PHOTORESISTANCE COMPOSITIONS AND STRUCTURE FORMATION METHODS

Abstract

A photoresist composition comprising one or more alkali-insoluble, non-solvent base materials present in a combined amount of more than 50 wt% based on the total solids of the photoresist composition; a non-polymeric ionic photoacid generator compound comprising an anion and an iodonium or sulfonium cation, the anion being represented by formula (1); a photodegradable quencher, a basic quencher or a combination thereof and a solvent: where Ar 1 for a monocyclic or polycyclic aromatic C 3-60 -Group stands; L 1 L represents a single bond or one or more binary linkage groups. 1 is free of fluorine; Z 1 an anion-stabilizing group, wherein Z 1is designed in such a way that it forms an intramolecular non-covalent bond with the sulfonate anion group, forming a ring with 5 to 8 atoms; and the remaining substituents are defined as shown here.

Description

CROSS-REFERENCE TO RELATED REGISTRATIONS

[0001] The present application is an entry into the national phase of PCT / US2024 / 042626, filed on August 16, 2024, which claims the priority and benefit of the preliminary US application with serial number 65 / 533,270, filed on August 17, 2023, the entire contents of which are hereby expressly incorporated by reference. AREA

[0002] The present invention relates to photoresist compositions and structure formation processes using such photoresist compositions. The invention is particularly applicable to lithographic applications in the semiconductor industry. BACKGROUND

[0003] Photoresist compositions are light-sensitive materials used to transfer a structure onto one or more underlying layers, such as a metal, semiconductor, or dielectric layer, deposited on a substrate. Chemically enhanced positive-tone photoresist compositions are commonly used for high-resolution processing. Such photoresist compositions typically contain a polymer with acid-labile groups and a photoacid generator (PAG). A layer of the photoresist composition is structurally exposed to activating radiation, and the PAG generates an acid in the exposed regions. During annealing after exposure, the acid cleaves the acid-labile groups of the polymer, resulting in a polarity reversal of the polymer in the exposed regions.This causes a difference in solubility properties between the exposed and unexposed areas of the photoresist layer in a developer solution. In a positive tone development (PTD) process, exposed areas of the photoresist layer become soluble in a developer, typically an aqueous basic developer, and are removed from the substrate surface, while unexposed areas remain on the substrate, forming a positive relief image. Alternatively, in a negative tone development (NTD) process, unexposed areas of the photoresist layer can be removed with an organic developer solvent, 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] One property of the photoresist composition that can directly affect the manufacturing costs of semiconductors is its photosensitivity, i.e., its sensitivity to the activating radiation generated by the exposure tool, where higher sensitivity corresponds to a higher process throughput for a given feature size. To increase photosensitivity, it is desirable for the photoresist compound (PAG) to generate an acid strong enough to cleave the acid-labile groups on the polymer. Typical for this purpose are ionic PAG compounds with a photoactive cation and an anion containing a fluorinated sulfonate group, where fluorine atoms and / or fluoroalkyl groups are located in close proximity to the sulfonate group, typically as substituents attached to one or more alkylene carbon atoms bonded to the sulfonate anion group.Upon exposure to activating radiation, the photoactive cation undergoes a cascade of photochemical and chemical processes leading to the formation of a fluorinated sulfonic acid. While certain fluorinated PAGs in this class of compounds enable the production of photoacids with high acidity, the semiconductor manufacturing industry and government regulatory bodies are increasingly seeking to replace them with more sustainable alternatives.

[0005] Examples of existing PAGs are p-toluenesulfonate anions and camphorsulfonic acid anions. However, these anions have relatively low acid dissociation constants (e.g., about 18 orders of magnitude smaller than that of tris(trifluoromethylsulfonyl)methane), which limits their usefulness in photoresists requiring a stronger photoacid. It would therefore be desirable to have a photoresist composition containing an ionic photoacid generator compound that produces a sulfonic acid of sufficient strength, one that does not rely on a specific fluorine substitution for increased acidity.

[0006] There is still a need for photoresist compositions that address one or more problems associated with the state of the art, and for structuring methods using such photoresist compositions. SUMMARY

[0007] One aspect provides a photoresist composition containing one or more alkali-insoluble, non-solvent base materials present in a combined amount of more than 50% by weight, based on the total solids of the photoresist composition; a non-polymeric ionic photoacid generator compound with an anion and an iodonium or sulfonium cation, wherein the anion is represented by formula (1): where in formula (1) Ar 1 for a monocyclic or polycyclic aromatic C 3-60 -Group stands; L 1 L represents a single bond or one or more binary linkage groups. 1 is free of fluorine; R 1 each independently for halogen, hydroxyl, substituted or unsubstituted C 1-30 -Alkyl, substituted or unsubstituted C 3-30 -Cycloalkyl, substituted or unsubstitutedC 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 -Alkyl heteroaryl, substituted or unsubstituted C 4-30 -Heteroarylalkyl or substituted or unsubstituted C 3-30 -Heteroaryloxy stands; R 1 each may further include one or more binary linking groups as part of its structure; Z 1 an anion-stabilizing group, wherein Z 1 is designed in such a way that it forms an intramolecular non-covalent bond with the sulfonate anion group, forming a ring with 5 to 8 atoms, and wherein Z 1from - OH, -C(O)OH, -SH, -C(O)SH, -NHS(O)2R 2 , -S(O)2R 2 , -S(O)2NHS(O)2R 2 , -CH(=NOH) or - B(R 3 )2 is selected; and where Z 1 It may also include one or more binary linking groups as part of its structure; R 2 each independently from 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 -Heteroaryl is selected; R 3 each independently from 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 -Heteroaryl is selected; two R 1 together possibly with Ar1 form an fused ring, the fused ring optionally further comprising one or more divalent linkage groups as part of its structure; and Z 1 and an R 1 together possibly with Ar 1 a fused ring, wherein the fused ring may optionally further include one or more divalent linking groups as part of its structure; and b represents an integer from 0 to 4; a photodegradable quencher, a basic quencher or a combination thereof and a solvent.

[0008] Another aspect provides a structuring process that includes applying a layer of the photoresist composition to a substrate to provide a photoresist composition layer; structurally exposing the photoresist composition layer with activating radiation to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer to provide a resist relief image. DETAILED DESCRIPTION

[0009] Reference will now be made in detail to exemplary embodiments, for which examples are illustrated in the present description. In this respect, the exemplary embodiments presented here can have different forms and are not to be interpreted as being limited to the descriptions set forth herein. Accordingly, the exemplary embodiments are described below by reference to the figures only to explain aspects of the present description. Within the scope of the present invention, the term "and / or" includes all combinations of one or more of the associated listed items. Expressions such as "at least one of" when placed before a list of elements modify the entire list of elements and not the individual elements of the list.

