular non-covalent bond may be formed in situ, for example, when a nonpolymeric ionic photoacid generator compound is included in the photoresist composition. In some embodiments, an intramolecular non-covalent bond, such as an intramolecular hydrogen bond, may be formed between the anion stabilizing group and the sulfonate anion. The resulting intramolecular hydrogen bond structure may form a ring having 5 to 8 atoms, most preferably 6 to 8 atoms. For example, an exemplary intramolecular hydrogen bond interaction between the anion stabilizing group and the sulfonate anion group is shown in the following formula (I), where the intramolecular hydrogen bond structure forms a ring having 6 atoms, but embodiments are not limited thereto. [ka]

[0067] The nonpolymeric ionic photoacid generator compound further comprises an iodonium or sulfonium cation. In some embodiments, the cation may be a sulfonium cation of formula (4a) or an iodonium cation of formula (4b). [ka]

[0068] In equations (4a) and (4b), R 30 ~R 34 These are, independently, substituted or non-substituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 2~30 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 7~30 Arylalkyl or substituted or unsubstituted C 4~30 It is a heteroarylalkyl group or a combination thereof. 30 ~R 34 Each of them is either independent or connected to another group R via a single bond or a divalent linking group. 30 ~R 34 It can be connected to form a ring. 30 ~R 34 Each of these may optionally contain a divalent linking group as part of its structure. 30 ~R 34 Each of these may independently optionally contain an acid-unstable group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

[0069] The exemplary sulfonium cation of formula (4a) may include one or more of the following: [ka]

[0070] The exemplary iodonium cation of formula (4b) may include one or more of the following: [ka]

[0071] Cations of nonpolymeric ionic photoacid-generating compounds can be obtained from commercial sources or prepared using common synthetic procedures.

[0072] Suitable nonpolymeric ionic photoacid generator compounds include those obtained from any combination of the anions and cations described above. Nonpolymeric ionic photoacid generator compounds can be prepared by combining anionic and cationic species under appropriate conditions.

[0073] Nonpolymeric ionic photoacid generator compounds may be included in the photoresist composition in an amount of 1 to 65 weight percent (Wt%), more typically 15 to 30%, 8 to 14 weight%, or 2 to 7 weight%, based on the total solids content of the photoresist composition. In some embodiments, the photoresist composition may contain two or more different nonpolymeric ionic photoacid generator compounds described herein. For example, the photoresist composition may contain one or more nonpolymeric ionic photoacid generator compounds in a total amount of 1 to 65 weight%, more typically 15 to 30%, 8 to 14 weight%, or 2 to 7 weight%, based on the total solids content of the photoresist composition.

[0074] The photoresist composition may further contain additional photoacid generators. The additional PAG may be in ionic or nonionic form, provided that the photoresist composition does not contain a photoacid generator that produces a photoacid having a higher acidity than that produced by the nonpolymeric ionic photoacid generator compound described above. The additional PAG may be in polymeric or nonpolymeric form. In polymeric form, the additional PAG may exist as a portion of repeating units of a polymer derived from polymerizable PAG monomers.

[0075] Appropriate additional PAG compounds are, formula G + A - (In the formula, G + A is a photoactive cation, - The photoactive cation may be an anion capable of generating photoacid. The photoactive cation is preferably an onium cation, preferably an iodonium or sulfonium cation, selected from those described above with respect to the nonpolymeric ionic photoacid generator compounds of the present invention (e.g., those of formula (4a) and / or (4b)). Particularly suitable anions include those whose conjugate acid has a pKa of -15 to 0, or -14 to 0, or -13 to 0. The anions are typically organic anions having a sulfonate group or a non-sulfonate type group, such as a sulfonamide, sulfonimidate, methide, arsenate, or borate. In some embodiments, the additional PAG may have an anion having the structure of formula (1) defined for the anion of the nonpolymeric ionic photoacid generator compound, and the anion of the additional PAG compound may have a group Z, which is an anion stabilizing group. 1 It does not include.

[0076] In some embodiments, the anion of the additional PAG is fluorine-free, meaning it does not contain -F, -CF3, or -CF2- groups. It should be understood that "-F, -CF3, or -CF2- group-free" means that the anion of the additional PAG excludes groups such as -CH2CF3 and -CH2CF2CH3. In yet other embodiments, the anion of the additional PAG is fluorine-free (i.e., it does not contain a fluorine atom and is not substituted with a fluorine-containing group). In some embodiments, the additional PAG is fluorine-free (i.e., neither the photoactive cation nor the anion contains fluorine).

[0077] Exemplary onium salts include, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Other useful additional PAG compounds are known in the field of chemically amplified photoresists and include, for example, the following: Nonionic sulfonyl compounds, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, e.g., bis Examples include -O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinidomethanesulfonic acid ester and N-hydroxysuccinidomitetrifluoromethanesulfonic acid ester, and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Appropriate additional PAGs are further described in U.S. Patent Nos. 8,431,325 and 4,189,323.

[0078] Typically, when a photoresist composition contains additional nonpolymeric PAGs, the additional PAGs are present in the photoresist composition in an amount of 0.1 to 55% by weight, more typically 1 to 25% by weight, based on the total solids of the photoresist composition. When present in polymeric form, the additional PAGs are typically present in the polymer in an amount of 1 to 25 mol%, more typically 1 to 8 mol%, or 2 to 6 mol%, based on the total repeating units in the polymer.

[0079] The photoresist composition also includes one or more non-solvent alkali-insoluble substrates present in a total amount exceeding 50% by weight based on the total solids content of the photoresist composition. The one or more non-solvent alkali-insoluble substrates, which may hereafter be referred to as matrix materials, may be polymers or nonpolymers. Suitable alkali-insoluble substrates will be apparent to those skilled in the art based on the descriptions provided herein. In some embodiments, the alkali-insoluble substrate does not contain phenolic hydroxyl groups, such as phenolic hydroxyl group-containing novolac resins. In some embodiments, the alkali-insoluble substrate does not contain carboxylic acid groups. In some embodiments, the alkali-insoluble substrate may contain phenolic hydroxyl groups and / or carboxylic acid groups, provided that the alkali-insolubility of the substrate is maintained.

[0080] To determine whether a particular substrate is alkali-insoluble, the substrate can be subjected to a solubility test using an alkaline developing aqueous solution, such as an aqueous solution of 0.26 n (N) tetramethylammonium hydroxide (TMAH). Alkali solubility can be determined, for example, by the following method: The substrate film can be coated onto the surface of a Si substrate by spin coating and the initial film thickness can be measured. The substrate film can be immersed in a 0.26 N TMAH aqueous solution at room temperature for 60 seconds, followed by typical developing conditions of DI water rinsing and air drying, and then the film thickness can be measured again. Alkali insolubility is indicated by a thickness change of less than 2 nanometers (nm), preferably less than 1 nm, less than 0.5 nm, less than 0.1 nm, or 0 nm.

[0081] In some embodiments, the substrate may include polymers, metal-containing materials, or combinations thereof. It should be understood that "substrate" does not define the material as basic (for example, the substrate is not necessarily basic according to the definition of acid / base chemistry).

[0082] The polymer in the photoresist composition may be a homopolymer or copolymer containing two or more structurally different repeating units. For example, the polymer may contain one or more repeating units containing functional groups selected from hydroxyaryl groups, acid-unstable groups, base-solubilizing groups, lactone-containing groups, sultone-containing groups, polar groups, crosslinking groups, or combinations thereof.

[0083] In one or more embodiments, the polymer may comprise repeating units formed from monomers containing acid-unstable groups. Suitable acid-unstable groups include, for example, tertiary esters, acetals, ketals, and tertiary ethers. [ka] [ka] In the formula, R d This includes hydrogen, halogens (e.g., F, Cl, Br, I), and substituted or unsubstituted C. 1~6 Alkyl or substituted or unsubstituted C 3~6 It is a cycloalkyl group.

[0084] When repeating units with acid-unstable groups are present in a polymer, they are typically present in amounts of 25–75 mol%, more typically 25–50 mol%, and even more typically 30–50 mol%, based on the total number of repeating units in the polymer.

[0085] In some embodiments, the polymer may comprise repeating units derived from one or more lactone-containing monomers. Suitable lactone-containing monomers include, for example, [ka] and in the formula, R d is hydrogen, halogen (e.g., F, Cl, Br, I), substituted or unsubstituted C 1~6 alkyl or substituted or unsubstituted C 3~6 cycloalkyl.

[0086] When a repeating unit derived from one or more lactone-containing monomer is present in the polymer, it is typically present in an amount of 0.5 to 75 mol%, more typically 1 to 50 mol%, even more typically 5 to 50 mol%, based on the total repeating units in the polymer.

[0087] In some embodiments, the polymer may comprise a repeating unit having a base-solubilizing group and / or having a pKa of 12 or less. Exemplary base-solubilizing groups may include fluoroalcohol groups, carboxylic acid groups, carboximide groups, sulfonamide groups or sulfonimide groups.

[0088] Non-limiting examples of monomers comprising a base-solubilizing group include:

Chemical Formula

Chemical Formula

[0089] When a repeating unit having a base-solubilizing group and / or having a pKa of 12 or less is present in the polymer, it is typically present in an amount of 0.5 to 30 mol%, more typically 15 to 25 mol%, even more typically 5 to 10 mol%, based on the total repeating units in the polymer.

[0090] The polymer may further optionally comprise one or more aromatic group-containing repeating units. For example, such a repeating unit is

Chem.

[0091] When present, the polymer typically comprises aromatic group-containing repeating units in an amount of 1 to 80 mol%, more typically 5 to 75 mol%, even more typically 5 to 50 mol%, based on the total repeating units in the polymer.

[0092] In some embodiments, the polymer may optionally comprise repeating units derived from an acetal monomer that does not contain an ester acetal, for example, a monomer of formula (5):

Chem.

[0093] In formula (5), X b is a polymerizable group which can be a carbon-carbon unsaturated vinyl group, and L2 is substituted or unsubstituted C 1-10 alkylene, substituted or unsubstituted C3-10 cycloalkylene, substituted or unsubstituted C 3~10 heterocycloalkylene, substituted or unsubstituted C 6~12 arylene, substituted or unsubstituted C 4~12 heteroarylene, or a divalent linking group selected from combinations thereof.

[0094] In formula (5), R 7 and R 8 are each independently hydrogen, substituted or unsubstituted C 1~20 alkyl, substituted or unsubstituted C 3~20 cycloalkyl, substituted or unsubstituted C 3~20 heterocycloalkyl, substituted or unsubstituted C 6~20 aryl, substituted or unsubstituted C 7~30Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~20 Heteroaryl, substituted, or unsubstituted C 4~30 Heteroarylalkyl or substituted or unsubstituted C 4~30 It is an alkyl heteroaryl. Preferably, R 7 and R 8 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 It is heterocycloalkyl. 7 and R 8 Each of them optionally further includes a divalent linking group as part of its structure.

[0095] In equation (5), R 9 is a substitution or non-substitution C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 It is heterocycloalkyl. 9 It optionally further includes a divalent linking group as part of its structure.

[0096] In equation (5), R 7 or R 8 One of them is connected via a single bond or a divalent linking group, R 9 Together with , a complex ring can be optionally formed, which may be substituted or non-substituted. The ring can be monocyclic, non-condensed polycyclic, or condensed polycyclic, and is typically monocyclic when formed.

[0097] Non-restrictive examples of monomers represented by formula (5) include: [ka] These are listed, and in the formula, R d C is hydrogen, fluorine, cyano or substituted or unsubstituted C 1~10 It is alkyl.

[0098] If present, the polymer typically contains repeating units having acetal monomers that do not contain ester acetals, in amounts of 1 to 80 mol%, more typically 5 to 75 mol%, and even more typically 5 to 50 mol%, based on the total repeating units in the polymer.

[0099] The polymer may optionally further optionally contain one or more additional repeating units. These additional repeating units may be, for example, one or more additional units for the purpose of modifying properties of the photoresist composition such as etch rate and solubility. Exemplary additional units may include those derived from one or more (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. If one or more additional repeating units are present in the polymer, they may be used in an amount of 50 mol% or less, typically 3–50 mol%, based on the total repeating units of the polymer.

[0100] Examples of non-limiting polymers of the present invention include: [ka] One or more of the following can be listed, where a, b, and c represent the mole fractions of each repeating unit of the polymer, and a+b+c=1. It should be understood that the mole fractions of a, b, and c are selected such that the polymer is alkali-insoluble.

[0101] In some embodiments, the non-solvent alkali-insoluble substrate may include chain-severing polymers, unclipping polymers, or combinations thereof.

[0102] A chain-cleavable polymer can undergo a chain cleavage reaction under appropriate conditions. Any suitable chain-cleavable polymer may be used. Exemplary direct photodegradable chain-cleavable polymers include, for example, copolymers of α-substituted styrene and substituted α-halogen acrylate, such as α-methylstyrene / methyl-α-chloroacrylate copolymers, 2-trifluoroethyl-α-chloroacrylate / α-methyl-4-fluorostyrene copolymers, or combinations thereof.

[0103] Unzipping polymers include polymers having unzipping polymer end groups upon appropriate stimuli (photo-induced or chemically induced stimuli) that trigger breaking of the polymer backbone into smaller fragments. Typically, the unzipping polymer is selected such that stimulation of a first chemical modification or degradation event causes a partial or overall unzipping effect. Any suitable unzipping polymer may be used.

[0104] The polymer typically has a weight average molecular weight (M w ) of 1,000 to 200,000 Daltons (Da), preferably 10,000 to 150,000 Da, more preferably 15,000 to 150,000 Da, even more preferably 25,000 to 150,000 Da or 50,000 to 150,000 Da. The polydispersity index (PDI) of the first polymer (the ratio of M w to the number average molecular weight (M n )) is typically 1.1 to 3, more typically 1.1 to 2. Molecular weight values are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0105] The polymer may be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein may be combined using an appropriate solvent and an initiator, or may be fed separately and polymerized in a reactor. For example, the polymer may be obtained by polymerization of the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with actinic radiation at an effective wavelength, or a combination thereof.

[0106] In some embodiments, one or more non-solvent alkali-insoluble substrates may be metal-containing materials. Exemplary metal-containing materials include organometallic resists (e.g., photo-induced crosslinkable organometallic resists), metal oxide resists, or combinations thereof. In some embodiments, the metal-containing material may include Sn, Zr, Hf, Si, Ge, Se, Cr, Mo, W, V, Nb, Ta, P, Sb, Ti, Ce, Ru, Sb, Y, Ga, Cr, Fe, Co, Ru, Al, In, Sc, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zn, Co, Ni, Mn, Mg, Ca, Sr, Ba, or combinations thereof. Typically, the metal-containing material may include Sn, Zr, Hf, Si, Ge, Se, or combinations thereof.