[0010] Within the scope of the present invention, the terms "a," "an," "the," "a," and "a" do not imply any quantitative limitation and are to be interpreted as encompassing both the singular and the plural unless otherwise specified herein or clearly contrary to the context. "Or" means "and / or" unless clearly specified otherwise. The modifier "approximately," when used in conjunction with a quantity, includes the specified value and has the meaning determined by the context (e.g., it includes the degree of error associated with the measurement of the respective quantity). All domains disclosed herein include the endpoints, and the endpoints are independently combinable with one another. The suffix "(e)" is intended to include both the singular and the plural of the term it modifies, thereby encompassing at least one of that term.The terms "optional" or "if applicable" mean that the event or circumstance described below may or may not occur, and that the description includes cases in which the event occurs as well as cases in which it does not. The terms "first," "second," and the like do not denote order, quantity, or importance, but are used to distinguish one element from another. If an element is described as "on" another element, it may be in direct contact with the other element, or there may be intermediate elements between them. Conversely, if an element is described as "directly on" another element, there are no intermediate elements. It is understood that the described components, elements, constraints, and / or features of aspects may be combined in any suitable way within the various aspects.

[0011] Unless otherwise stated or defined, all terms used herein (including technical and scientific terms) have the meanings commonly understood by a person skilled in the art in the field to which the present invention belongs. It is further understood that terms such as those defined in commonly used dictionaries are to be interpreted in a manner consistent with their meaning in the context of the relevant prior art and the present disclosure, and not in an idealized or overly formal sense, unless expressly defined herein as such.

[0012] Within the scope of the present invention, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp, far-ultraviolet rays represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, particle beams such as electron beams and ion beams, or the like. Furthermore, "light" in the present invention means actinic rays or radiation. The krypton fluoride laser (KrF laser) is a special type of excimer laser, sometimes also called an exciplex laser. "Excimer" is short for "excited dimer," while "exciplex" is short for "excited complex."An excimer laser uses a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine) which, under suitable conditions of electrical stimulation and high pressure, emits coherent stimulated radiation (laser light) in the ultraviolet range. Furthermore, unless otherwise specified, the term "exposure" in this application includes not only exposure with a mercury lamp, far-ultraviolet radiation represented by an excimer laser, X-rays, extreme ultraviolet (EUV) radiation, or the like, but also writing with particle beams such as electron beams and ion beams.

[0013] Within the scope of the present invention, the term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight- or branched-chain saturated hydrocarbon group having the specified number of carbon atoms and a valence of one; "alkylene" refers to an alkyl group having a valence of two; "hydroxyalkyl" refers to an alkyl group substituted by at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid group" refer 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 valence of two."Alkenyl" refers to a straight- or branched-chain monovalent hydrocarbon group with at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group with a valence of two; "cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group with at least three carbon atoms and at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group with at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic aromatic ring system that satisfies Hückel's rule (4n+2 π electrons) and contains carbon atoms in the ring;The term "heteroaromatic group" refers to an aromatic group containing one or more heteroatoms (e.g., 1-4 heteroatoms) selected from N, O, and S in place of a carbon atom in the ring; "aryl" refers to a monovalent monocyclic or polycyclic aromatic ring system in which each ring member is carbon and may include a group with an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene" refers to an aryl group with a valence of two; "alkylaryl" refers to an aryl group substituted by an alkyl group; "arylalkyl" refers to an alkyl group substituted by an aryl group; "aryloxy" refers to "aryl-O-" and "arylthio" refers to "aryl-S-".

[0014] The prefix "hetero" means that the compound or group contains at least one member that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatom(s)) instead of a carbon atom, where the heteroatom is a carbon or carbon atom.the heteroatoms are N, O, S, Si or P; “heteroatom-containing group” refers to a substituent group containing at least one heteroatom; “heteroalkyl” refers to an alkyl group with at least one heteroatom instead of carbon; “heterocycloalkyl” refers to a cycloalkyl group with 1-4 heteroatoms as ring members instead of carbon; “heterocycloalkylene” refers to a heterocycloalkyl group with a valence of two; “Heteroaryl” refers to an aromatic 4-8-membered monocyclic, 8-12-membered bicyclic or 11-14-membered tricyclic ring system with 1-4 heteroatoms (if monocyclic), 1-6 heteroatoms (if bicyclic) or 1-9 heteroatoms (if tricyclic) each independently selected from N, O, S, Si or P (e.g. carbon atoms and 1-3, 1-6 or 1-9 heteroatoms of N, O or S, depending on whether monocyclic, bicyclic or tricyclic).Examples of heteroaryl groups are pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl and the like; and “heteroaryls” refers to a heteroaryl group with a valence of two.

[0015] The term "halogen" means a monovalent substituent, which is fluorine, chlorine, bromine, or iodine. The prefix "halogen" means a group that contains one or more fluorine, chlorine, bromine, or iodine substituents in place of a hydrogen atom. It may be a combination of halogen groups (e.g., bromine and fluorine), or it may consist only of fluorine groups. For example, "halogenalkyl" refers to an alkyl group substituted by one or more halogens. In the context of the present invention, "substituted C" refers to 1-8 -Halogenalkyl" on a C 1-An 8-alkyl group substituted by at least one halogen and further substituted by one or more other non-halogenated substituent groups. It is understood that the substitution of a group by a halogen atom is not to be considered a heteroatom-containing group, since a halogen atom does not replace a carbon atom.

[0016] Any of the preceding substituent groups may be substituted, if applicable, unless explicitly stated otherwise. The term "substituted, if applicable" refers to substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of the chemical structure or group is replaced by another terminal substituent group, typically monovalent, provided that the normal valence of the designated atom is not exceeded. If the substituent is oxo (i.e., O), two geminal hydrogen atoms on the carbon atom are replaced by the terminal oxo group. It is further noted that the oxo group is bonded to the carbon via a double bond, resulting in a carbonyl (C=O), the carbonyl group here represented as -C(O)-. Combinations of substituents or variables are permitted.Examples of substituent groups that can be present at a “substituted” position include Nitro (-NO2), Cyano (-CN), Hydroxyl (-OH), Oxo (O), Amino (-NH2), Mono- or Di(C). 1-6 )alkylamino, alkanoyl (like a C 2-6 -Alkanoyl group such as acyl), formyl (-C(O)H), carboxylic acid or an alkali metal or ammonium salt thereof; esters (including acrylates, methacrylates and lactones) such as 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); Amido (-C(O)NR2, where R is hydrogen or C 1-6 -Alkyl stand), Carboxamido (-CH2C(O)NR2, where 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 -Alkenyl, C 2-6 -Alkynyl, C 1-6 -Haloalkyl, C 1-9 -Alkoxy, C 1-6 -Halogenalkoxy, C 3-12 -Cycloalkyl, C 5-18 -Cycloalkenyl, C 2-18-Heterocycloalkenyl, C 6-12 -Aryl with at least one aromatic ring (e.g. phenyl, biphenyl, naphthyl or the like, each ring being either substituted or unsubstituted aromatic), C 7-19 -Arylalkyl with 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, arylalkoxy with 1 to 3 separate or fused rings and 6 to 18 ring 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 -Arylsulfonyl (-S(O)2-Aryl) or tosyl (CH3C6H4SO2-).

[0017] In the context of the present invention, unless otherwise defined, a “bivalent linking group” refers to a bivalent group comprising one or more of the following: -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)-, substituted or unsubstituted C 1-30-Alkylene, substituted or unsubstituted C 3-30 -Cycloalkylenes, substituted or unsubstituted C 3-30 -Heterocycloalkylene, substituted or unsubstituted C 6-30 -Arylene, substituted or unsubstituted C 3-30 -contains heteroarylene or a combination thereof, where each R' is independent for 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 is present. Typically, the "divalent linking group" contains one or more of -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 -Cycloalkylenes, substituted or unsubstituted C 3-30 -Heterocycloalkylene, substituted or unsubstituted C6-30 -Arylene, substituted or unsubstituted C 3-30 -Heteroarylene or a combination thereof, where 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 stands for. Typically, the "divalent linkage group" contains at least one of -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 -Cycloalkylenes, substituted or unsubstituted C 3-10 -Heterocycloalkylene, substituted or unsubstituted C 6-10 -Arylene, substituted or unsubstituted C 3-10 -Heteroarylene or a combination thereof, where R represents hydrogen, substituted or unsubstituted C 1-10 -Alkyl, substituted or unsubstituted C1-10 -Heteroalkyl, substituted or unsubstituted C 6-10 -Aryl or substituted or unsubstituted C 3-10 -Heteroaryl is present.

[0018] Within the scope of the present invention, an “acid-labile group” refers to a group in which a bond is cleaved by the action of an acid, optionally and typically with heat treatment, leading to the formation of a polar group, such as a carboxylic acid or alcohol group. In some cases, the acid-labile group can be formed on a polymer, optionally and typically with the detachment of a grouping associated with the cleaved bond from the polymer. In other systems, a non-polymeric compound can contain an acid-labile group that can be cleaved by the action of an acid, leading to the formation of a polar group, such as a carboxylic acid or alcohol group, on a cleaved portion of the non-polymeric compound.Such an acid is typically a photogenerated acid, with bond cleavage occurring during post-exposure baking (PEB); however, embodiments are not limited to this, and, for example, such an acid can be thermally generated. Suitable acid-labile groups include, for example, tertiary alkyl ester groups, secondary or tertiary ester groups containing aryl groups, secondary or tertiary ester groups containing a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-labile groups are also commonly referred to in the prior art as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-labile protecting groups," "acid-leaving groups," "acid-decomposable groups," and "acid-sensitive groups."

[0019] The sensitivity of photoresist performance is often correlated with the final throughput in fixture fabrication. Particularly in high-resolution lithography techniques, such as 193 nm lithography (ArF), there are typically difficulties in obtaining photoresists with optimal sensitivity. To achieve good sensitivity, many photoresists employ photoacid generators (PAGs) containing a sulfonate-class anion coupled to a polymer containing a leaving group with a low activation energy (e.g., an ester acetal or an acetal ester). Numerous sulfonate derivatives, such as fluorinated sulfonates, have been developed for this purpose over the last decade. This class of compounds, which has proven highly effective in lithography due to its remarkably high acidity, is being considered worldwide for replacement in favor of more sustainable alternatives.There remains a persistent need for PAG anions with good acidity and better sustainability.

[0020] In the course of the present invention, photoacid generators were discovered that contain an anionic core comprising an aromatic group substituted by a sulfonate anion group and an anion-stabilizing group configured to stabilize the sulfonate anion group with an intramolecular non-covalent bond. In other words, the anion-stabilizing group is configured to form an intramolecular non-covalent bond with the sulfonate anion group. Without specifying any particular theory, the anion-stabilizing group may, for example, be capable of forming an intramolecular non-covalent bond with the sulfonate anion group.In some embodiments, the intramolecular non-covalent bond can be formed in situ, as when the non-polymeric ionic photoacid generator compound is included in the photoresist composition. When used in photoresist compositions, PAGs according to the invention can lead to suitable lithographic properties, such as dimensional energy (ED). size ), Exposure latitude (EL) in % and / or line width roughness.

[0021] A photoresist composition is provided, comprising one or more alkali-insoluble, non-solvent base materials present in a combined amount of more than 50 wt% based on the total solids of the photoresist composition, a non-polymeric ionic photoacid generator compound with an anion and an iodonium or sulfonium cation, wherein the anion is represented by formula (1): a photodegradable quencher, a basic quencher, or a combination thereof, and a solvent. It is understood that the total solids comprise one or more alkali-insoluble, non-solvent base materials, the non-polymeric ionic photoacid generator compound, and other non-solvent components.

[0022] In formula (1) Ar 1 for a monocyclic or polycyclic aromatic C 3-60 -group. For example, it can be the monocyclic or polycyclic aromatic C 3-60 -group around a monocyclic aromatic C 3-60 -group or a polycyclic aromatic C 6-60 -group. In one embodiment, the monocyclic or polycyclic aromatic C 3-60 -group around a monocyclic or polycyclic C 6-60 -arylene group or a monocyclic or polycyclic C 3-60-Heteroarylene group, typically a monocyclic or polycyclic C 6-30 -arylene group or a monocyclic or polycyclic C 3-30 -Heteroaryl group, act.

[0023] It goes without saying that when the “monocyclic or polycyclic C 6-60 The "-arylene group" is polycyclic, meaning the number of carbon atoms is sufficient to make the group chemically realizable. For example, the "monocyclic or polycyclic C 6-60 -arylene group" to "a monocyclic C6 arylene group or a polycyclic C 10-60 -arylene group" or, for example, "a monocyclic C6 arylene group or a polycyclic C 10-30 -arylene group". Likewise, it is sufficient if the "monocyclic or polycyclic C 3-60 The term "-heteroarylene group" is polycyclic, and the number of carbon atoms determines whether the group is chemically realizable. For example, the "monocyclic or polycyclic C" can be3-60 -Heteroarylene group" on "a monocyclic C 3-6 -Heteroarylene group or a polycyclic C 5-60 -heteroarylene group" or, for example, "a monocyclic C 3-6 -Heteroarylene group or a polycyclic C 5-30 -Heteroaryl group" refers to.

[0024] Exemplary monocyclic or polycyclic aromatic C 3-60 Groups include benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene or benzo[a]pyrene.

[0025] In formula (1) L 1 for a single bond or one or more divalent linkage groups, where L 1 is free of fluorine. In other words, it is free when L 1 L stands for one or more binary linking groups 1 Fluorine-free.

[0026] The one or more divalent linking groups can each be substituted or unsubstituted. Examples of divalent linking groups can each be independently composed of -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C. 1-30 -Alkylene, substituted or unsubstituted C 3-30 -Cycloalkylenes, substituted or unsubstituted C 3-30 -Heterocycloalkylene, substituted or unsubstituted C 6-30 -Arylene, substituted or unsubstituted C 3-30 -Heteroaryls or a combination thereof are selected, where R' represents 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 can be present. Typically, L 1for a single bond or substituted or unsubstituted C 1-20 -Alkylene, preferably a single bond or substituted or unsubstituted C 1-10 -Alkylenes, where L 1 does not contain an α-carbon atom directly covalently bonded to the sulfur atom of the sulfonate anion group, which is substituted by a fluorine atom or a fluoroalkyl group.

[0027] In formula (1) R 1 each independently for 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 -Alkyl heteroaryl, substituted or unsubstituted C 4-30 -Heteroarylalkyl or substituted or unsubstituted C 3-30 -Heteroaryloxy. For example, R 1 each independently for 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-Alkyl heteroaryl, substituted or unsubstituted C 4-30 -Heteroarylalkyl or substituted or unsubstituted C 3-30 -Heteroaryloxy. In some embodiments, at least one R 1 for a substituted C 6-30 -Aryl or a substituted C 7-30 -Arylalkyl.