[0107] One or more non-solvent alkali-insoluble substrates are present in a total amount exceeding 50% by weight based on the total solids content of the photoresist composition. For example, one or more non-solvent alkali-insoluble substrates may be present in a total amount of 50% to 99% by weight, typically 60% to 95% by weight or 70% to 90% by weight based on the total solids content of the photoresist composition.

[0108] The photoresist composition further comprises a solvent for dissolving the components of the composition and facilitating its coating on a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and 1-chlorohexane, alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) (DAA), ethers such as propylene glycol monomethyl ether (PGME), diethyl ether, tetrahydrofuran, 1,4-dioxane and anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and These solvents include ketones such as cyclohexanone (CHO), esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and acetate acetate, lactones such as gamma-butyrolactone (GBL) and epsilon-caprolactone, lactams such as N-methylpyrrolidone, nitriles such as acetonitrile and propionitrile, cyclic or acyclic carbonate esters such as propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and propylene carbonate, polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide, water, or combinations thereof. Of these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, DAA, or combinations thereof.

[0109] The total solvent content in a photoresist composition (i.e., the cumulative solvent content for all solvents) is typically 40–99% by weight, for example, 60–99% or 85–99% by weight, based on the total solids content of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the coated photoresist layer and the coating conditions.

[0110] In some embodiments, the photoresist composition may further include a substance containing one or more base-unstable groups ("base-unstable substance"). As referred to herein, a base-unstable group is a functional group that can undergo a cleavage reaction in the presence of an aqueous alkaline developer after the exposure and post-exposure baking steps to provide polar groups such as hydroxyl, carboxylic acid, sulfonic acid, etc. The base-unstable group will not react significantly (e.g., not undergo bond cleavage) before the development step of the photoresist composition containing the base-unstable group. Therefore, for example, the base-unstable group will be substantially inert during the pre-exposure soft bake, exposure, and post-exposure bake steps. "Substantially inert" means that 5% or less, typically 1% or less, of the base-unstable group (or site) decomposes, cleaves, or reacts during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-unstable group reacts under typical photoresist development conditions using an aqueous alkaline photoresist developer, such as an aqueous solution of 0.26 N (N) tetramethylammonium hydroxide (TMAH). For example, a 0.26N TMAH aqueous solution can be used for single-paddle development or dynamic development, and the 0.26N TMAH developer is distributed to the imaged photoresist layer for an appropriate time, such as 10 to 120 seconds (s). Exemplary base-unstable groups are ester groups, typically fluorinated ester groups. Preferably, the base-unstable material is substantially miscible with the first and / or second polymer and other solid components of the photoresist composition, and has a lower surface energy than the first and / or second polymer and other solid components of the photoresist composition. When coated onto a substrate, the base-unstable material can thereby be separated from the other solid components of the photoresist composition to the upper surface of the formed photoresist layer.

[0111] In some embodiments, the base-unstable material may be a polymeric material, also referred to herein as a base-unstable polymer, and a base-unstable polymer may comprise one or more repeating units containing one or more base-unstable groups. For example, a base-unstable polymer may comprise two or more repeating units containing the same or different base-unstable groups. A preferred base-unstable polymer comprises at least one repeating unit containing two or more base-unstable groups, for example, a repeating unit containing two or three base-unstable groups.

[0112] Base-unstable polymers can be prepared using any suitable method in the art, including those described herein for the first and second polymers. For example, base-unstable polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays at an effective wavelength, or a combination thereof. In addition or alternatively, one or more base-unstable groups can be grafted onto the polymer backbone using a suitable method.

[0113] In some embodiments, the base-unstable substance is a single molecule comprising one or more base-unstable ester groups, preferably one or more fluorinated ester groups. A base-unstable substance that is a single molecule typically has a molecular weight in the range of 50 to 1,500 Da. w It holds.

[0114] If present, the base-instability substance is typically present in the photoresist composition in an amount of 0.01 to 10% by weight or 2 to 7% by weight, typically 1 to 5% by weight, based on the total solids content of the photoresist composition.

[0115] In addition or alternatively, for base-unstable polymers, the photoresist composition may further include one or more polymers different from the above-mentioned non-solvent alkali-insoluble substrate. For example, a photoresist composition may include additional polymers as described above, but with different compositions. In addition or alternatively, one or more additional polymers may be selected from those well known in the art of photoresists, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene polymers, polyvinyl alcohols, or combinations thereof.

[0116] The photoresist composition may further contain one or more additional optional additives. For example, optional additives may include chemical dyes and contrast agents, striation inhibitors, plasticizers, rate accelerators, sensitizers, photodegradable deactivators (PDQ) (also known as photodegradable bases), basic deactivators, thermoacid generators, surfactants, or combinations thereof. If present, the optional additives are typically present in the photoresist composition in an amount of 0.01 to 10% by weight based on the total solids content of the photoresist composition.

[0117] PDQ generates a weak acid when irradiated. The acid generated from the photodegradable deactivator is not strong enough to react rapidly with acid-unstable groups present in the resist matrix. Exemplary photodegradable deactivators include, for example, photodegradable cations, preferably for example, C 1~20 Carboxylic acid or C 1~20This includes compounds useful for preparing strong acid-generating compounds paired with anions of weak acids (pKa>1), such as sulfonic acid anions. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, and salicylic acid. Exemplary sulfonic acids include p-toluenesulfonic acid and camphorsulfonic acid. In preferred embodiments, the photodegradable deactivator is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0118] The photodegradable inactivator may be in a non-polymeric or polymer-bound form. In the polymeric form, the photodegradable inactivator is present within the polymerization units on the first or second polymer. Polymerization units containing the photodegradable inactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0119] Examples of basic quenchers include, for example, linear aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(2-hydroxypropyl)ethylenediamine:n-tert-butyldiethanolamine, tris(2-acetoxyethyl)amine, 2,2',2'',2'''-(ethane-1,2-diyrbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol and 2,2',2''-nitrilotriethanol, and 1-(tert Cyclic aliphatic amines such as -butoxycarbonyl)-4-hydroxypiperidine, tert-butyl1-pyrrolidinecarboxylate, tert-butyl2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate and N-(2-acetoxyethyl)morpholine, aromatic amines such as pyridine, di-tert-butylpyridine and pyridinium, N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 , N 1 , N 3 , N 3Examples include linear and cyclic amides such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate, and their derivatives; ammonium salts such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines such as primary and secondary aldimines and ketimines; diazines such as optionally substituted pyrazines, piperazines, and phenazines; diazoles such as optionally substituted pyrazoles, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0120] Basic quenchers may be in a non-polymeric or polymer-bound form. If in a polymeric form, the quencher may be present within the repeating units of the polymer. Repeating units containing the quencher are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0121] Exemplary surfactants include fluorinated and non-fluorinated surfactants, and can be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation, and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656 and PF-6520 fluorosurfactants from Omnova. In some embodiments, the photoresist composition further comprises a surfactant polymer containing fluorine-containing repeating units.

[0122] A pattern-forming method using the photoresist composition of the present invention will now be described. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates, such as semiconductor wafers, polycrystalline silicon substrates, packaging substrates such as multi-chip modules, flat panel display substrates, substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), etc., can be used in the present invention, with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates may be in the form of wafers used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. Such substrates may be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), but wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that optionally contain the active or operable portion of the device to be formed.

[0123] Typically, one or more lithography layers, such as a hard mask layer (e.g., spin-on carbon (SOC), amorphous carbon, or metallic hard mask layer), a CVD layer (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer), an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of the substrate before coating with the photoresist composition of the present invention. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0124] Optionally, a layer of adhesion promoter may be applied to the substrate surface before coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, and hexamethyldisilazane, or aminosilane couplers such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from DuPont Electronics & Industrial (Marlborough, Massachusetts) under the names AP® 3000, AP® 8000, and AP® 9000S.

[0125] The photoresist composition can be coated onto a substrate by any suitable method such as spin coating, spray coating, dip coating, doctor blading, etc. For example, the application of a photoresist layer can be achieved by spin coating the photoresist in a solvent using a coating track, in which case the photoresist is distributed onto a rotating wafer. During distribution, the wafer is typically rotated for 15 to 120 seconds at a speed of up to 4,000 revolutions per minute (rpm), e.g., 200 to 3,000 rpm, e.g., 1,000 to 2,500 rpm, to obtain a layer of the photoresist composition on the substrate. It will be well understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and / or the total solid content of the composition. A photoresist composition layer formed from the composition of the present invention typically has a dry layer thickness of 1 nanometer (nm) to 120 micrometers (μm), preferably more than 5 nm to 110 μm, more preferably 6 to 100 μm. In some embodiments, the photoresist composition layer formed from the composition may have a dry layer thickness of 10 nm to 5 μm or 3 to 20 μm.

[0126] Photoresist compositions are typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The temperature and time of soft baking will depend, for example, on the photoresist composition and thickness. Soft baking temperatures are typically 80–170°C, more typically 90–150°C. Soft baking times are typically 10 seconds–20 minutes, more typically 1 minute–10 minutes, and even more typically 1 minute–2 minutes. The heating time can be easily determined by those skilled in the art based on the composition's components.

[0127] The photoresist layer is then pattern-exposed to activating radiation to create a difference in solubility between exposed and unexposed areas. The herein reference to exposure of a photoresist composition to activating radiation indicates that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions corresponding to the exposed and unexposed areas of the resist layer, respectively. Such exposure can instead be performed without a photomask in a direct writing method, typically used for electron beam lithography. The activating radiation typically has a wavelength of less than 400 nm, less than 300 nm, or less than 200 nm, and is 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV), or electron beam lithography is preferred. Preferably, the activating radiation is 248 nm radiation. This method is utilized in immersion or dry (non-immersion) lithography techniques. The exposure energy depends on the components of the exposure tool and photoresist composition, and is typically 1 to 200 millijoules (mJ / cm²) per square centimeter. 2 ), preferably 10 to 100 mJ / cm² 2 More preferably 20-50 mJ / cm² 2 That is the case.

[0128] Following the exposure of the photoresist layer, a post-exposure bake (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for PEB will depend, for example, on the photoresist composition and layer thickness. PEB is typically performed at a temperature of 70-150°C, preferably 75-120°C, and for 30-120 seconds. A latent image is formed in the photoresist, defined by a polarity switching region (exposed region) and a non-switching region (unexposed region).

[0129] The exposed photoresist layer is then developed with a suitable developer to selectively remove the soluble regions of the layer, while the remaining insoluble regions form the resulting photoresist pattern relief image. In a positive-tone development (PTD) process, the exposed regions of the photoresist layer are removed during development, leaving the unexposed regions. Conversely, in a negative-tone development (NTD) process, the exposed regions of the photoresist layer remain, and the unexposed regions are removed during development. The application of the developer can be achieved by any suitable method as described above for the application of the photoresist composition, with spin coating being a typical example. The development time is the effective period for removing the soluble regions of the photoresist, typically 5 to 60 seconds. Development is usually carried out at room temperature.

[0130] Suitable developers for the PTD process include aqueous base developers, such as quaternary ammonium hydroxide solutions like tetramethylammonium hydroxide (TMAH), preferably 0.26 N (N) TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent systems, meaning that the cumulative organic solvent content in the developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0131] A coated substrate can be formed from the photoresist composition of the present invention. Such a coated substrate comprises (a) a substrate having one or more layers patterned on its surface, and (b) a layer of the photoresist composition covering one or more patterned layers.

[0132] A photoresist pattern can be used, for example, as an etching mask, thereby enabling the transfer of the pattern to one or more consecutive underlying layers by known etching techniques, typically dry etching such as reactive ion etching. A photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, and it can subsequently be used as an etching mask for pattern transfer to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such patterning processes, photoresist compositions can be used to manufacture semiconductor devices and other electronic devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, etc.

[0133] The present invention is further illustrated by the following non-limiting embodiments. [Examples]

[0134] All reactions were carried out under ambient atmospheric conditions. All chemicals were used directly from suppliers. Unless otherwise specified, nuclear magnetic resonance (NMR) spectra of all compounds were obtained using a 400 MHz spectrometer. Chemical shifts are reported as δ (parts per million, ppm) values ​​relative to the internal deuterated chloroform residual signal. Multiplicity is indicated by s (singlet), d (doublet), t (triplet), m (multiplet), dd (doublet of doublets), dt (doublet of triplets), tt (triplet of triplets), and br (broad singlet).

[0135] Synthesis of potassium 4-carboxy-2-hydroxybenzenesulfonate. [ka] 50 grams of 3-hydroxybenzoic acid were dissolved in 100 milliliters of sulfuric acid, heated to 90°C, and then 20 mL of a 30% SO3 solution in H2SO4 was added dropwise. The reaction mixture was held at 90°C for 16 hours, cooled to room temperature, and quenched with 120 mL of ice water. 150 mL of 25% by weight KOH aqueous solution was added, the resulting solid was filtered, co-distilled with toluene (3 × 100 mL), washed with acetone (2 × 100 mL), and dried at 50°C for 8 hours to obtain potassium 4-carboxy-2-hydroxybenzenesulfonate as a light brown solid (68 g, 73%). 1 ¹H-NMR (400MHz, dimethyl sulfoxide-d6 (DMSO-d6)): δ 10.6 ppm (broad singlet; 1H), 7.54 ppm (d, J=8.4Hz, 1H), 7.37 ppm (dd, J=8.0, 1.6Hz, 1H), and 7.28 ppm (d, J=1.6Hz, 1H). Electrospray ionization mass spectrometry (ESI-MS): [MK] - :217.16.