[0028] In formula (1) R includes 1 Each compound may also include one or more divalent linking groups as part of its structure. These one or more divalent linking groups can be substituted or unsubstituted. Examples of divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C. 1-30 -Alkylene, substituted or unsubstituted C 3-30 -Cycloalkylenes, substituted or unsubstituted C 3-30 -Heterocycloalkylene, substituted or unsubstituted C 6-30-Arylene, substituted or unsubstituted C 3-30 -Heteroaryls or a combination thereof are selected, where R' represents 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 can be present.

[0029] In some embodiments, when R 1 R stands for hydroxyl 1 Furthermore, one or more divalent linkage groups are part of its structure. Examples of divalent linkage groups can consist of substituted or unsubstituted C. 1-30 -Alkylene, substituted or unsubstituted C 3-30 -Cycloalkylenes, substituted or unsubstituted C 3-30 -Heterocycloalkylene, substituted or unsubstituted C 6-30 -Arylene, substituted or unsubstituted C 3-30-Heteroaryls or a combination thereof are selected, where R' represents 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 can be present.

[0030] In some embodiments, R 1 do not include hydroxyl if Z 1 Hydroxyl includes. For example, R 1 in some embodiments do not include hydroxyl if Z 1 stands for hydroxyl.

[0031] In some embodiments, one or more R 1 Each independently contains an acid-labile group, a lactone-containing group, a base-solubilizing group or the like, or a combination thereof.

[0032] In formula (1) Z 1 an anion-stabilizing group, wherein Z 1is designed in such a way that it forms an intramolecular non-covalent bond with the sulfonate anion group, forming a ring with 5 to 8 atoms, and wherein Z 1 from -OH, -C(O)OH, -SH, -C(O)SH, - NHS(O)2R 2 , -S(O)2R 2 , -S(O)2NHS(O)2R 2 , -CH(=NOH) or -B(R 3 )2 is selected, where R 2 and R 3 each as defined here. Typically, the anion-stabilizing group Z 1 be selected independently from -OH, C(O)OH, SH or -B(OH)2, and preferably comprises the anion-stabilizing group Z 1 -OH.

[0033] The anion-stabilizing group Z 1 It is designed in such a way that it forms an intramolecular non-covalent bond with the sulfonate anion group, forming a ring with 5 to 8 atoms. For example, Z 1It should be designed in such a way that it forms an intramolecular non-covalent bond with the sulfonate anion group, forming a ring with 6 or 7 atoms.

[0034] In the context of the present invention, the "anion-stabilizing group" refers to any suitable group capable of stabilizing the sulfonate anion group via an intramolecular non-covalent bond, as provided herein. Therefore, the anion-stabilizing group is configured to form an intramolecular non-covalent bond with the sulfonate anion group; or, in other words, the anion-stabilizing group is capable of forming an intramolecular non-covalent bond with the sulfonate anion group. In the context of the present invention, the "non-covalent bond" can refer to any non-covalent bonding interaction between the anion-stabilizing group and the sulfonate anion group. As mentioned above, the non-covalent bonding interaction is intramolecular, with the anion-stabilizing group and the sulfonate anion group being located on the same molecule.Examples of non-covalent bonds include hydrogen bonds or ionic bonds. The anion-stabilizing group may comprise 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.Within the scope of the present invention, “non-covalent bonding” does not include bonding based exclusively on van der Waals forces.

[0035] In some embodiments, the anion-stabilizing group may have a pKa value of 25 or less, typically 20 or less or 18 or less, and preferably 16 or less.

[0036] In some embodiments, the anion-stabilizing group Z comprises 1 a group that is protic. For example, if the anion-stabilizing group is protic, then Z 1 from -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 be selected, where R 2 each independently from 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 -Heteroaryl is selected; each R 2a Hydroxyl is and R 3a each independently from 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 -Heteroaryl is selected, provided that at least one R 3a stands for hydrogen or hydroxyl.

[0037] In formula (1) Z includes 1 Optionally, one or more divalent linking groups may also be part of its structure. The one or more divalent linking groups may be substituted or unsubstituted. Examples of divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C.1-30 -Alkylene, substituted or unsubstituted C 3-30 -Cycloalkylenes, substituted or unsubstituted C 3-30 -Heterocycloalkylene, substituted or unsubstituted C 6-30 -Arylene, substituted or unsubstituted C 3-30 -Heteroaryls or a combination thereof are selected, where R' represents 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 can be present. Typically, Z can 1 optionally also containing one or more divalent linking groups consisting of - O-, -C(O)-, -C(O)O-, -S(O)-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-10 -Alkylene, substituted or unsubstituted C 3-10 -Cycloalkylenes, substituted or unsubstituted C 3-10-Heterocycloalkylene, substituted or unsubstituted C 6-30 -Arylene, substituted or unsubstituted C 3-30 -Heteroaryls or a combination thereof are selected, where 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 can be present. In some embodiments, Z contains 1 no divalent linking group, so the anion-stabilizing group attaches directly to Ar 1 is bound.

[0038] In formula (1) R 2 each independently from fluorine, hydroxyl, substituted or unsubstituted C 1-20 -Alkyl, substituted or unsubstituted C 1-2 o-Heteroalkyl, substituted or unsubstituted C 6-30 -Aryl or substituted or unsubstituted C 3-30-Heteroaryl selected.

[0039] In formula (1) R 3 each independently from 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 -Heteroaryl selected.

[0040] In formula (1) two R 1 together possibly with Ar 1 an fused ring, wherein the fused ring may further comprise one or more divalent linkage groups as part of its structure. Each of the one or more divalent linkage groups is substituted or unsubstituted, and the fused ring is substituted or unsubstituted.

[0041] In formula (1) Z 1 and an R 1 together possibly with Ar 1an fused ring, wherein the fused ring optionally further comprises one or more divalent linkage groups as part of its structure. Each of the one or more divalent linkage groups is substituted or unsubstituted, and the fused ring is substituted or unsubstituted. The one with Ar 1 The resulting fused ring can be aliphatic or aromatic.

[0042] In formula (1) b represents an integer from 0 to 4. Typically, b represents an integer from 0 to 2, preferably b represents 0 or 1.

[0043] In some embodiments, the anion may be free of trifluoromethyl and difluoromethylene groups. In other words, the anion of formula (1) may be free of trifluoromethyl and difluoromethylene groups in some embodiments. For example, in some embodiments, the anion does not contain fluorine (the anion of formula (1) may be fluorine-free).

[0044] In some embodiments, Ar 1 for a monocyclic aromatic C 3-60 -Group stand and stands Z 1 in an ortho position to that defined by -L 1 -SO3 - reproduced group. For example, Ar 1 for a monocyclic aromatic C 3-6 -group stand and can Z 1 in an ortho position to that defined by -L 1 -SO3 - The group shown is present. In some embodiments, Ar 1 for a monocyclic aromatic C 3-6 -group stand, L 1 for a single binding and Z 1 in an ortho position to that defined by -L 1 -SO3 - group shown.

[0045] In some embodiments, Ar 1 for a polycyclic aromatic C 6-60 -group stand and the Z 1 -group attached to a ring carbon atom of Ar 1, which is in an ortho position on the same ring as the one defined by -L 1 -SO3 - The reproduced group is bound to be. For example, Ar 1 for a polycyclic aromatic C 6-60 -Group stands, stands L 1 for a single binding and can the Z 1 -group attached to a ring carbon atom of Ar 1 , which is in an ortho position on the same ring as the one defined by -L 1 -SO3 - The group shown is bound.

[0046] In some embodiments, formula (1) Ar 1 for a polycyclic aromatic C 6-60 -Group stand and Z 1 to a ring carbon atom of Ar 1 , which is in a beta position to a ring carbon atom, to the -L 1 -SO3 - bound is, stands, be bound and are Z 1 and -L 1 -SO3 -to different rings of the polycyclic aromatic group. Within the scope of the present invention, the term “substituent groups in a beta position” refers to substituent groups that are bonded to a respective aromatic ring carbon atom on different rings of the polycyclic ring system, wherein the ring carbon atoms are separated by a common ring carbon atom.

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

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

[0049] In formula (1a) Ar 1 for a monocyclic or polycyclic aromatic C 3-60 -group, as defined in formula (1).

[0050] In formula (1a) Z 1 an anion-stabilizing group, as defined in formula (1).

[0051] In formula (1a) R 1 each independently as defined in formula (1).

[0052] In formula (1a) b represents an integer from 0 to 4.

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

[0054] In formulas (2a) to (2f) Z is contained 1 an anion-stabilizing group, as defined in formula (1).

[0055] In formulas (2a) to (2f) R 1 each independently as defined for formula (1).

[0056] In formulas (2a) to (2f) b represents an integer from 0 to 4.

[0057] In some embodiments, the anion of formula (1) can be represented by one of the formulas (3a) to (3h):

[0058] In formulas (3a) to (3h) Z is contained 1 an anion-stabilizing group, as defined in formula (1).

[0059] In formulas (3a) to (3h) R 1 each independently as defined for formula (1).

[0060] In formulas (3a) to (3h) b represents an integer from 0 to 4.

[0061] Exemplary groups where Z 1 in an ortho position to that defined by -L 1 -SO3 - The group shown includes those represented by formulas (3a), (3b), (3d), (3f) and / or (3g).

[0062] Exemplary groups where Ar 1 for an fused polycyclic aromatic C 6-60 -Group stands and Z 1 to a ring carbon atom of Ar 1, which is in a beta position to a ring carbon atom, to the -L 1 -SO3 - is bound, stands, is bound and the Z 1 -Group and - L 1 -SO3 - to different rings of the fused polycyclic aromatic C 6-60 The -group bound include those represented by formulas (3c), (3e) and / or (3h).

[0063] Exemplary anions of the nonpolymeric ionic photoacid generator compound represented by formula (1) include the following:

[0064] The anions of the nonpolymeric ionic photoacid generator compound can be obtained from commercial sources or prepared by any suitable method. For example, such anions can be prepared as described in the examples presented here.

[0065] As discussed above, the anion-stabilizing group is designed to form an intramolecular non-covalent bond with the sulfonate anion group. Without committing to any specific theory, the anion-stabilizing group may, for example, form an intramolecular non-covalent bond with the sulfonate anion group. In some embodiments, the intramolecular non-covalent bond may form in situ, such as when the non-polymeric ionic photoacid generator compound is included in the photoresist composition. In some aspects, the intramolecular non-covalent bond, such as an intramolecular hydrogen bond, may form between the anion-stabilizing group and the sulfonate anion.The resulting intramolecular hydrogen-bonding structure can form a ring with 5-8 atoms, and most preferably 6-8 atoms. For example, an exemplary intramolecular hydrogen-bonding interaction between an anion-stabilizing group and the sulfonate anion group is shown below in formula (I), wherein the intramolecular hydrogen-bonding structure forms a ring with 6 atoms, but embodiments are not limited thereto.

[0066] The nonpolymeric ionic photoacid generator compound further contains 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):

[0067] In formulas (4a) and (4b) R 30 to R 34 each independently for substituted or unsubstituted C 1-30 -Alkyl, substituted or unsubstituted C3-30 -Cycloalkyl, substituted or unsubstituted C 2-30 -Alkenyl, substituted or unsubstituted C 2-30 -Alkynyl, 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 -Heteroarylalkyl or combinations thereof. R 30 to R 34 can be either separate or linked to another group R via a single bond or a binary linkage group 30 to R 34 be connected, forming a ring. R 30 to R 34 They may each contain a binary linking group as part of their structure. R 30 to R 34may independently include an acid-labile group, which may be selected, for example, from tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups or ketal groups.

[0068] Exemplary sulfonium cations of formula (4a) may include one or more of the following:

[0069] Exemplary iodonium cations of formula (4b) may include one or more of the following:

[0070] The cations for the non-polymeric ionic photoacid generator compounds can be obtained from commercial sources or prepared using common synthesis methods.

[0071] Suitable nonpolymeric ionic photoacid generator compounds are those resulting from any combination of the anions and cations described above. These nonpolymeric ionic photoacid generator compounds can be prepared by combining the anion and cation species under appropriate conditions.

[0072] The nonpolymeric ionic photoacid generator compound may be present in the photoresist composition in an amount of 1 to 65 wt%, typically 15 to 30 wt%, 8 to 14 wt%, or 2 to 7 wt%, based on the total solids of the photoresist composition. In some embodiments, the photoresist composition may contain two or more different nonpolymeric ionic photoacid generator compounds as described herein. For example, the photoresist composition may contain one or more nonpolymeric ionic photoacid generator compounds in a combined amount of 1 to 65 wt%, typically 15 to 30 wt%, 8 to 14 wt%, or 2 to 7 wt%, based on the total solids of the photoresist composition.

[0073] The photoresist composition may further contain an additional photoacid generator. The additional PAG may be in ionic or nonionic form. The additional PAG may be in polymeric or nonpolymeric form. In polymeric form, the additional PAG may be present as a grouping within a repeating unit of a polymer derived from a polymerizable PAG monomer.

[0074] In some embodiments, the additional photoacid generator can produce a photoacid with a higher acidity than a photoacid produced by the nonpolymeric ionic photoacid generator compound described above. In other embodiments, the additional photoacid generator does not decompose a photoacid with a higher acidity than a photoacid produced by the nonpolymeric ionic photoacid generator compound described above.

[0075] Suitable additional PAG compounds can be formulated as G + A- correspond, where G + stands for a photoactive cation and A -for an anion capable of generating a photoacid. The photoactive cation is preferably selected from onium cations, preferably iodonium or sulfonium cations, such as those described above with respect to the nonpolymeric ionic photoacid generator compounds according to the invention (e.g., those of formulas (4a) and / or (4b)). Anions whose conjugated acids have a pKa value of -18 to 0, or -15 to 0, or -14 to 0, or -13 to 0 are particularly suitable. The anion is typically an organic anion with a sulfonate group or a non-sulfonate group, such as sulfonamidate, sulfonimidate, methide, arsenate, or borate. In some embodiments, the additional PAG may have an anion with a structure of formula (1), as defined for the anion of the nonpolymeric ionic photoacid generator compound, wherein the anion of the additional PAG compound does not contain group Z. 1contains an anion-stabilizing group.