[0136] Synthesis of potassium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate. [ka] Concentrated H2SO4 (1.5 mL) and n-butanol (54 mL, n-BuOH) were added to a stirred solution of potassium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (15 g) in toluene (150 mL) equipped with a Dean Stark apparatus. The resulting mixture was heated under reflux at 100°C for 48 hours. The reaction mixture was cooled to room temperature, the resulting solid was filtered, the filtrate was concentrated under reduced pressure, dissolved in ethyl acetate (300 mL), washed with water (3 × 100 mL), washed with brine (100 mL), dried over Na2SO4, and then concentrated under reduced pressure. The crude product was purified by washing with n-pentane (50 mL) and then acetonitrile (50 mL), and concentrated under reduced pressure to obtain potassium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate as a pale yellow solid (6.0 g, 33%). 1 H-NMR(400MHz,DMSO-d6):δ 10.6ppm(s,1H),7.57ppm(d,J=8.0Hz,1H),7.39ppm(dd,J=8.0,1.6Hz,1H),7.30ppm(d,J=1.6Hz,1H),4.25 ppm(t,J=6.4Hz,2H),1.72-1.65ppm(m,2H),1.44-1.38ppm(m,2H) and 0.93ppm(t,J=7.6Hz,3H);ESI-MS:[MK] - :273.22.

[0137] Synthesis of triphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-1). [ka] Potassium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (9.09 g) and triphenylsulfonium bromide (10.0 g) were added to water (50 mL) and dichloromethane (200 mL, DCM), and the resulting mixture was stirred at room temperature for 4 hours. The reaction mixture was diluted with dichloromethane (200 mL), washed with water (3 × 100 mL), followed by brine (100 mL), dried over Na2SO4, and concentrated under reduced pressure to obtain triphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-1) as a viscous oil (13.0 g, 83%). 1 H-NMR(400MHz,DMSO-d6):δ 10.65ppm(s,1H),7.89-7.77ppm(m,15H),7.58ppm(d,J=8.0Hz,1H),7.39ppm(dd,J=8.0,1.6Hz,1H),7.30ppm(d,J=1.6 Hz,1H), 4.25ppm(t,J=6.8Hz,2H),1.71-1.64ppm(m,2H),1.45-1.38ppm(m,2H) and 0.92ppm(t,J=7.6Hz,3H);ESI-MS:[M] - :273.13 and [M] + :263.25.

[0138] Synthesis of bis(4-(tert-butyl)phenyl)iodonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-2). [ka] Sodium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (9.78 g) and bis(4-(tert-butyl)phenyl)iodonium acetate (13.6 g) were added to water (300 mL) and dichloromethane (300 mL), and the resulting mixture was stirred at room temperature for 16 hours. The organic fraction was washed with water (4 × 300 mL), concentrated under reduced pressure to remove most of the volatile substances, and the remaining solution was slowly poured into methyl t-butyl ether (700 mL). The precipitate was collected and dried under vacuum to obtain bis(4-(tert-butyl)phenyl)iodonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-2) as a white solid (13.0 g, 59%). 1 H NMR(499MHz,acetone-d6)δ 10.70ppm(s,1H),8.26-8.15ppm(m,4H),7.64-7.57ppm(m,4H),7.56-7.51ppm(m,1H),7.41-7.31ppm(m,2H),4.29ppm(t ,J=6.5Hz,2H),1.75ppm(dd,J=9.0,7.8,6.5Hz,2H),1.57-1.45ppm(m,2H),1.32ppm(s,18H) and 0.99ppm(t,J=7.4Hz,3H).

[0139] Synthesis of potassium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate. [ka] Concentrated H2SO4 (1.0 mL) and n-heptanol (45.7 mL) were added to a stirred solution of potassium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (10 g) in toluene (100 mL) equipped with a Dean Stark apparatus, and the mixture was heated under reflux at 100°C for 32 hours. The reaction mixture was cooled to room temperature, the resulting solid was filtered, the filtrate was concentrated under reduced pressure, dissolved in ethyl acetate (600 mL), washed with water (3 × 150 mL), washed with brine (150 mL), dried over Na2SO4, and concentrated under reduced pressure. The crude product was purified by washing with acetonitrile (40 mL) and concentrated under reduced pressure to obtain potassium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate as a grayish-white solid (8.0 g, 58%). 1 H-NMR(400MHz,DMSO-d6):δ 10.64ppm(s,1H),7.57ppm(d,J=8.0Hz,1H),7.38ppm(dd,J=8.0,1.6Hz,1H),7.29ppm(d,J=1.2Hz,1H),4.25 ppm(t,J=6.8Hz,2H),1.73-1.66ppm(m,2H),1.40-1.27ppm(m,8H) and 0.86ppm(t,J=4.0Hz,3H);ESI-MS:[MK] - :315.26.

[0140] Synthesis of triphenylsulfonium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate (PAG-3). [ka] Potassium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate (4.0 g) and triphenylsulfonium bromide (4.12 g) were dissolved in water (20 mL) and dichloromethane (80 mL), and the mixture was stirred at room temperature for 4 hours. The reaction mixture was diluted with CH2Cl2 (200 mL), washed with water (5 × 75 mL), washed with brine (75 mL), dried over Na2SO4, and concentrated under reduced pressure to obtain triphenylsulfonium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate (PAG-3) as a viscous oil (5.5 g, 82%). 1 H-NMR(400MHz,DMSO-d6):δ 10.65ppm(s,1H),7.88-7.77ppm(m,15H),7.57ppm(d,J=8.0Hz,1H),7.38ppm(dd,J=8.0,1.6Hz,1H),7.30ppm(d,J=1.6 Hz,1H),4.25ppm(t,J=6.8Hz,2H),1.73-1.66ppm(m,2H),1.39-1.27ppm(m,8H) and 0.86ppm(t,J=6.8Hz,3H);ESI-MS:[M] - :315.26,[M] + :263.21.

[0141] Synthesis of adamantane methanol. [ka] A 46 mL solution of 2 M lithium aluminum hydride in tetrahydrofuran (THF) was added dropwise to a 100 mL solution of adamantane-1-carboxylic acid (5 g) in THF at 0°C under nitrogen. The mixture was slowly warmed to room temperature and stirred for 16 hours. The reaction mixture was then cooled to 0°C, quenched with 50 mL of cold saturated Na₂SO₄ aqueous solution, diluted with 50 mL of ethyl acetate, and stirred for 15 minutes. The resulting solution was filtered through Celite and washed with 20 mL of ethyl acetate. The filtrate was separated, the ethyl acetate layer was washed with 30 mL of brine, dried over Na₂SO₄, and concentrated under reduced pressure to obtain adamantane methanol as a grayish-white solid (4.1 g, 88.9%). 1H-NMR(400MHz,DMSO-d6):δ 4.27ppm(t,J=5.6Hz,1H),2.95ppm(dd,J=5.6Hz,2H),1.92ppm(m,3H),1.68-1.65ppm(m,3H),1.60-1.56ppm(m,3H) and 1.43ppm(d,J=2.4Hz,6H).

[0142] Synthesis of 4-(((adamantan-1-yl)methoxy)carbonyl)-2-hydroxybenzenesulfonate (PAG-4). [ka] To a stirred solution of triphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (2.0 g), adamantane methanol (3.1 g) and p-toluenesulfonic acid-H2O (0.15 g) were added in toluene (20 mL) at room temperature. A Dean-Stark apparatus was attached to the reaction apparatus, and the reaction mixture was heated to 140 °C for 3 days. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, dissolved in dichloromethane (20 mL), washed with 10% NaHCO3 solution (10 mL), washed with brine (10 mL), dried over Na2SO4, and concentrated under reduced pressure. The crude product was washed with THF:petroleum ether (2 × 1:2, 20 mL:40 mL), and concentrated under reduced pressure to obtain 4-(((adamantan-1-yl)methoxy)carbonyl)-2-hydroxybenzenesulfonate (PAG-4) as a grayish-white solid (1.4 g, 59.8%). 1 H-NMR(400MHz,DMSO-d6):δ 10.67ppm(s,1H),7.88-7.76ppm(m,15H),7.59ppm(d,J=8.0Hz,1H)7.41ppm(dd,J=8.0,1.6Hz,1H),7.31ppm(d,J=1.6Hz, 1H)3.87ppm(s,2H),1.97ppm(m,3H),1.71-1.63ppm(m,6H) and 1.58ppm(d,J=2.4Hz,6H).LC-MS[M]+=263.21,[M]-=365.31.

[0143] Synthesis of triphenylsulfonium 4-carboxy-2-hydroxybenzenesulfonate (PAG-5). [ka] Triphenylsulfonium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate (10 g) was dissolved in 6N HCl (100 mL) and heated to 90°C with stirring for 16 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, co-distilled with toluene (2 × 50 mL), concentrated under reduced pressure, washed with THF:hexane (1:2, 150 mL), filtered, and dried to obtain triphenylsulfonium 4-carboxy-2-hydroxybenzenesulfonate (PAG-5) as a grayish-white solid (7.5 g, 84%). 1 H-NMR(400MHz,DMSO-d6):δ 12.98ppm(s,1H),10.61ppm(s,1H),7.88-7.76ppm(m,15H),7.54ppm(d,J=8.0H z,1H),7.36ppm(dd,J=8.0,1.2Hz,1H) and 7.28ppm(d,J=1.2Hz,1H);ESI-MS:[M] - :217.16,[M] + :263.25.

[0144] Synthesis of (3-chloropropyl)diphenylsulfonium tetrafluoroborate [ka] 4.18 g of tetrafluoroborate was added to a solution of nitromethane (10 ml) containing diphenyl sulfide (5.0 g) and 1-chloro-3-iodopropane (18.67 g), and the resulting mixture was stirred at room temperature for 16 hours. The reaction mixture was then diluted with dichloromethane (50 mL), filtered through a Fluorosil pad, and washed with CH2Cl2 (25 mL). The filtrate was concentrated under reduced pressure, washed with diethyl ether (20 mL), washed with petroleum ether (20 mL), and dried to obtain (3-chloropropyl)diphenylsulfonium tetrafluoroborate as a grayish-white solid (6.2 g, 66%). 1H-NMR(400MHz,DMSO-d6):δ 8.12-8.09ppm(m,4H),7.83-7.81ppm(m,2H),7.79-7.73ppm(m,4H),4.43ppm(t,J =7.6Hz,2H), 3.80ppm(t,J=6.4Hz,2H), and 2.17-2.11ppm(m,2H).ESI-MS:[M-BF4] + :263.17.

[0145] Synthesis of cyclopropyldiphenylsulfonium tetrafluoroborate. [ka] 60% by weight of NaH (850 mg) was added at 0°C to a solution of (3-chloropropyl)diphenylsulfonium tetrafluoroborate (6.2 g) in THF (124 mL). The reaction mixture was warmed to room temperature and stirred for a total of 16 hours. Then, 48% by weight of HBF4 aqueous solution (1.3 mL) was added, followed by 0.78 g of NaBF4 aqueous solution (21 mL), and the mixture was stirred for a further 30 minutes. The reaction mixture was diluted with dichloromethane (60 mL), washed with water (2 × 30 mL), and the aqueous layer was extracted with dichloromethane (30 mL). The combined organic layers were dried over Na₂SO₄ and concentrated under reduced pressure. The crude product was washed with diethyl ether (20 mL), filtered, and dried to obtain cyclopropyldiphenylsulfonium tetrafluoroborate as a grayish-white solid (2.7 g, 48%). 1 H-NMR(400MHz,DMSO-d6):δ 8.05-8.03ppm(m,4H),7.85-7.75ppm(m,6H),3.89ppm(m,1H),1.63-1.59ppm(m,2H) and 1.55-1.49ppm(m,2H).ESI-MS:[M-BF4] + :227.21.

[0146] Synthesis of cyclopropyldiphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-6). [ka] Potassium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (2.48 g) and cyclopropyldiphenylsulfonium tetrafluoroborate (2.5 g) were dissolved in dichloromethane (50 mL) and water (12.5 mL), and the reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was diluted with dichloromethane (120 mL), washed with water (5 × 30 mL), washed with brine (30 mL), dried over Na₂SO₄, and concentrated under reduced pressure to obtain cyclopropyldiphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-6) as a light brown liquid (3.8 g, 95%). 1 H-NMR(400MHz,DMSO-d6):δ 10.65ppm(s,1H),8.05-8.03ppm(m,4H),7.84-7.75ppm(m,6H),7.58ppm(d, J=8.0Hz,1H),7.39ppm(dd,J=8.0,1.6Hz,1H),7.30ppm(d,J=1.6Hz,1H),4.2 6ppm(t,J=6.8Hz,2H),3.94-3.89ppm(m,1H),1.71-1.59ppm(m,4H),1.57-1. 50ppm(m,2H), 1.48-1.42ppm(m,2H) and 0.93ppm(t,J=7.2Hz,3H).ESI-MS:[M] - :273.36,[M] + :227.26.

[0147] Synthesis of 2,4-dihydroxybenzenesulfonic acid. [ka] Chlorosulfonic acid (0.61 mL) was added dropwise to a solution of resorcinol (1.0 g) in nitrobenzene (10 mL) at 0°C. The reaction mixture was heated to room temperature, stirred for a further 4 hours, filtered, washed with petroleum ether (50 mL), dried, dissolved in THF (20 mL), concentrated under reduced pressure, washed with ethyl acetate:petroleum ether (1:3, 20 mL), and dried to obtain 2,4-dihydroxybenzenesulfonic acid as a brown liquid, which was used directly in the next step (0.9 g, 52%). ESI-MS:[M] - :189.08.

[0148] Synthesis of triphenylsulfonium 2,4-dihydroxybenzenesulfonate (PAG-7). [ka] Silver oxide (0.74 g) was added to a solution of triphenylsulfonium bromide (1.0 g) in methanol (20 mL), and the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was then filtered through Celite and washed with methanol (10 mL). 2,4-dihydroxybenzenesulfonic acid (0.66 g) was added to the methanol layer, and the mixture was stirred at room temperature for 1 hour. The mixture was concentrated under reduced pressure, washed with ethyl acetate (2 × 10 mL), and dried to obtain triphenylsulfonium 2,4-dihydroxybenzenesulfonate (PAG-7) as a gray solid (1.2 g, 91.6%). 1 H-NMR(400MHz,DMSO-d6):δ 10.53ppm(s,1H),9.48ppm(s,1H),7.88-7.76ppm(m,15H),7.21ppm(d,J=8.4H z,1H),6.19ppm(dd,J=8.4,2.4Hz,1H) and 6.10ppm(d,J=2.0Hz,1H);ESI-MS:[M] - :189.08 and [M] + :263.25.

[0149] Synthesis of potassium 1-hydroxynaphthalene-2-sulfonate. [ka] 1-Hydroxynaphthalene (5.0 g) was dissolved in acetic acid (2.5 mL, AcOH) and heated at 55°C for 10 minutes. Then, H2SO4 (2.8 mL) was added dropwise, and the reaction mixture was held at 55°C to 60°C for a further 16 hours. Next, potassium chloride (15 g) in water (50 mL) was added to the reaction mixture at 60°C, and then cooled to 20°C. The resulting solid was filtered, washed with ethyl acetate (50 mL), dried, and recrystallized from water (3 × 50 mL) to obtain potassium 1-hydroxynaphthalene-2-sulfonate as a grayish-white solid (1.7 g, 18.7%).1 H-NMR(400MHz,DMSO-d6):δ 11.60ppm(s,1H),8.15-8.17ppm(m,1H),7.82-7.80ppm(m,1H),7.55-7.46ppm(m,3H),7.31ppm(d,J=8.4Hz,1H) and 7.31ppm(d,J=8.4Hz,1H);ESI-MS:[MK] - :223.16.

[0150] Synthesis of triphenylsulfonium 1-hydroxynaphthylene-2-sulfonate (PAG-8). [ka] Triphenylsulfonium bromide (1.96 g) and potassium 1-hydroxynaphthylene-2-sulfonate (1.5 g) were dissolved in dichloromethane (30 mL) and water (15 mL), and the reaction mixture was stirred at room temperature for 16 hours. The layers were separated, and the aqueous layer was extracted with dichloromethane (30 mL). The combined organic layers were washed with water (5 × 10 mL) and concentrated under reduced pressure. The resulting product was washed with ethyl acetate and petroleum ether (1:3, 40 mL), dried, and triphenylsulfonium 1-hydroxynaphthylene-2-sulfonate (PAG-8) was obtained as a grayish-white solid (2.8 g, 30.7%). 1 H-NMR(400MHz,DMSO-d6):δ 11.61ppm(s,1H),8.16(d,J=8.0Hz,1H),7.88-7.76ppm(m,16H),7.54-7.46ppm(m,3H) and 7.31ppm(d,J=8.8Hz,1H);ESI-MS:[M] - :223.21 and [M] + :263.25.

[0151] Synthesis of potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate and potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate. [ka] Chlorosulfonic acid (17.5 mL) was added to 4-hydroxyisobenzofuran-1,3-dione (3.5 g) at 0°C. The reaction mixture was heated to room temperature and stirred at room temperature for 8 days. The reaction mixture was then cooled to 0°C, quenched with ice water (35 mL), and then 50% KOH aqueous solution (7.5 g, 15 mL) was added. The mixture was stirred for 30 minutes. The resulting solid was filtered, washed with THF (20 mL), washed with petroleum ether (80 mL), and dried to obtain a mixture of potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate and potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate (4.8 g, 75%) as a grayish-white solid, which was used directly in the next step. Liquid chromatography-mass spectrometry (LC-MS): [MK] - =261.07, [MK] + =245.12.

[0152] Synthesis of potassium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate. [ka] A mixture of potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate and potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate (3.5 g) in 1-butanol (40 mL) was mixed with p-toluenesulfonic acid monohydrate (300 mg, PTSA), and the reaction mixture was heated at 100°C for 6 days. The reaction mixture was then cooled to room temperature, filtered, washed with petroleum ether (70 mL), and dried under reduced pressure to obtain potassium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate (2.6 g, 54.1%) as a grayish-white solid, which was used directly in the next step. LC-MS: [MK] - =373.27.

[0153] Synthesis of triphenylsulfonium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-9). [ka] Potassium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate (2.3 g) and triphenylsulfonium bromide (1.60 g) were dissolved in dichloromethane (50 mL) and water (25 mL), and the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted with dichloromethane (50 mL), washed with 10 wt% aqueous sodium bicarbonate (2 × 30 mL), washed with water (5 × 30 mL), dried over Na₂SO₄, and concentrated under reduced pressure. The crude compound was suspended in THF (15 mL), stirred for 10 minutes, filtered, washed with an additional THF (15 mL), and dried under reduced pressure to obtain triphenylsulfonium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-9) as a grayish-white solid (2.4 g, 67.6%). 1 H-NMR(400MHz,DMSO-d6):δ 10.36ppm(s,1H),7.88-7.76ppm(m,15H),7.65ppm(d,J=8.8Hz,1H),6.90ppm(d,J=8.8Hz,1H),4.12ppm(t,J=6 .4Hz,2H),4.02ppm(t,J=6.8Hz,2H),1.61-1.53ppm(m,4H),1.41-1.31ppm(m,4H) and 0.91ppm(m,6H);LC-MS:[M] + =263.23,[M] - =373.39.

[0154] Synthesis of sodium 5-fluoro-2-hydroxybenzenesulfonate. [ka] Sulfuric acid (45.9 g) was added to 4-fluorophenol (15 g) at -10°C. The reaction mixture was slowly warmed to room temperature and stirred for 16 hours, then diluted with cold water (30 mL). After that, aqueous NaOH solution (1.0 eq) was added and stirred for 30 minutes. The resulting solid was filtered and dried under reduced pressure to obtain sodium 5-fluoro-2-hydroxybenzenesulfonate as a white solid (26 g, 90%). 1H-NMR(400MHz,DMSO-d6):δ 7.12ppm(dd,J=8.8,3.2Hz,1H),6.79ppm(td,J=8.8,3.6Hz,1H) and 6.63-6.60ppm(m,1H).ESI-MS:[M-Na] - :191.23.

[0155] Synthesis of triphenylsulfonium 5-fluoro-2-hydroxybenzenesulfonate (PAG-10). [ka] Sodium 5-fluoro-2-hydroxybenzenesulfonate (10.0 g) and triphenylsulfonium chloride (12.5 g) were dissolved in dichloromethane (200 mL) and water (100 mL), and the reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was diluted with dichloromethane (400 mL), washed with water (5 × 100 mL), and concentrated under reduced pressure. The crude product was washed with hexane (50 mL), filtered, and dried under reduced pressure to obtain 7.5 g of a white solid, which is 1 1H-NMR revealed an excess of triphenylsulfonium cations.

[0156] Impure triphenylsulfonium 5-fluoro-2-hydroxybenzenesulfonate (21.0 g) and sodium 5-fluoro-2-hydroxybenzenesulfonate (9.89 g), synthesized by the above method, were dissolved in dichloromethane (420 mL) and water (210 mL), and the reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was diluted with dichloromethane (400 mL) and washed with water (5 × 200 mL). The organic layer was concentrated under reduced pressure, washed with methyl t-butyl ether (250 mL), filtered, dried, dissolved in ethanol (40 mL), and hexane (160 mL) was added while vigorously stirring. The resulting solid was filtered and dried to obtain triphenylsulfonium 5-fluoro-2-hydroxybenzenesulfonate (PAG-10) as a white solid (20.1 g). 1H-NMR(400MHz,DMSO-d6):δ 10.2ppm(s,1H),7.80-7.76ppm(m,15H),7.14ppm(dd,J=8.4,3.2Hz,1H),7.09-7.04ppm(m,1H) and 6.78ppm(dd,J=9.2,4.8Hz,1H).ESI-MS:[M-Na] - :191.21 and [M] + :263.29.

[0157] Synthesis of butyl 3,5-dihydroxybenzoate. [ka] 2.5 g of p-toluenesulfonic acid monohydrate was added to a solution of 1-butanol (20 mL) and toluene (100 mL) containing 3,5-dihydroxybenzoic acid (10.0 g), and the reaction mixture was heated to 120°C for 16 hours. The reaction mixture was cooled to room temperature, quenched with ice water, and then extracted with ethyl acetate. The combined organic layer was washed with 10% NaHCO3 aqueous solution (2 × 100 mL) and concentrated under reduced pressure. The crude product was washed with ethyl acetate and petroleum ether (100 mL, 1:9 v / v), followed by dichloromethane and petroleum ether (100 mL, 1:9 v / v), and then dried to obtain butyl 3,5-dihydroxybenzoate as a brown viscous oil (10.1 g, 74%). 1 H-NMR(400MHz,DMSO-d6):δ 9.60ppm(s,2H),6.82ppm(d,J=2.4Hz,2H),6.43ppm(d,J=2.4Hz,1H),4.21ppm(t,J=6. 8Hz,2H),1.69-1.62(m,2H),1.45-1.36ppm(m,2H) and 0.93(t,J=7.4Hz,3H).LC-MS[MH] - =209.25.

[0158] Synthesis of sodium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate. [ka] Chlorosulfonic acid (7.6 mL) was added at 0±5°C to a solution of nitrobenzene (400 mL) containing butyl 3,5-dihydroxybenzoate (20.0 g), and the mixture was stirred at room temperature for 5 days. The reaction mixture was cooled to 0±5°C, quenched with cold water (200 mL), and sodium hydroxide aqueous solution (2 equivalents) was added. The product was extracted with petroleum ether (4 × 200 mL), and the organic layer was discarded. The aqueous layer was extracted with ethyl acetate and methanol (9:1, 3 × 200 mL), and the combined organic layer was concentrated under reduced pressure. The resulting crude product was washed with ethyl acetate and petroleum ether (1:1, 200 mL), followed by ethyl acetate and methanol (19:1, 200 mL), to obtain sodium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate as a grayish-white solid (9.0 g, 30%). 1 H-NMR(400MHz,DMSO-d6):δ 9.93ppm(s,2H),6.84ppm(s,2H),4.23ppm(t,J=6.4Hz,2H),1.70-1.63ppm(m,2H),1.45-1.35ppm(m,2H) and 0.93ppm(t,J=7.4Hz,3H).LC-MS[M-Na] - =289.26.

[0159] Synthesis of triphenylsulfonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-11). [ka] Triphenylsulfonium bromide (8.2 g) and sodium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (7.3 g) were dissolved in dichloromethane (150 mL) and water (80 mL), and the reaction mixture was stirred at room temperature for 16 hours. The organic layer was washed with water (3 × 100 mL), concentrated under reduced pressure, and triphenylsulfonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-11) was obtained as a viscous brown oil (12.3 g, 95%). 1H-NMR(400MHz,DMSO-d6):δ 9.92ppm(s,2H),7.89-7.76ppm(m,15H),6.85ppm(s,2H),4.23ppm(t,J=6.4Hz,2H), 1.70-1.63ppm(m,2H), 1.43-1.37ppm(m,2H) and 0.92ppm(t,J=7.6Hz,3H).LC-MS:[M] + =263.33,[M] - =289.26.

[0160] Synthesis of 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium-4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-12). [ka] 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium triflate (6.80 g) and sodium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (5.0 g) were mixed in dichloromethane (160 mL) and water (160 mL), and the reaction mixture was stirred at room temperature for 16 hours. The organic layer was washed with water (7 × 400 mL) and concentrated under reduced pressure to obtain 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-12) as a white solid (6.80 g, 81%). 1 H-NMR (499MHz, acetone-d6):δ 10.13-9.87ppm(m,2H),8.20-8.04ppm(m,2H),7.93-7.75ppm(m,2H),6.95ppm(s,2H),4.54-4.42ppm(m,2H),4.27ppm(t,J=6.6Hz,2H), 4.25-4.15ppm(m,2H), 4.14-3.95ppm(m,4H), 1.79-1.70ppm(m,2H), 1.55-1.43ppm(m,2H), 1.38ppm(s,9H) and 0.98ppm(t,J=7.4Hz,3H).

[0161] Synthesis of 3-(butylthio)phenol. [ka] 10 g of 3-mercaptophenol in 50 mL of methanol was added dropwise to a solution of 3.3 g of sodium hydroxide in 50 mL of methanol, and the reaction mixture was stirred at room temperature for 30 minutes. Then, 8.8 mL of 1-bromobutane was added dropwise at room temperature, and the reaction mixture was heated to 70°C and stirred for 2 hours. The reaction mixture was then cooled to room temperature, concentrated under reduced pressure, dissolved in 200 mL of ethyl acetate, washed with 100 mL of water, concentrated under reduced pressure, and purified by flash column chromatography to obtain 3-(butylthio)phenol as a viscous brown oil (13.5 g, 93.5%). 1 H-NMR(400MHz,DMSO-d6):δ 9.48ppm(s,1H),7.08ppm(t,J=8Hz,1H),6.71-6.68ppm(m,2H),6.57-6.54ppm(m,1H),2.89ppm(t, LC-MS[M+H] + =183.28.

[0162] Synthesis of 3-(butylsulfonyl)phenol. [ka] A 30% by weight aqueous solution of H2O2 (55 mL) was added to a solution of 3-(butylthio)phenol (11.0 g) in acetic acid (55 mL), and the reaction mixture was stirred at room temperature for 2 days. The reaction mixture was then quenched with cold water (100 mL), extracted with ethyl acetate (2 × 220 mL), washed with a 10% aqueous solution of NaHCO3 (5 × 200 mL), washed with water (5 × 200 mL), dried on Na2SO4, and concentrated under reduced pressure to obtain 3-(butylsulfonyl)phenol as a viscous brown oil (11.5 g, 89%). 1H-NMR(400MHz,DMSO-d6):δ 10.21ppm(s,1H),7.45ppm(t,J=8Hz,1H),7.31-7.28ppm(m,1H),7.23ppm(t,J=2.0Hz,1H),7.12-7.09ppm(m,1H ),3.25ppm(t,J=8.0Hz,2H),1.53-1.46ppm(m,2H),1.37-1.33ppm(m,2H) and 0.82ppm(t,J=7.6Hz,3H).LC-MS[MH] - =213.25.

[0163] Synthesis of sodium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate. [ka] Fuming sulfuric acid (10 mL) was added at 50°C to a solution of 3-(butylsulfonyl)phenol (9.0 g) in H2SO4 (5 mL), and the reaction mixture was heated to 80°C for 16 hours. The reaction mixture was then cooled to 0°C, diluted with cold water (50 mL), titrated with sodium hydroxide to pH 7-8, and stirred for a further 30 minutes. The resulting solid was filtered, washed with THF (100 mL), washed with ethyl acetate (100 mL), and dried under reduced pressure to obtain sodium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate as a grayish-white solid (9.5 g, 72%). 1 H-NMR(400MHz,DMSO-d6):δ 10.86ppm(s,1H),7.69ppm(d,J=8.4Hz,1H),7.30ppm(dd,J=8.0,1.6Hz,1H),7.24ppm(t,J=1.6Hz,1H),3.28 ppm(t,J=8.0,Hz,2H),1.50-1.47ppm(m,2H),1.35-1.29ppm(m,2H) and 0.82ppm(t,J=7.2Hz,3H).LC-MS[M-Na] - =293.22.