[0076] In some aspects, the anion of the additional PAG does not contain -F, -CF3, or -CF2 groups and is free of these groups. It is understood that "free of -F, -CF3, or -CF2 groups" means that the anion of the additional PAG excludes groups such as -CH2CF3 and -CH2CF2CH3. In other aspects, the anion of the additional PAG is free of fluorine (i.e., it contains no fluorine atom and is not substituted by a fluorine-containing group). In some aspects, the additional PAG is free of fluorine (i.e., both the photoactive cation and the anion are free of fluorine).

[0077] Examples of onium salts include triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, di-t-butyphenyliodonium perfluorobutanesulfonate, and di-t-butyphenyliodonium camphorsulfonate. Further useful additional PAG compounds are known in the prior art of chemically enhanced photoresists and include, for example, nonionic sulfonyl compounds such as 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, and 2,4-dinitrobenzyl p-toluenesulfonate. Sulfonic acid esters, for example 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, for example bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane;Glyoxime derivatives, for example, bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of an N-hydroxyimide compound, for example, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester; and halogen-containing triazine compounds, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Suitable additional PAGS are further described in U.S. Patents 8,431,325 and 4,189,323.

[0078] If the photoresist composition contains an additional non-polymeric PAG, the additional PAG is typically present in the photoresist composition in an amount of 0.1 to 55 wt%, typically 1 to 25 wt%, based on the total solids of the photoresist composition. If it is present in polymeric form, the additional PAG is typically present in a polymer in an amount of 1 to 25 mol%, typically 1 to 8 mol% or 2 to 6 mol%, based on the total repeating units in the polymer.

[0079] The photoresist composition also contains one or more alkali-insoluble, non-solvent base materials present in a combined amount of more than 50% by weight, based on the total solids of the photoresist composition. The one or more alkali-insoluble, non-solvent base materials, which may alternatively be referred to here as the matrix material, may be polymeric or non-polymeric. Suitable alkali-insoluble base materials are readily apparent to a person skilled in the art based on the description provided herein. In some embodiments, the alkali-insoluble base material does not contain a phenolic hydroxyl group, such as a novolac resin containing phenolic hydroxyl groups. In some embodiments, the alkali-insoluble base material does not contain a carboxylic acid group.In some embodiments, the alkali-insoluble base material may contain a phenolic hydroxyl group and / or a carboxylic acid group, provided that the alkali insolubility of the base material is maintained.

[0080] To determine whether a particular base material is alkali-insoluble, it can be subjected to a solubility test with an aqueous alkaline developer solution, such as 0.26 N aqueous tetramethylammonium hydroxide (TMAH). Alkali solubility can be determined, for example, by the following method. A film of the base material can be applied to the surface of a silicon substrate by spin coating, and an initial film thickness can be measured. The film can then be immersed in 0.26 N aqueous TMAH solution for 60 seconds at room temperature, rinsed with deionized water, and air-dried under typical development conditions, after which the film thickness is 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 base material may comprise a polymer, a metal-containing material, or a combination thereof. It is understood that "base material" does not define the material as basic (e.g., the base material is not necessarily basic according to the definition of acid / base chemistry).

[0082] The polymer of the photoresist composition can be a homopolymer or a copolymer containing two or more structurally distinct repeating units. For example, the polymer can contain one or more repeating units that include a functional group selected from a hydroxyaryl group, an acid-labile group, a base-solubilizing group, a lactone-containing group, a sultone-containing group, a polar group, a crosslinkable group, a crosslinking group, or the like, or a combination thereof.

[0083] In one or more embodiments, the polymer can contain a repeating unit formed from a monomer with an acid-labile group. Suitable acid-labile groups include, for example, tertiary ester, acetal, ketal, and tertiary ether groups. where R d for hydrogen, halogen (e.g. F, Cl, Br, I), substituted or unsubstituted C 1-6 -Alkyl or substituted or unsubstituted C 3-6 -Cycloalkyl stands.

[0084] If a repeating unit with an acid-labile group is present in the polymer, it is typically present in an amount of 25 to 75 mol%, more typically 25 to 50 mol%, and even more typically 30 to 50 mol%, based on the total repeating units in the polymer.

[0085] In some embodiments, the polymer may contain a repeating unit derived from one or more lactone-containing monomers. Suitable lactone-containing monomers include, for example: where R d for hydrogen, halogen (e.g. F, Cl, Br, I), substituted or unsubstituted C 1-6 -Alkyl or substituted or unsubstituted C 3-6 -Cycloalkyl stands.

[0086] If the polymer contains a repeating unit derived from one or more lactone-containing monomers, it is typically present in an amount of 0.5 to 75 mol%, more typically 1 to 50 mol%, and still more typically 5 to 50 mol%, relative to the total repeating units in the polymer.

[0087] In some embodiments, the polymer may contain a repeating unit with a base-solubilizing group and / or with a pKa value less than or equal to 12. Exemplary base-solubilizing groups may include a fluoroalcohol group, a carboxylic acid group, a carboximide group, a sulfonamide group, or a sulfonimide group.

[0088] Non-restrictive examples of monomers with a base-solubulating group are the following: where R i for hydrogen, halogen (e.g. F, Cl, Br, I), substituted or unsubstituted C 1-6 -Alkyl or substituted or unsubstituted C 3-6 -Cycloalkyl stands.

[0089] If the polymer contains a repeating unit with a base-solubilizing group and / or with a pKa value less than or equal to 12, it is typically present in an amount of 0.5 to 30 mol%, more typically 15 to 25 mol%, and still more typically 5 to 10 mol%, based on the total number of repeating units in the polymer.

[0090] The polymer may also optionally contain one or more repeating units containing aromatic groups. For example, such repeating units may include one or more of the following: where R b for hydrogen, halogen (e.g. F, Cl, Br, I), substituted or unsubstituted C 1-6 -Alkyl or substituted or unsubstituted C 3-6 -Cycloalkyl stands.

[0091] If present, the polymer typically includes one repeating unit containing aromatic groups in an amount of 1 to 80 mol%, more typically 5 to 75 mol%, and still more typically 5 to 50 mol%, based on the total repeating units in the polymer.

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

[0093] In formula (5) X b L represents a polymerizable group, which may be a vinylic group with carbon-carbon unsaturation. 2 for a divalent linking group consisting of substituted or unsubstituted C 1-10 -Alkylene, substituted or unsubstituted C 3-10 -Cycloalkylenes, substituted or unsubstituted C 3-10-Heterocycloalkylene, substituted or unsubstituted C 6-12 -Arylene, substituted or unsubstituted C 4-12 -Heteroaryls or a combination thereof is selected.

[0094] In formula (5) R 7 and R 8 each independently for 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 7-30 -Arylalkyl, 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 -Alkyl heteroaryl. Preferably R 7 and R 8each independently for hydrogen, substituted or unsubstituted C 1-20 -Alkyl, substituted or unsubstituted C 3-20 -Cycloalkyl or substituted or unsubstituted C 3-20 -Heterocycloalkyl. Both R 7 as well as R 8 They may also include a binary linking group as part of their structure.