[0164] Synthesis of triphenylsulfonium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate (PAG-13). [ka] Triphenylsulfonium bromide (8.2 g) and sodium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate (7.5 g) were dissolved in dichloromethane (160 mL) and water (160 mL), and the reaction mixture was stirred at room temperature for 16 hours. The organic layer was separated, washed with water (3 × 150 mL), concentrated under reduced pressure, and polished with hexane and ethanol (3:1, 100 mL) to obtain triphenylsulfonium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate (PAG-13) as a white solid (12.3 g, 94%). 1 H-NMR(400MHz,DMSO-d6):δ 10.87ppm(s,1H),7.88-7.76ppm(m,15H),7.70ppm(d,J=8Hz,1H),7.31ppm(dd,J=8.0,2.0Hz,1H),7.24ppm(d,J= 2.0Hz,1H), 3.29ppm(m,2H), 1.52-1.44ppm(m,2H), 1.35-1.29ppm(m,2H) and 0.82ppm(t,J=7.2Hz,3H).LC-MS:[M] + 263.33,[M] - =293.22.

[0165] Synthesis of 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium-4-(butylsulfonyl)-2-hydroxybenzenesulfonate (PAG-14). [ka] 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium triflate (6.8 g) and sodium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate (5.1 g) were dissolved in dichloromethane (160 mL) and water (160 mL), and the reaction mixture was stirred at room temperature for 16 hours. The organic layer was separated, washed with water (3 × 250 mL), and concentrated under reduced pressure to obtain 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate (PAG-14) as a white solid (1.7 g, 20%).1 H-NMR(499MHz, acetone-d6)δ 11.28ppm(s,1H),8.18-8.07ppm(m,2H),7.89-7.84ppm(m,2H),7.81ppm(dd,J=8.0,1. 2Hz,2H),7.30ppm(dd,J=8.0,1.8Hz,1H),7.26ppm(d,J=1.8Hz,1H),4.56-4.41ppm(m, 2H),4.25-4.18ppm(m,2H),4.15-4.00ppm(m,4H),3.22-3.16ppm(m,2H),1.69-1.58pp m(m,2H), 1.44ppm(dt,J=14.8,7.4Hz,2H), 1.39ppm(s,9H) and 0.90ppm(t,J=7.4Hz,3H).

[0166] Synthesis of sodium 2,4,6-trihydroxybenzenesulfonate. [ka] Fuming sulfuric acid (6 mL) was added at 0°C to a solution of acetonitrile (200 mL) containing benzene-1,3,5-triol (10.0 g). The reaction mixture was then heated to room temperature, stirred for 4 hours, diluted with cold water (200 mL), extracted with methyl t-butyl ether (4 × 100 mL), and the organic layer was discarded. The aqueous layer was adjusted to pH 7-8 at 0°C using an aqueous sodium hydroxide solution, the resulting solid was filtered and dried to obtain sodium 2,4,6-trihydroxybenzenesulfonate (13.6 g, 83%), which was used directly in the next step without further purification.

[0167] Synthesis of triphenylsulfonium 2,4,6-trihydroxybenzenesulfonate (PAG-15). [ka] Triphenylsulfonium bromide (8.0 g) and sodium 2,4,6-trihydroxybenzenesulfonate (10.0 g) were dissolved in dichloromethane (250 mL) and water (125 mL), and the reaction mixture was stirred at room temperature for 16 hours. The organic layer was washed with water (3 × 125 mL) and concentrated under reduced pressure to obtain triphenylsulfonium 2,4,6-trihydroxybenzenesulfonate (PAG-15) as a viscous brown oil (5.2 g, 25%). Further purification was achieved by washing with hexane and ethanol (2:1). 1 H-NMR(400MHz,DMSO-d6)δ:9.61ppm(s,2H),9.46ppm(s,1H),7.89-7.77ppm(m,15H) and 5.70ppm(s,2H).LC-MS:[M] + =263.33,[M] - =205.21.

[0168] Synthesis of triphenylsulfonium 2-sulfobenzoic acid (PAG-16). [ka] Triphenylsulfonium bromide (33.98 g) and ammonium 2-sulfobenzoic acid (23.87 g) were dissolved in dichloromethane (550 mL) and water (550 mL), and the reaction mixture was stirred at room temperature for 16 hours. The organic layer was washed with water (6 × 500 mL) and concentrated under reduced pressure to obtain triphenylsulfonium 2-sulfobenzoic acid (PAG-16) as a white solid (16.6 g, 36%). 1 H-NMR(499MHz,DMSO-d6)δ 14.21ppm(s,1H),7.92-7.72ppm(m,17H),7.56ppm(td,J=7.6,1.5Hz,1H) and 7.50ppm(td,J=7.5,1.5Hz,1H).

[0169] Synthesis of 4-(tert-butyl)phenyl)diphenylsulfonium 2-sulfobenzoic acid (PAG-17). [ka] (4-(tert-butyl)phenyl)diphenylsulfonium bromide (47.93 g) and ammonium 2-sulfobenzoic acid (31.57 g) were dissolved in dichloromethane (600 mL) and water (600 mL), and the reaction mixture was stirred at room temperature for 16 hours. The organic layer was washed with water (6 × 500 mL) and concentrated under reduced pressure to obtain 4-(tert-butyl)phenyl)diphenylsulfonium 2-sulfobenzoic acid (PAG-17) as a rubbery solid (37.5 g, 60%). 1 ¹H-NMR (499MHz, acetone-d6)δ 15.09 ppm (s, 1H), 8.02 ppm (dd, J=7.6, 1.5Hz, 1H), 7.97 ppm (dd, J=7.6, 1.6Hz, 1H), 7.95-7.80 ppm (m, 14H), 7.52 ppm (td, J=7.5, 1.6Hz, 1H), 7.47 ppm (td, J=7.5, 1.5Hz, 1H), and 1.38 ppm (s, 9H).

[0170] Synthesis of sodium 4-carboxy-2-hydroxybenzene sulfonate. [ka] Sulfur trioxide trimethylamine (SO3.TMA, 5g) was added to a solution of 3-hydroxybenzoic acid (50.2g) in H2SO4 (100mL), heated to 90°C, and stirred for 16 hours. The reaction mixture was cooled to 0°C and diluted with water (500mL). Water (100mL) containing sodium hydroxide (29g) was added at 0°C, and the resulting mixture was stirred for 30 minutes. The precipitate was washed with acetone (600mL), ethyl acetate (200mL), and petroleum ether (500mL) in the above order, and then dried to obtain sodium 4-carboxy-2-hydroxybenzenesulfonate (82.5g, 94.9%) as a grayish-white solid. 1 ¹H-NMR (400MHz, DMSO-d6): δ 12.93 (1H, broad singlet), 10.58 (1H, S), 7.55 (d, J=8Hz, 1H), 7.37 (dd, J=8, 1.6Hz, 1H), 7.29 (d, J=1.6Hz, 1H).

[0171] Synthesis of sodium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate. [ka] PTSA-H2O (5 g) was added to a solution of sodium 4-carboxy-2-hydroxybenzenesulfonate (50.0 g) in MeOH (500 mL) and heated at 70°C for 3 days. The reaction mixture was concentrated to half its volume, cooled to 0°C, and stirred for 30 minutes. The resulting solid was filtered, washed with methanol (200 mL) and petroleum ether (500 mL), and then dried to obtain sodium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (37.0 g, 70%) as a grayish-white solid. 1 H NMR (400MHz, DMSO-d6): δ 10.63(1H,S)7.57(d,J=8.0Hz,1H),7.39(dd,J=8.0,2.0Hz,1H),7.30(d,J=1.6Hz,1H),3.83(3H,S).

[0172] Synthesis of triphenylsulfonium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (PAG-18). [ka] Triphenylsulfonium bromide (8.2 g) and sodium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (10.3 g) were dissolved in water (100 mL) and DCM (200 mL), and the mixture was stirred at room temperature for 16 hours. The organic layer was then washed with 10% NaHCO3 aqueous solution (100 mL), and then with water (5 × 100 mL). The organic layer was concentrated under reduced pressure, washed with THF:petroleum ether (1:3,100 mL), and dried to obtain triphenylsulfonium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (18 g, 92.5%) as a grayish-white solid. 1H NMR (400MHz, DMSO-d6): δ 10.64(1H,S),7.88-7.76(m,15H),7.57(d,J=8.0Hz,1H),7.39(dd,J=8.0,2.0Hz,1H),7.30(d,J=1.6Hz,1H),3.83(3H,S).

[0173] Synthesis of bis(4-(tert-butyl)phenyl)iodonium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (PAG-19). [ka] Sodium 4-(methoxycarbonyl)-2-hydroxybenzenesulfonate (16.8 g) and bis(4-(tert-butyl)phenyl)iodonium acetate (27.1 g) were added to water (600 mL) and DCM (600 mL), and the resulting mixture was stirred at room temperature for 16 hours. The organic fraction was washed with water (5 × 500 mL), concentrated under reduced pressure to remove the solvent, and the remaining solution was slowly poured into methyl t-butyl ether (700 mL). The precipitate was collected and dried under vacuum to obtain bis(4-(tert-butyl)phenyl)iodonium 4-(methoxycarbonyl)-2-hydroxybenzenesulfonate as a white solid (28.5 g, 69%). 1 H NMR(499MHz,DMSO-d6)δ 10.66(s,1H),8.19-8.13(m,3H),7.61-7.52(m,4H),7.40(dd,J=8.1,1.7Hz,1H),7.32(d,J=1.7Hz,1H),3.84(s,2H),1.26(s,14H).

[0174] Synthesis of 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium-4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-20). [ka] 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium triflate (34.8 g) and sodium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (29.6 g) were dissolved in DCM (450 mL) and water (450 mL), and the reaction mixture was stirred at room temperature for 16 hours. The organic layer was washed with water (7 × 500 mL), concentrated under reduced pressure to remove the solvent, and the remaining solution was slowly poured into methyl t-butyl ether (700 mL). The precipitate was collected and dried under vacuum to obtain 4-(4-(tert-butyl)phenyl)-1,4-oxatian-4-ium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate as a white solid (39.1 g, 78%). 1 H NMR(499MHz,acetone-d6)δ 8.17-8.11(m,2H),7.89-7.82(m,2H),7.70(dd,J=8.0,1.1Hz,1H),7.45-7.37(m,2H),4.49(dt,J=14.0,3.8Hz,2H),4.32-4.19(m,4H),4 .16-4.03(m,4H),3.14(s,1H),2.84-2.77(m,2H),1.80-1.71(m,2H),1.55-1.44(m,2H),1.39(s,8H),1.14(s,3H),0.99(t,J=7.4Hz,3H).

[0175] Synthesis of sodium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate. [ka] A solution of sodium 4-carboxy-2-hydroxybenzenesulfonate (100 g) in ethanol (2 L) was mixed with concentrated hydrochloric acid (200 mL), and the resulting mixture was heated under reflux for 32 hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, dissolved in water (300 mL), extracted with 5% methanol (2 × 500 mL) in ethyl acetate, and concentrated under reduced pressure. The resulting crude product was further purified by washing with acetonitrile and dried to obtain sodium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate as a grayish-white solid (50.0 g, 45%). 1H NMR(400MHz,DMSO-d6):δ 10.6(s,1H),7.58(d,J=8.0Hz,1H),7.39(dd,J=8.0,1.6Hz,1H),7.31(d,J=1.6Hz,1H),4.29(q,J=7.2Hz,2H),1.31(t,J=7.2Hz,3H).

[0176] Synthesis of triphenylsulfonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-21). [ka] Sodium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (15.0 g) and triphenylsulfonium bromide (15.3 g) were dissolved in water (150 mL) and DCM (300 mL), and the resulting mixture was stirred at room temperature for 16 hours. The organic layer was washed with saturated sodium bicarbonate aqueous solution (100 mL), followed by water (3 × 100 mL), and then concentrated under reduced pressure to obtain triphenylsulfonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate as a light brown oil (14 g, 49%). 1 H NMR(400MHz,DMSO-d6):δ 10.64(s,1H),7.88-7.63(m,15H),7.57(d,J=8.0Hz,1H),7.39(dd,J=8.0,1. 6Hz,1H),7.30(d,J=1.6Hz,1H),4.29(q,J=7.2Hz,2H),1.31(t,J=7.2Hz,3H).

[0177] Synthesis of bis(4-(tert-butyl)phenyl)iodonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-22). [ka] Sodium 4-(butoxycarbonyl)-2,6-hydroxybenzenesulfonate (50.6 g) and bis(4-(tert-butyl)phenyl)iodonium acetate (55.7 g) were added to water (800 mL) and DCM (800 mL), and the resulting mixture was stirred at room temperature for 16 hours. The organic fraction was washed with water (6 × 700 mL), concentrated under reduced pressure to remove the solvent, and the remaining solution was slowly poured into methyl t-butyl ether (700 mL). The resulting precipitate was collected and dried under reduced pressure to obtain bis(4-(tert-butyl)phenyl)iodonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate as a white solid (69.4 g, 82.2%). 1 H NMR(400MHz,acetone-d6)δ 8.31-8.24(m,2H),7.71-7.65(m,2H),6.94(s,1H),4.27(t,J=6.5Hz,1H),2.85-2.78(m,4H),1.7 9-1.69(m,1H),1.54-1.43(m,1H),1.34(s,2H),1.34(s,7H),1.14(s,1H),0.98(t,J=7.4Hz,2H).

[0178] Synthesis of bis(4-(tert-butyl)phenyl)iodonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-23). [ka] Sodium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (40.2 g) and bis(4-(tert-butyl)phenyl)iodonium acetate (61.7 g) were added to water (600 mL) and DCM (600 mL), and the resulting mixture was stirred at room temperature for 16 hours. The organic fraction was washed with water (7 × 500 mL), concentrated under reduced pressure to remove the solvent, and the remaining solution was slowly poured into methyl t-butyl ether (700 mL). The precipitate was collected and dried under reduced pressure to obtain bis(4-(tert-butyl)phenyl)iodonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate as a white solid (67.0 g, 77%). 1¹H NMR (400MHz, acetone-d6) δ 7.97-7.82 (m, 6H), 7.44-7.36 (m, 1H), 4.28 (t, J=6.5Hz, 1H), 3.14 (s, 1H), 2.80 (t, J=1.0Hz, 1H), 1.79-1.70 (m, 1H), 1.55-1.43 (m, 1H), 1.39 (s, 4H), 1.14 (s, 3H), 0.98 (t, J=7.4Hz, 1H).

[0179] Synthesis of (4-(tert-butyl)phenyl)diphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-24). [ka] Sodium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (47.5 g) and (4-(tert-butyl)phenyl)diphenylsulfonium bromide (51.5 g) were added to water (640 mL) and DCM (640 mL), and the resulting mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted with DCM (200 mL), washed with water (7 × 500 mL), concentrated under reduced pressure to remove the solvent, and the remaining solution was slowly poured into methyl t-butyl ether (700 mL). The gel was collected and dried under reduced pressure to obtain (4-(tert-butyl)phenyl)diphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate as a viscous oil (57.8 g, 66%). 1 ¹H-NMR (400MHz, acetone-d6):δ 7.97-7.82 (m, 6H), 7.44-7.36 (m, 1H), 4.28 (t, J=6.6Hz, 1H), 3.14 (s, 1H), 2.80 (t, J=1.0Hz, 1H), 1.79-1.70 (m, 1H), 1.55-1.43 (m, 1H), 1.39 (s, 4H), 1.14 (s, 3H), 0.98 (t, J=7.4Hz, 1H).

[0180] Synthesis of (4-(tert-butyl)phenyl)diphenylsulfonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-25). [ka] Sodium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (40.2 g) and (4-(tert-butyl)phenyl)diphenylsulfonium bromide (54.3 g) were added to water (600 mL) and DCM (600 mL), and the resulting mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted with DCM (200 mL), washed with water (7 × 500 mL), concentrated under reduced pressure to remove the solvent, and the remaining solution was slowly poured into methyl t-butyl ether (700 mL) to obtain the product as a gel. The gel was collected and dried under reduced pressure to obtain (4-(tert-butyl)phenyl)diphenylsulfonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate as a viscous oil (7180 g, 93%). 1 ¹H NMR (400MHz, acetone-d6) δ 8.29-8.22 (m, 1H), 7.64 (dd, J=15.9, 8.3Hz, 1H), 4.33 (q, J=7.1Hz, 1H), 3.14 (s, 1H), 2.82-2.78 (m, 3H), 2.10 (s, 1H), 1.37 (t, J=7.1Hz, 1H), 1.34 (s, 5H), 1.14 (s, 4H); ESI-MS: [M] - :245.01 and [M] + :319.15.

[0181] Preparation of photoresist polymers The chemical structures of the polymers and quenchers used in the examples and comparative examples are shown below. Polymer P1 was prepared using methods commonly available in the art, and polymer P2 and quencher Q1 were obtained from commercial sources. [ka]

[0182] Solubility test of the base material (polymer P1) A 3 wt% solution of polymer P1 in propylene glycol methyl ether acetate (PGMEA) was shaken in a 20 mL glass container on a mechanical shaker and filtered through a PTFE disc filter with a pore size of 0.20 micrometers. The Si wafer was primed with hexamethyldisilazane (HMDS) at a curing temperature of 120°C for 30 seconds. The polymer film was applied to the primed Si wafer by spin coating and soft-baked at 90°C for 60 seconds using a TEL CleanTrack ACT 8 coating tool. The initial thickness (t0) was determined by KLA Therma-Wave Opti-Probe 7341. The wafer was then treated with a 0.26N TMAH aqueous solution (MF(trademark)-CD26, DuPont Electronics & Industrial) at room temperature for 60 seconds. The wafer was then rinsed with DI water and spin-dried. After treatment, the thickness (t1) was measured again, and the change in thickness (Δt) was calculated according to Equation 1. Δt=t1-t0 formula 1

[0183] The results are shown in Table 1.

[0184] [Table 1]

[0185] Preparation and processing of photoresist compositions ArF photoresist compositions. Positive-type photoresist compositions were prepared by dissolving solid components (PAG, Q1, P1, and P2) in a solvent using the materials and quantities shown in Table 2A, with the quantities expressed in weight percent based on 100% of the total weight of the solids. The total solids content of the photoresist compositions was 3.10%. The solvent system contained propylene glycol methyl ether acetate (S1) (35% by weight) and 2-hydroxyisobutyrate methyl ester (S2) (65% by weight). Each mixture was shaken in a 100 mL glass container on a mechanical shaker and filtered through a PTFE disc filter with a pore size of 0.20 micrometers.

[0186] [Table 2]

[0187] [ka]

[0188] KrF photoresist composition. Positive-type photoresist compositions were prepared by dissolving solid components (PAG, Q2, P3, and SLA1) in a solvent using the materials and quantities shown in Table 2B, with quantities expressed as weight% based on 100% of the total weight of the solids. The components in Table 2B were as follows: Q2: tetrabutylammonium lactate, P3: poly(para-hydroxystyrene-co-styrene-co-t-butyl acrylate) 70 / 20 / 10 wt / wt / wt ratio, SLA1: SILWET™ L-7604 (silicone surfactant, Momentive Performance Materials). The total solids content of the photoresist composition was 3.10%. The solvent was ethyl lactate (S3). Each mixture was shaken in a 100 mL glass container on a mechanical shaker and filtered through a PTFE disc filter with a pore size of 0.20 micrometers.

[0189] [Table 3]

[0190] [ka]

[0191] Lithography Testing - Examples 1-9 E sizeEL% and LWR evaluation were performed. A 300 mm silicon wafer was spin-coated with AR® 40A anti-reflective agent (DuPont Electronics & Industrial) at a curing temperature of 205°C for 60 seconds to form a first BARC layer with a thickness of 800 Å. Next, the wafer was spin-coated with AR® 104 anti-reflective agent (DuPont Electronics & Industrial) at a curing temperature of 175°C for 60 seconds to form a second BARC layer with a thickness of 400 Å. Then, the wafer was spin-coated with each of the photoresist compositions shown in Table 1 and soft-baked at 90°C for 60 seconds to obtain a photoresist layer with a thickness of 900 Å. The BARC layer and photoresist layer were coated using the TEL Clean Track Lithius coating tool. Wafers were exposed to 193 nm activating radiation at various doses using an ASML 1900i immersion scanner (1.35 NA, 0.988 / 0.90 inside / outside sigma, 35 Y polarized dipole illumination) with a mask having a 1:1 line-space pattern (38 nm line width / 76 nm pitch). The exposed wafers were exposed at 95°C for 60 seconds, baked, and developed in a 0.26 N tetramethylammonium hydroxide (TMAH) aqueous solution (MF(trademark)-CD26, DuPont Electronics & Industrial) for 12 seconds. The wafers were then rinsed with DI water and spin-dried to form a photoresist pattern. CD linewidth measurements of the formed patterns were performed using a Hitachi High Technologies Co. CG4000CD-SEM.

[0192] The line space pattern in nanometer (nm) units was analyzed for the limiting dimension (CD). Here, the sizing energy "E size " is the irradiation energy when the CD of the formed line space pattern is equal to the CD of the mask pattern. size This is millijoules (mJ / cm²) per square centimeter. 2Expressed in units of ). Exposure degrees of freedom (EL%) is the difference in exposure energy required to print a line space pattern within ±10% of the target diameter, normalized by the sizing energy. Line width roughness (LWR) is expressed in units of nanometers (nm) and was determined as the 3-sigma value from a distribution of 100 arbitrary points totaling line width measurements, followed by removing measurement noise. E size Table 3 shows the EL% and LWR data.

[0193] E0 evaluation. A 200 mm silicon wafer was spin-coated with AR(trademark) 40A anti-reflective agent (DuPont Electronics & Industrial) at a curing temperature of 205°C for 60 seconds to form an 800 Å thick BARC layer. The wafer was then spin-coated with each of the photoresist compositions listed in Table 1 and soft-baked at 90°C for 60 seconds to obtain a 900 Å thick photoresist layer. The BARC and photoresist layers were coated with a TEL CleanTrack ACT 8 coating tool. The wafers were exposed to 193 nm activating radiation at various doses using an ASML 1100 scanner (0.75 NA, Quadrapole-30 with 0.89 / 0.64 inside / outside sigma). The exposed wafers were exposed at 95°C for 60 seconds, baked, and developed in a 0.26 N TMAH aqueous solution (MF(trademark)-CD26, DuPont Electronics & Industrial) for 60 seconds. The wafer was then rinsed with DI water and spin-dried. The film thickness was measured in each exposure area using a KLA Therma-Wave Opti-Probe 7341 and plotted against the dose. E0 value (mJ / cm 2 ) was determined as the first dose value where the remaining film thickness was less than 7% of the original coated thickness. The E0 data are shown in Table 3.

[0194] [Table 4]

[0195] Lithography Testing - Examples 10-43 ArF photolithography E0, E size EL% and LWR evaluation were performed. A 200 mm silicon wafer was spin-coated with AR(trademark) 40A anti-reflective agent (DuPont Electronics & Industrial) at a curing temperature of 205°C for 60 seconds to form a BARC layer with a thickness of 800 Å. The wafer was then spin-coated with each of the photoresist compositions listed in Table 1 and soft-baked at 90°C for 60 seconds to obtain a photoresist layer with a thickness of 900 Å. The BARC and photoresist layers were coated with a TEL CleanTrack ACT 8 coating tool. The wafer was exposed to 193 nm activating radiation using an ASML 1100 scanner (0.75 NA, 0.89 / 0.64 inside / outside sigma, 35 Y polarized dipole illumination) with a mask having a 1:1 line-space pattern (90 nm line width / 180 nm pitch). The exposed wafer was exposed at 95°C for 60 seconds, baked, and developed in a 0.26N TMAH aqueous solution (MF(trademark)-CD26, DuPont Electronics & Industrial) for 60 seconds. The wafer was then rinsed with deionized water and spin-dried to form a photoresist pattern. The CD linewidth of the formed pattern was measured using a Hitachi High-Technologies Corp. CD-SEM CG9380. E0, E size The EL% and LWR were determined as described above, and the results are shown in Table 4.

[0196] [Table 5]

[0197] KrF Photolithography E0, E sizeEL% and LWR evaluation were performed. A 200 mm silicon wafer was spin-coated with AR™ 3 bottom anti-reflective coating (DuPont Electronics & Industrial) at a curing temperature of 205 °C for 60 seconds to form a 600 Å thick BARC layer. The wafer was then spin-coated with KrF photoresist and soft-baked at 130 °C for 60 seconds to obtain a 6035 Å thick photoresist layer. The BARC layer and photoresist layer were coated with the TEL CLEAN TRACK™ ACT™ 8 coating tool. The wafer was exposed to 248 nm activating radiation using a CANON FPA 5000 ES4 DUV stepper (conventional illumination 0.63 NA, 0.8 partial coherence) with a mask having a 1:1 line-space pattern (250 nm line width / 500 nm pitch). The exposed wafer was post-exposure baked at 130°C for 90 seconds and developed with a 0.26N TMAH aqueous solution (DuPont MF(trademark)-CD26, DuPont Electronics & Industrial) for 45 seconds. The wafer was then rinsed with deionized water and spin-dried to form a photoresist pattern. The CD linewidth of the formed pattern was measured using a Hitachi High-Technologies Corp. CD-SEM CG9380. E0, E size The EL% and LWR were determined as described above, and the results are shown in Table 5.

[0198] [Table 6]

[0199] The following photoacid generators were prepared in the following synthesis examples for use in the photolithography examples shown in Tables 6 and 7 below. [ka]

[0200] Synthesis of tetraethylammonium 2-hydroxy-4-((4-iodophenoxy)carbonyl)benzenesulfonate [ka] To a room-temperature mixture of potassium 4-carboxy-2-hydroxybenzenesulfonate (6.41 g, 25 mmol), 4-iodophenol (8.25 g, 37.5 mmol), tetraethylammonium chloride (8.29 g, 50 mmol), and 4-pyrrolidinopyridine (185 mg, 1.25 mmol) in N,N-dimethylformamide (DMF, 75 mL), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (5.75 g, 30 mmol) was added. The reaction mixture was stirred for 3 hours (hr). The reaction was then quenched by adding an aqueous solution of tetraethylammonium chloride (20% w / v, 500 ml (mL)). The resulting mixture was extracted with dichloromethane (DCM, 4 × 100 mL), and the combined organic layer was washed with aqueous tetraethylammonium chloride (20% w / v, 3 × 50 mL) and water (3 × 100 mL). The organic layer was dried on filter paper and concentrated under vacuum. The resulting residue was resuspended in acetone (50 mL) and added dropwise to a stirred solution of methyl tert-butyl ether (500 mL). The oil precipitate was isolated by decanting the mother liquor and washing with excess methyl tert-butyl ether. The residual solvent was removed by storing the mixture overnight in a vacuum oven at 3°C ​​to obtain the product as a colorless oil (6.08 g, 44%). 1 H NMR(499MHz,DMSO-d6)δ 10.71(s,1H),7.81(d,J=8.9Hz,2H),7.66(d,J=8.0Hz,1H),7.56(dd,J=8.0,1.7Hz,1H),7.47 (d,J=1.6Hz,1H),7.15(d,J=8.7Hz,2H),3.19(q,J=7.3Hz,8H),1.15(tt,J=7.3,1.7Hz,12H).

[0201] Synthesis of phenyl(3-(trifluoromethyl)phenyl)iodonium 2-hydroxy-4-((4-iodophenoxy)carbonyl)benzenesulfonate (D1): [ka] Tetraethylammonium 2-hydroxy-4-((4-iodophenoxy)carbonyl)benzenesulfonate (2.0 g, 3.63 mmol) and phenyl (3-(trifluoromethyl)phenyl)iodonium chloride (1.40 g, 3.63 mmol) were vigorously stirred for 3 hours in a two-phase room temperature mixture of DCM (50 mL) and water (50 mL). Stirring was stopped, and the two-phase mixture was separated into individual layers. n-heptane was added to the organic layer in a final ratio of 1:3n-heptane:DCM. The organic layer was washed with water (5 × 20 mL), dried on filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (20 mL) and added to a stirred solution of n-heptane (500 mL) to form a precipitate. The precipitate was isolated by decanting the mother liquor and washing with excess n-heptane. The residual solvent was removed by storing the mixture overnight in a vacuum oven at 35°C to obtain product D1 as an amorphous, colorless solid (1.76 g, 63%). 1 H NMR(499MHz,DMSO-d6)δ 10.71(s,1H),8.75(s,1H),8.55(d,J=8.1Hz,1H),8.31(d,J=7.7Hz,2H),8.02(d,J=7.9Hz,1H),7.80(d,J=8.7Hz ,2H),7.75(t,J=8.0Hz,1H),7.67(t,J=7.9Hz,2H),7.59-7.51(m,3H),7.49(d,J=1.7Hz,1H),7.17-7.12(m,2H). 19 F NMR (470 MHz, DMSO) δ -61.22.