[0095] In formula (5) R 9 for substituted or unsubstituted C 1-20 -Alkyl, substituted or unsubstituted C 3-20 -Cycloalkyl or substituted or unsubstituted C 3-20 -Heterocycloalkyl R 9 It may also include a binary linking group as part of its structure.

[0096] In formula (5) one of R can be 7 or R 8 possibly together with R 9A heterocyclic ring is formed via a single bond or a divalent linkage group, and the ring may be substituted or unsubstituted. The ring can be monocyclic, non-annelated polycyclic, or annelated polycyclic and is typically monocyclic when formed.

[0097] Non-restrictive examples of monomers represented by formula (5) are: where R d for hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 -Alkyl stands for.

[0098] If present, the polymer typically comprises a repeating unit with an acetal monomer that does not contain an ester acetal, in an amount of 1 to 80 mol%, more typically 5 to 75 mol%, and still more typically 5 to 50 mol%, based on the total repeating units in the polymer.

[0099] The polymer may optionally contain one or more additional repeating units. These additional repeating units may, for example, be used to adjust properties of the photoresist composition, such as etch rate and solubility. Exemplary additional units may include those derived from one or more (meth)acrylate, vinyl aromatic, vinyl ether, vinyl ketone, and / or vinyl ester monomers. If present in the polymer, the one or more additional repeating units may be used in an amount of up to 50 mol%, typically from 3 to 50 mol%, based on the total repeating units of the polymer.

[0100] Non-limiting exemplary polymers of the present invention include one or more of the following: where a, b and c represent the mole fractions for the respective repeating units of the polymer and a + b + c = 1. It is understood that the mole fractions of a, b and c are chosen such that the polymer is alkali-insoluble.

[0101] In some embodiments, the alkali-insoluble, non-solvent base material may contain a chain-cleavable polymer, an unzipping polymer, or a combination thereof.

[0102] Chain-cleavable polymers can undergo chain-cleaving reactions under suitable conditions. Any suitable chain-cleavable polymer can be used. Examples of polymers that can be chain-cleaved by direct photolysis include copolymers of one or more α-substituted styrenes and substituted α-haloacrylates, such as α-methylstyrene / methyl-α-chloroacrylate copolymer, 2-trifluoroethyl-α-chloroacrylate / α-methyl-4-fluorostyrene copolymer, or the like, or a combination thereof.

[0103] Unzipping polymers are polymers with an unzipping polymer end group that, upon suitable stimulation (photo-induced or chemically induced stimulus), triggers the unbundling of the polymer backbone into smaller fragments. Typically, the unzipping polymer is chosen such that the stimulation of an initial chemical modification or degradation event induces a partial or complete unzipping effect. Any suitable unzipping polymer can be used.

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

[0105] The polymer can be prepared using any suitable prior art process. For example, one or more monomers corresponding to the repeating units described herein can be combined or added separately and polymerized in a reactor using one or more suitable solvents and a suitable initiator. The polymers can be obtained, for example, by polymerizing the respective monomers under any suitable conditions, such as heating to an effective temperature, irradiation with actinic radiation at an effective wavelength, or a combination thereof.

[0106] In some embodiments, one or more of the alkali-insoluble, non-solvent base materials may be a metal-containing material. Examples of metal-containing materials include organometallic resists (e.g., photoinduced crosslinkable organometallic resists or the like), metal oxide resists or the like, or a combination thereof. In one embodiment, the metal-containing material may contain 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 a combination thereof. Typically, the metal-containing material may contain Sn, Zr, Hf, Si, Ge, Se, or a combination thereof.

[0107] The one or more alkali-insoluble, non-solvent base materials are present in a combined amount of more than 50 wt%, based on the total solids of the photoresist composition. For example, the one or more alkali-insoluble, non-solvent base materials may be present in a combined amount of 50 wt% to 99 wt%, typically 60 wt% to 95 wt% or 70 wt% to 90 wt%, based on the total solids of the photoresist composition.

[0108] The photoresist composition further comprises a solvent for dissolving the components of the composition and facilitating their application to 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); propylene glycol monomethyl ether (PGME); and ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone and cyclohexanone (CHO);Esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), and ethyl acetoacetic acid; lactones such as gamma-butyrolactone (GBL) and epsilon-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or non-cyclic carbonic acid 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 a combination thereof. Preferred solvents include PGME, PGMEA, EL, GBL, HBM, CHO, DAA, or a combination thereof.

[0109] The total solvent content (i.e., the cumulative solvent content for all solvents) in photoresist compositions is typically 40 to 99 wt.%, for example, 60 to 99 wt.% or 85 to 99 wt.%, based on the total solids of the photoresist composition. The desired solvent content depends, for example, on the desired thickness of the applied photoresist layer and the application conditions.

[0110] In some aspects, the photoresist composition may further include a material containing one or more base-labile groups (a "base-labile material"). Within the scope of the present invention, base-labile groups are functional groups that, after exposure and post-exposure pre-annealing in the presence of an aqueous alkaline developer, can undergo a cleavage reaction, providing polar groups such as hydroxyl, carboxylic acid, sulfonic acid, and the like. Prior to a development step of the photoresist composition comprising the base-labile group, the base-labile group does not react to any significant extent (e.g., it does not undergo a bond-breaking reaction). For example, a base-labile group is largely inert during pre-annealing, exposure, and post-exposure annealing."Largely inert" means that ≤ 5%, typically ≤ 1%, of the base-labile groups (or groupings) decompose, cleave, or react during pre-exposure annealing, exposure, and post-exposure annealing. The base-labile group is reactive under typical photoresist development conditions, for example, using an aqueous alkaline photoresist developer such as a 0.26 N aqueous solution of tetramethylammonium hydroxide (TMAH). For example, a 0.26 N aqueous solution of TMAH can be used for single-puddle or dynamic development, e.g., applying the 0.26 N TMAH developer to an imaged photoresist layer for a suitable time, such as 10 to 120 seconds. An example of a base-labile group is an ester group, typically a fluorinated ester group.Preferably, the base-labile material is largely immiscible with the first and / or second polymer and other solid components of the photoresist composition and has a lower surface energy than these. When applied to a substrate, the base-labile material can therefore segregate from other solid components of the photoresist composition to form an upper surface of the resulting photoresist layer.

[0111] In some aspects, the base-labile material can be a polymeric material, also referred to here as a base-labile polymer, which may contain one or more repeating units comprising one or more base-labile groups. For example, the base-labile polymer may comprise a repeating unit with two or more base-labile groups, which may be the same or different. A preferred base-labile polymer contains at least one repeating unit with two or more base-labile groups, for example, a repeating unit with two or three base-labile groups.

[0112] The base-labile polymer can be prepared using any suitable prior art methods, including those described here for the first and second polymers. For example, the base-labile polymer can be obtained by polymerizing the respective monomers under any suitable conditions, such as heating to an effective temperature, irradiation with actinic radiation at an effective wavelength, or a combination thereof. Additionally or alternatively, one or more base-labile groups can be grafted onto the main chain of a polymer using suitable methods.