[0202] Synthesis of tris(4-fluorophenyl)sulfonium 2-hydroxy-4-((4-iodophenoxy)carbonyl)benzenesulfonate (D2): [ka] Tetraethylammonium 2-hydroxy-4-((4-iodophenoxy)carbonyl)benzenesulfonate (2.0 g, 3.63 mmol) and tris(4-fluorophenyl)sulfonium bromide (1.45 g, 3.63 mmol) were vigorously stirred for 3 hours in a two-phase room temperature mixture of DCM (50 mL) and water (50 mL). Stirring was stopped, and the two-phase mixture was separated into individual layers. n-heptane was added to the organic layer in a final ratio of 1:3n-heptane:DCM. The organic layer was washed with water (5 × 20 mL), dried on filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (20 mL) and added to a stirred solution of n-heptane (500 mL) to form a precipitate. The precipitate was isolated by vacuum filtration and washed with excess n-heptane. The residual solvent was removed by storing the product D2 as a white solid (1.53 g, 57%) in a vacuum oven at 35°C overnight. 1 H NMR(499MHz,DMSO-d6)δ 10.70(s,1H),7.97-7.89(m,6H),7.81(dt,J=8.7,2.0Hz,2H),7.66(t,J=8.1H z,7H),7.55(dd,J=8.0,1.7Hz,1H),7.46(d,J=1.7Hz,1H),7.18-7.12(m,2H). 19 F NMR (470 MHz, DMSO) δ -103.50.

[0203] Synthesis of tetraethylammonium 4-((2-fluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate: [ka] Potassium 4-carboxy-2-hydroxybenzenesulfonate (4.00 g, 15.6 mmol), 2-fluorophenol (2.62 g, 23.4 mmol), tetraethylammonium chloride (5.17 g, 31.2 mmol), and 4-pyrrolidinopyridine (100 mg) were mixed at room temperature in DMF (30 mL) and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (3.59 g, 18.2 mmol) was added. The mixture was stirred overnight at room temperature. The reaction was quenched by pouring into an aqueous solution of tetraethylammonium chloride (20% w / v, 500 mL). The resulting mixture was extracted with DCM (4 × 100 mL), and the combined organic layer was washed with aqueous solution of tetraethylammonium chloride (20% w / v, 3 × 50 mL) and water (3 × 100 mL). The organic layer was dried on filter paper and concentrated under reduced pressure. The obtained residue was resuspended in acetone (50 mL) and added dropwise to a stirred solution of methyl tert-butyl ether (500 mL) to form a precipitate. The oil precipitate was isolated by decanting the mother liquor and washing with excess methyl tert-butyl ether. The residual solvent was removed by storing the product overnight in a vacuum oven at 35°C to obtain the product as a colorless oil (3.20 g, 46%). 1 H NMR(499MHz,DMSO-d6)δ 7.71(d,J=8.0Hz,1H),7.61(dd,J=8.1,1.7Hz,1H),7.51(d,J=1.7Hz,1H),7.50-7. 36(m,3H),7.31(td,J=7.6,1.7Hz,1H),3.20(q,J=7.3Hz,8H),1.27-1.12(t,12H).

[0204] Synthesis of bis(4-(tert-butyl)phenyl)iodonium 4-((2-fluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate (D3): [ka] Tetraethylammonium 4-((2-fluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate (3.20 g, 7.2 mmol) and bis(4-(tert-butyl)phenyl)iodonium acetate (2.95 g, 6.5 mmol) were vigorously stirred for 3 hours in a two-phase room temperature mixture of DCM (70 mL) and water (70 mL). Stirring was stopped, and the two-phase mixture was separated into individual layers. The organic layer was washed with water (5 × 20 mL), dried on filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (20 mL) and added to a stirred solution of methyl tert-butyl ether (500 mL) to obtain a precipitate. The precipitate was isolated by vacuum filtration and washed with excess n-heptane. The residual solvent was removed by storing overnight in a vacuum oven at 35°C to obtain product D3 as a white solid (2.60 g, 50%). 1 H NMR(499MHz,DMSO-d6)δ 10.80(s,1H),8.20-8.14(m,4H),7.71(d,J=8.0Hz,1H),7.59(dd,J=8.0,1.7Hz,1H ),7.56-7.49(m,5H),7.48-7.33(m,3H),7.29(td,J=7.7,1.8Hz,1H),1.26(s,18H). 19 F NMR (470 MHz, DMSO) δ 129.50.

[0205] Synthesis of tetraethylammonium 4-((2,6-difluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate: [ka] Potassium 4-carboxy-2-hydroxybenzenesulfonate (4.00 g, 15.6 mmol), 2,6-difluorophenol (3.04 g, 23.4 mmol), tetraethylammonium chloride (5.17 g, 31.2 mmol), and 4-pyrrolidinopyridine (100 mg) were mixed at room temperature in DMF (30 mL) and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (3.59 g, 18.2 mmol) was added. The mixture was stirred overnight at room temperature. The reaction product was quenched by pouring it into an aqueous solution of tetraethylammonium chloride (20% w / v, 500 mL). The resulting mixture was extracted with DCM (4 × 100 mL), and the combined organic layer was washed with aqueous solution of tetraethylammonium chloride (20% w / v, 3 × 50 mL) and water (3 × 100 mL). The organic layer was dried on filter paper and concentrated under reduced pressure. The obtained residue was resuspended in acetone (50 mL) and added dropwise to a stirred solution of methyl tert-butyl ether (500 mL) to form a precipitate. The oil precipitate was isolated by decanting the mother liquor and washing with excess methyl tert-butyl ether. The residual solvent was removed by storing the product overnight in a vacuum oven at 35°C to obtain the product as a colorless oil (4.20 g, 59%). 1 H NMR(499MHz,acetone-d6)δ 7.84(d,J=8.1Hz,1H),7.66(dd,J=8.0,1.8Hz,1H),7.61(d,J=1.7Hz,1H),7.44(tt,J=8.5, 6.1Hz, 1H), 7.25 (t, J=8.3Hz, 2H), 3.45 (q, J=7.3Hz, 8H), 1.36 (t, J=9.1, 5.5, 1.9Hz, 12H).

[0206] Synthesis of bis(4-(tert-butyl)phenyl)iodonium 4-((2,6-difluorophenoxy)carbonyl)2-hydroxybenzenesulfonate (D4): [ka] Tetraethylammonium 4-((2,6-difluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate (4.20 g, 9.1 mmol) and bis(4-(tert-butyl)phenyl)iodonium acetate (3.70 g, 8.2 mmol) were vigorously stirred for 3 hours in a two-phase room temperature mixture of DCM (70 mL) and water (70 mL). Stirring was stopped, and the two-phase mixture was separated into individual layers. The organic layer was washed with water (5 × 20 mL), dried on filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (20 mL) and added to a stirred solution of methyl tert-butyl ether (500 mL) to form a precipitate. The precipitate was isolated by vacuum filtration and washed with excess n-heptane. The residual solvent was removed by storing overnight in a vacuum oven at 35°C to obtain product D4 as a white solid (3.43 g, 58%). 1 H NMR(499MHz,CDCl3)δ 7.85-7.83(m,4H),7.51(t,J=1.1Hz,1H),7.42(d,J=1.0Hz,2H),7.29-7.26 (m,4H),7.14-7.12(m,J=8.5,5.9Hz,1H),6.97-6.92(m,2H),1.18(s,18H). 19 F NMR(470MHz,DMSO-d6)δ 126.06.

[0207] Synthesis of tetraethylammonium 2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate: [ka] Potassium 4-carboxy-2-hydroxybenzenesulfonate (20.50 g, 80 mmol), 2,4,6-triiodophenol (56.61 g, 120 mmol), tetraethylammonium chloride (26.51 g, 160 mmol), and 4-pyrrolidinopyridine (590 mg, 4 mmol) were mixed at room temperature in DMF (150 mL) and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (18.40 g, 96 mmol) was added. The reaction mixture was stirred for 3 hours. The reaction was then quenched by pouring the mixture into an aqueous solution of tetraethylammonium chloride (20% w / v, 750 mL). The resulting mixture was extracted with DCM (4 × 200 mL), and the combined organic layer was washed with aqueous solution of tetraethylammonium chloride (20% w / v, 3 × 100 mL) and water (3 × 200 mL). The organic layer was dried on filter paper and concentrated under reduced pressure. The resulting residue was resuspended in acetone (100 mL) and added dropwise to a stirred solution of methyl tert-butyl ether (900 mL) to form a precipitate. The oil precipitate was isolated by decanting the mother liquor and washing with excess methyl tert-butyl ether. The residual solvent was removed by storing the product overnight in a vacuum oven at 35°C to obtain the product as a white solid (28.50 g, 44%). 1 H NMR(499MHz,DMSO-d6)δ 10.77(s,1H),8.24(s,2H),7.72(d,J=8.1Hz,1H),7.63(dd,J=8.1,1.8Hz,1H),7.52(d,J=1.7Hz,1H),3.19(q,J=7.3Hz,8H),1.19-1.12(m,12H).

[0208] Synthesis of tri-p-tolylsulfonium 2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate (D5): [ka] Tetraethylammonium 2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate (4.0 g, 5 mmol) and tri-p-tolylsulfonium bromide (1.93 g, 5 mmol) were vigorously stirred for 3 hours in a two-phase mixture of room temperature DCM (50 mL) and water (50 mL). Stirring was stopped, and the two-phase mixture was separated into individual layers. n-heptane was added to the organic layer in a final ratio of 1:3n-heptane:DCM. The organic layer was washed with water (5 × 20 mL), dried on filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (20 mL) and added to a stirred solution of n-heptane (500 mL) to form a precipitate. The precipitate was isolated by vacuum filtration and washed with excess n-heptane. The residual solvent was removed by storing the mixture overnight in a vacuum oven at 35°C to obtain product D5 as a white solid (4.61 g, 94%). 1 H NMR(499MHz,DMSO-d6)δ 10.78(s,1H),8.23(s,2H),7.71(d,J=8.0Hz,1H),7.67(d,J=8.5Hz,6H),7.61(d d,J=8.1,1.7Hz,1H),7.57(d,J=8.2Hz,6H),7.51(d,J=1.7Hz,1H),2.43(s,9H).

[0209] Synthesis of 5-phenyl-5H-dibenzo[b,d]thiophene-5-ium 2-hydroxy-4-((2,4,6triiodophenoxy)carbonyl)benzenesulfonate (D6): [ka] Tetraethylammonium 2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate (4.0 g, 5 mmol) and 5-phenyl-5H-dibenzo[b,d]thiophene-5-ium bromide (1.71 g, 5 mmol) were vigorously stirred for 3 hours in a biphasic room-temperature mixture of DCM (50 mL) and water (50 mL). Stirring was stopped, and the two-phase mixture was separated into individual layers. n-heptane was added to the organic layer in a final ratio of 1:3n-heptane:DCM. The organic layer was washed with water (5 × 20 mL), dried on filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (20 mL) and added to a stirred solution of n-heptane (500 mL) to form a precipitate. The precipitate was isolated by vacuum filtration and washed with excess n-heptane. The residual solvent was removed by storing the mixture overnight in a vacuum oven at 35°C to obtain product D6 as a white solid (3.53 g, 76%). 1 H NMR(499MHz,DMSO-d6)δ 10.77(s,1H),8.52(d,J=7.9Hz,2H),8.38(d,J=7.9Hz,2H),8.23(s,2H),7.95(td ,J=7.6,1.1Hz,2H),7.79-7.66(m,4H),7.64-7.55(m,5H),7.52(d,J=1.7Hz,1H).

[0210] Synthesis of phenyl(3-(trifluoromethyl)phenyl)iodonium 2-hydroxy-4-((2,4,6triiodophenoxy)carbonyl)benzenesulfonate (D7): [ka] Tetraethylammonium 2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate (6.70 g, 8.4 mmol) and phenyl(3-(trifluoromethyl)phenyl)iodonium chloride (3.38 g, 8.8 mmol) were vigorously stirred for 3 hours in a two-phase room-temperature mixture of DCM (60 mL) and water (60 mL). Acetone (50 mL) was added, and stirring was continued overnight. Stirring was stopped, and the two-phase mixture was separated into individual layers. The aqueous layer was back-extracted with DCM (3 × 50 mL), and the combined organic layers were washed with water (5 × 50 mL), dried on filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (100 mL) and added to a stirred solution of n-heptane and methyl tert-butyl ether (1:1, 900 mL) to form a precipitate. The precipitate was isolated by vacuum filtration and washed with excess n-heptane. The residual solvent was removed by storing the product D7 as a white solid (2.58 g, 30%) in a vacuum oven at 35°C overnight. 1 H NMR(499MHz,DMSO-d6)δ 10.76(s,1H),8.75(s,1H),8.55(d,J=8.1Hz,1H),8.31(d,J=7.6Hz,2H),8.24(s,2H),8.05(d,J=7.9Hz,1H),7.7 6(t,J=8.0Hz,1H),7.73-7.66(m,2H),7.62(dd,J=8.1,1.7Hz,1H),7.56(t,J=7.8Hz,2H),7.52(d,J=1.7Hz,1H). 19 F NMR(470MHz,DMSO-d6)δ -61.19.

[0211] Synthesis of 2-(4-iodophenoxy)ethane-1-ol: [ka] A mixture of 4-iodophenol (8.80 g, 40 mmol) and potassium carbonate (16.58 g, 120 mmol) in N,N-dimethylformamide (100 mL) was heated to 75°C. 2-bromoethanol (15 g, 120 mmol) was neatly added to the reaction mixture, and the reaction mixture was stirred for 3 hours. The reaction mixture was quenched by pouring it into water (500 mL). Methyl tert-butyl ether (300 mL) was added, and the mixture was stirred for 15 minutes. The two-phase mixture was separated into individual layers, and the aqueous layer was extracted with methyl tert-butyl ether (2 × 100 mL). The combined organic layers were washed with aqueous potassium hydroxide solution (1 M, 3 × 100 mL) and water (3 × 100 mL), dried on filter paper, and concentrated under reduced pressure to obtain the product as a white solid (5.82 g, 55%). 1 H NMR(499MHz,DMSO-d6)δ 7.57(dt,J=9.0,2.3Hz,2H),6.78(dt,J=9.0,2.2Hz,2H),4.87(t,J=5.3Hz,1H),3.95(dd,J=5.4,4.6Hz,2H),3.70(q,J=4.8Hz,2H).

[0212] Synthesis of tetraethylammonium 2-hydroxy-4-((2-(4-iodophenoxy)ethoxy)carbonyl)benzenesulfonate: [ka] Potassium 4-carboxy-2-hydroxybenzenesulfonate (5.82 g, 22.7 mmol), 2-(4-iodophenoxy)ethane-1-ol (9.00 g, 34.1 mmol), tetraethylammonium chloride (7.52 g, 45.4 mmol), and 4-pyrrolidinopyridine (170 mg, 1.1 mmol) were mixed at room temperature in DMF (50 mL) and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (5.21 g, 27.2 mmol) was added. After stirring the reaction mixture for 3 hours, it was quenched by pouring it into an aqueous solution of tetraethylammonium chloride (20% w / v, 300 mL). The resulting mixture was extracted with DCM (4 × 50 mL), and the combined organic layer was washed with aqueous solution of tetraethylammonium chloride (20% w / v, 3 × 50 mL) and water (3 × 50 mL). The organic layer was dried on filter paper and concentrated under reduced pressure. The resulting residue was resuspended in acetone (100 mL) and added dropwise to a stirred solution of methyl tert-butyl ether (900 mL) to form a precipitate. The precipitate was isolated by vacuum filtration and washed with excess methyl tert-butyl ether. The residual solvent was removed by storing the mixture overnight in a vacuum oven at 35°C to obtain the product as a white solid (2.80 g, 21%). 1 H NMR(499MHz,DMSO-d6)δ 10.65(s,1H),7.63-7.56(m,3H),7.38(dd,J=8.1,1.7Hz,1H),7.31(d,J=1.7Hz,1H),6.85(dt,J=8.8,2.0 Hz,2H),4.56(t,J=4.6Hz,2H),4.32(t,J=4.5Hz,2H),3.19(q,J=7.2Hz,8H),1.15(tt,J=7.2,1.8Hz,12H).

[0213] Synthesis of tri-p-tolylsulfonium 2-hydroxy-4-((2-(4-iodophenoxy)ethoxy)carbonyl)benzenesulfonate (D8): [ka] Tetraethylammonium 2-hydroxy-4-((2-(4-iodophenoxy)ethoxy)carbonyl)benzenesulfonate (2.80 g, 4.72 mmol) and tri-p-tolylsulfonium bromide (1.82 mg, 4.72 mmol) were vigorously stirred for 3 hours in a two-phase room-temperature mixture of DCM (50 mL) and water (50 mL). Stirring was stopped, and the two-phase mixture was separated into individual layers. n-heptane was added to the organic layer in a final ratio of 1:3n-heptane:DCM. The organic layer was washed with water (5 × 20 mL), dried on filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (20 mL) and added to a stirred solution of n-heptane (500 mL) to form a precipitate. The precipitate was isolated by vacuum filtration and washed with excess n-heptane. The residual solvent was removed by storing the mixture overnight in a vacuum oven at 35°C to obtain product D8 as a colorless oil (2.48 g, 69%). 1 H NMR(499MHz,DMSO-d6)δ 10.67(s,1H),7.67(d,J=8.5Hz,6H),7.62-7.54(m,9H),7.38(dd,J=8.0,1.7Hz,1H),7.31(d,J=1 .7Hz,1H),6.85(dt,J=8.9,1.9Hz,2H),4.57(t,J=4.5Hz,2H),4.32(t,J=4.6Hz,2H),2.43(s,9H).

[0214] Preparation of photoresist polymers The chemical structures of the polymer (P4), quencher (Q3), and comparative photoacid generator (cD1) used in the examples and comparative examples are shown below. Polymer P4 was prepared using methods commonly available in the art, and quencher Q3 and comparative PAG cD1 were obtained from commercially available sources. [ka]

[0215] Preparation and processing of photoresist compositions KrF photoresist composition. The photoresist composition was prepared by dissolving the solid components in a solvent using the materials and amounts shown in Tables 6 and 7. The amounts are expressed in weight percent based on 100% of the total weight of the solids. The total solids content of the photoresist composition was 2.1% by weight. The solvent system contained propylene glycol monomethyl ether acetate (50% by weight) and 4-hydroxy-4-methyl-2-pentanone (50% by weight). Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disc filter with a pore size of 0.2 microns.

[0216] Photolithography evaluation was performed using the CLEAN TRAC ACT8 (TEL, Tokyo Electron Co) wafer track. A 200nm wafer for photolithography testing was coated with AR(trademark)3 BARC (DuPont Electronics & Industrial) and soft-baked at 205°C for 60 seconds to obtain a 70nm film. Next, a coating of AR(trademark)40A BARC (DuPont Electronics & Industrial) was placed on top of the AR(trademark)3 layer and soft-baked at 215°C for 60 seconds to form a second BARC layer with a thickness of approximately 80nm. Subsequently, a photoresist composition was coated onto the double BARC stack and soft-baked at 110°C for 60 seconds to obtain a photoresist film layer with a thickness of approximately 50nm.

[0217] Using a mask with selected features, the wafer was exposed to 248 nm radiation using a Canon FPA-5000 ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57). After exposure, the wafer was baked at 100°C for 60 seconds, developed with MF™ CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with deionized (DI) water, and dried. Limiting dimension (CD) linewidth measurements of the formed pattern were performed using a Hitachi S-9380 CD-SEM. Linewidth roughness (LWR) values ​​were determined by top-down SEM with an acceleration voltage of 800 volts (V), probe current of 8.0 picoamperes (pA), digital zoom 1.0, magnification of 200Kx, and frame rate set to 64. LWR was measured over a line length of 2 μm in a 40 nm process and reported as the average LWR of the measured area. Sizing energy (E size The LWR of the line was determined based on CD measurements. The pseudo-Z factor is reported below. This was determined according to Equation 1: Pseudo Z-factor = (E size )×(LWR) 2 formula 1 (In the formula, E size This is millijoules per square centimeter (mJ / cm²). 2 The LWR is reported in units of ) and the pseudo-Z factor is reported in units of nanometers (nm) and mJ × 10⁻¹⁶. -11 (Reported in units of units). The pseudo-Z factor (Z'-factor) is a modified measure of photoresist performance based on the Z factor, a known parameter indicating RLS (Resolution, Line Edge Roughness, Sensitivity) photoresist performance (see, for example, Wallow, T. et al. Proc. SPIE 6921, 69211F, 2008). The pseudo-Z factor is calculated at a constant resolution (CD size).

[0218] [Table 7]

[0219] [Table 8]

[0220] As shown in Tables 6 and 7, each of the photoresist examples PR31 to PR39 produced patterns with good profiles (patterning quality). As shown in Table 7, the comparative photoresist example COMP PR7 contains a comparative photoacid generator cD1 containing anionic perfluorobutanesulfonate and cationic bis(4-(tert-butyl)phenyl)iodonium. For direct comparison, since PR38 and PR39 have the same polymer and quencher components as COMP PR7, each photoresist example PR38 and PR39 can be directly compared with COMP PR7. The photoacid generators in photoresist compositions PR38 and PR39 contain anionic 4-((2-fluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate or 4-((2,6-difluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate, respectively. The photoresists PR38 and PR39 achieved better lithography performance, as indicated by higher quality images with lower LWR and a lower Z-factor compared to COMP PR7.

[0221] While this disclosure has been described in relation to what is currently considered to be a practical and exemplary embodiment, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to encompass various modifications and equivalent configurations that fall within the spirit and scope of the appended claims.

Claims

1. A photoresist composition, Based on the total solid content of the photoresist composition, one or more non-solvent alkali-insoluble substrates are present in a total amount exceeding 50 weight percent, A nonpolymeric ionic photoacid generator compound comprising an anion and an iodonium or sulfonium cation, wherein the anion is of formula (1): 【Chemistry 1】 (In formula (1), Ar １ C is a monocyclic or polycyclic C ３～６０ It is an aromatic group, Each L １ Independently, L is a single bond or one or more divalent linking groups. １ It does not contain fluorine. Each R １ is independently halogen, hydroxyl, substituted or unsubstituted C １～３０ alkyl, substituted or unsubstituted C ３～３０ cycloalkyl, substituted or unsubstituted C ３～３０ cycloalkene, substituted or unsubstituted C ３～３０ heterocycloalkyl, substituted or unsubstituted C ６～３０ aryl, substituted or unsubstituted C ７～３０ arylalkyl, substituted or unsubstituted C ７～３０ alkylaryl, substituted or unsubstituted C ６～３０ aryloxy, substituted or unsubstituted C ３～３０ heteroaryl, substituted or unsubstituted C ４～３０ alkylheteroaryl, substituted or unsubstituted C ４～３０ heteroarylalkyl or substituted or unsubstituted C ３～３０ heteroaryloxy, and each R １ optionally further comprises one or more divalent linking groups as part of its structure, Each Z １ It independently contains an anionic stabilizing group and at least one Z １ It is configured to form a ring having 5 to 8 atoms by forming an intramolecular non-covalent bond with a sulfonate anion group, Z １ is -OH, -C(O)OH, -SH, -C(O)SH, -NHS(O) ２ R ２ , -S(O) ２ R ２ , -S(O) ２ NHS (O) ２ R ２ , -CH (=NOH) or -B (R ３ ) ２ Selected independently from each Z １ It optionally further includes one or more divalent linking groups as part of its structure, Each R ２ C is fluorine, hydroxyl, substituted or unsubstituted C １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl or substituted or unsubstituted C ３～３０ Selected independently from heteroaryls, and Each R ３ C is hydrogen, fluorine, hydroxyl, substituted or unsubstituted C １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl or substituted or unsubstituted C ３～３０ Selected independently from heteroaryls, Two R's １ Together, Ar １ A fused ring is optionally formed, and the fused ring optionally further includes one or more divalent linking groups as part of its structure. One Z １ and one R １ Together, Ar １ A fused ring is optionally formed, and the fused ring optionally further includes one or more divalent linking groups as part of its structure. Each a is independently 1 or 2, b is an integer between 0 and 4. c is an integer between 1 and 3. A nonpolymeric ionic photoacid generator compound represented by, solvent and A photoresist composition comprising a photoresist compound that does not contain a photoacid generator, which generates a photoacid having a higher acidity than the photoacid produced by the nonpolymeric ionic photoacid generator compound.

2. Each R １ These are independently hydroxyl, substituted, or unsubstituted C １～３０ Alkyl, substituted, or unsubstituted C ３～３０ Cycloalkyl, substituted, or unsubstituted C ３～３０ Cycloalkenes, substituted or unsubstituted C ３～３０ Heterocycloalkyl, substituted or unsubstituted C ６～３０ Aryl, substituted, or unsubstituted C ７～３０ Arylalkyl, substituted, or unsubstituted C ７～３０ Alkylaryl, substituted, or unsubstituted C ６～３０ Aryloxy, substituted, or unsubstituted C ３～３０ Heteroaryl, substituted, or unsubstituted C ４～３０ Alkyl heteroaryl, substituted or unsubstituted C ４～３０ Heteroarylalkyl or substituted or unsubstituted C ３～３０ It is a heteroaryloxy, and each R １ The photoresist composition according to claim 1, further comprising optionally one or more divalent linking groups as part of its structure.

3. Each Z １ The photoresist composition according to claim 1, wherein the sulfonate anion group is configured to form an intramolecular non-covalent bond with the sulfonate anion group to form a ring having six or seven atoms.

4. The photoresist composition according to claim 1, wherein each anion stabilizing group has a pKa of 25 or less.

5. The photoresist composition according to claim 1, wherein each anion stabilizing group includes a protic group.

6. The photoresist composition according to claim 1, wherein at least one anion stabilizing group comprises -OH.

7. The photoresist composition according to claim 1, wherein the anion does not contain a trifluoromethyl group and a difluoromethylene group.

8. The photoresist composition according to claim 7, wherein the anion does not contain fluorine.

9. Ar １ This is a single ring C ３～６ It is an aromatic group and at least one Z １ is, -L １ -SO ３ － The photoresist composition according to claim 1, wherein the group is located in the ortho position relative to the group represented by .

10. Ar １ This is a polycyclic C ６～６０ The photoresist composition according to claim 1, wherein the group is an aromatic group.

11. at least one Z １ The base is -L １ -SO ３ － Ar located in the ortho position on the same ring as the group represented by １ The photoresist composition according to claim 10, wherein it is bonded to a ring carbon atom.

12. The ortho position of the at least one Z １ The group is -OH, and L １ The photoresist composition according to claim 11, wherein the bond is a single bond.

13. Ar １ This is a condensed polycyclic C ６～６０ It is an aromatic group and has at least one Z １ The base is -L １ -SO ３ － Ar at the β position relative to the ring carbon atom to which it is bonded. １ It is bonded to the ring carbon atom, and the at least one Z １ Base and -L １ -SO ３ － The aforementioned condensed polycyclic C ６～６０ The photoresist composition according to claim 10, wherein aromatic groups are bonded to different rings.

14. The photoresist composition according to claim 1, wherein the conjugate acid of the nonpolymeric ionic photoacid generator compound has a pKa of 0 or less.

15. The photoresist composition according to claim 1, wherein the non-solvent alkali-insoluble substrate comprises a polymer.

16. The photoresist composition according to claim 15, wherein the non-solvent alkali-insoluble substrate comprises a chain-severing polymer, an unclipping polymer, or a combination thereof.

17. The photoresist composition according to claim 1, wherein the non-solvent alkali-insoluble substrate includes a metal-containing material.

18. At least one R １ is substituted C ６～３０ aryl or substituted C ７～３０ arylalkyl, optionally further comprising one or more divalent linking groups as part of the structure thereof. The photoresist composition according to claim 1.

19. c is 1, and L １ The photoresist composition according to claim 1, wherein the bond is a single bond.

20. It is a patterning method, To provide a photoresist composition layer by coating a layer of the photoresist composition described in claim 1 onto a substrate, The photoresist composition layer is pattern-exposed with activating radiation to provide the exposed photoresist composition layer. The exposed photoresist composition layer is developed to provide a resist relief image. Patterning methods including

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