[0113] In some aspects, the base-labile material is a single molecule with one or more base-labile ester groups, preferably one or more fluorinated ester groups. The base-labile materials, which are single molecules, typically exhibit an M w in the range of 50 to 1500 Da.

[0114] If present, the base-labile material in the photoresist compositions is typically in an amount of 0.01 to 10 wt.% or 2 to 7 wt.%, typically 1 to 5 wt.%, based on the total solids of the photoresist composition.

[0115] In addition to or as an alternative to the base-labile polymer, the photoresist compositions may further contain one or more polymers, different from the alkali-insoluble, non-solvent base material described above. For example, the photoresist compositions may contain an additional polymer as described above, but with a different composition. Additionally or as an alternative, the one or more additional polymers may include those well known in photoresist technology, such as those selected from polyacrylates, polyvinyl ethers, polyesters, polynorbornenes, 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. Examples of optional additives include actinic dyes and contrast dyes, anti-streak agents, plasticizers, accelerators, sensitizers, photodegradable quenchers (PDQs) (also known as photodegradable bases), basic quenchers, thermal acid generators, surfactants, and the like, or combinations thereof. If present, the optional additives in the photoresist compositions are typically in amounts of 0.01 to 10% by weight, based on the total solids of the photoresist composition.

[0117] PDQs generate a weak acid upon irradiation. The acid produced from a photodegradable quencher is not strong enough to react rapidly with acid-labile groups present in the resist matrix. Examples of photodegradable quenchers include photodegradable cations, and preferably those also useful for the synthesis of strong acid-producing compounds, paired with an anion of a weak acid (pKa > 1), such as an anion of a C 1-20 -Carboxylic acid or C 1-20-Sulfonic acid. Examples of carboxylic acids are formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, and the like. Examples of sulfonic acids are p-toluenesulfonic acid, camphorsulfonic acid, and the like. In a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0118] The photodegradable quencher can be present in non-polymeric or polymer-bound form. If the photodegradable quencher is present in polymerized units attached to the first or second polymer. The polymerized units containing the photodegradable 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 number of repeating units of the polymer.

[0119] Examples of basic quenchers include 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-diylbis(azantriyl))tetraethanol, 2-(dibutylamino)ethanol and 2,2',2"-nitrilotriethanol; cyclic aliphatic amines such as 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, 1-pyrrolidine carboxylic acid tert-butyl ester, 2-ethyl-1H-imidazole-1-carboxylic acid tert-butyl ester, piperazine-1,4-dicarboxylic acid di-tert-butyl ester and N-(2-acetoxyethyl)morpholine; Aromatic amines such as pyridine, di-tert-butylpyridine and pyridinium; linear and cyclic amides and derivatives thereof such as N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3-Tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one and 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamic acid tert-butyl ester; 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 pyrazine, piperazine and phenazine; diazoles such as optionally substituted pyrazole, thiadiazole and imidazole and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0120] The basic quenchers can be in non-polymeric or polymer-bound form. If the quencher is in polymeric form, it can be present in repeating units of the polymer. The 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 number of repeating units of the polymer.

[0121] Examples of surfactants include fluorinated and non-fluorinated surfactants, which can be ionic or non-ionic, with non-ionic surfactants being preferred. Examples of fluorinated non-ionic surfactants are 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 one aspect, the photoresist composition further includes a surfactant polymer with a fluorine-containing repeating unit.

[0122] Structuring methods using the photoresist compositions according to the invention are now described. Suitable substrates onto which the photoresist compositions can be applied are substrates for electronic devices. A wide range of substrates for electronic devices can be used in the present invention, such as: semiconductor wafers; polycrystalline silicon substrates; package substrates such as multichip modules; flat panel display substrates; light-emitting diode (LED) substrates, including organic light-emitting diodes (OLEDs), and the like, with semiconductor wafers being typical. Such substrates typically consist of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon dioxide nitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold.Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 mm, although according to the present invention, wafers with smaller and larger diameters can also be used. The substrates can contain one or more layers or structures, which may optionally include active or operational parts of devices to be formed.

[0123] Typically, one or more lithographic layers, such as a hard mask layer (for example, a hard mask layer made of SOC, amorphous carbon, or metal), a CVD layer (such as a layer of silicon nitride (SiN), silicon dioxide (SiO), or silicon dioxide nitride (SiON)), an organic or inorganic sublayer, or combinations thereof, are provided on a top surface of the substrate prior to the application of a photoresist composition of the present invention. Such layers, together with a photoresist layer applied over them, form a lithographic material stack.

[0124] If desired, a layer of adhesion promoter can be applied to the substrate surface before applying the photoresist compositions. Any suitable adhesion promoter for polymer films can be used, such as silanes, typically organosilanes like trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or an aminosilane coupler like gamma-aminopropyltriethoxysilane. Particularly suitable are, among others, the adhesion promoters marketed under the designations AP™ 3000, AP™ 8000, and AP™ 9000S, available from DuPont Electronics & Industrial (Marlborough, Massachusetts).

[0125] The photoresist composition can be applied to the substrate by any suitable method, including spin coating, spray coating, dip coating, doctor blade coating, or the like. For example, the photoresist layer can be applied by spin coating the photoresist in solvent using a coating line in which the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically rotated at a speed of up to 4000 revolutions per minute (rpm), for example, from 200 to 3000 rpm, or from 1000 to 2500 rpm, for a period of 15 to 120 seconds to obtain a layer of the photoresist composition on the substrate. It is understood by those skilled in the art that the thickness of the applied layer can be adjusted by changing the rotational speed and / or the total solids content of the composition.A photoresist composition layer formed from the compositions according to the invention typically has a dry film thickness of 1 nanometer (nm) to 120 micrometers (µm), preferably greater than 5 nm to 110 µm, and more preferably 6 to 100 µm. In some embodiments, the photoresist composition layer formed from the compositions can have a dry film thickness of 10 nm to 5 µm or 3 to 20 µm.

[0126] The photoresist composition is typically pre-annealed to minimize the solvent content in the layer, resulting in a tack-free coating and improving adhesion to the substrate. Pre-annealing is performed, for example, on a hot plate or in an oven, with a hot plate being the most common method.

[0127] The pre-tempering temperature and time depend, for example, on the photoresist composition and thickness. The pre-tempering temperature is typically 80 to 170 °C and more typically 90 to 150 °C. The pre-tempering time is typically 10 seconds to 20 minutes, more typically 1 to 10 minutes, and still more typically 1 to 2 minutes. The heating time can be readily determined by the average person with expertise based on the compositional components.

[0128] The photoresist layer is next structurally exposed with activating radiation to create a solubility difference between exposed and unexposed areas. Reference here to exposing a photoresist composition with radiation that is activating for the composition indicates that the radiation can form a latent image within the photoresist composition. Exposure is typically performed through a structured photomask that has optically transparent and optically opaque areas corresponding to the exposed and unexposed areas of the resist layer, respectively. Alternatively, such exposure can also be performed without a photomask in a direct-write process, typically used in electron beam lithography.The activating radiation typically has a wavelength of less than 400 nm, less than 300 nm, or less than 200 nm, with wavelengths of 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV), or electron beam lithography being preferred. Preferably, the activating radiation is 248 nm. The methods are used in immersion or dry lithography techniques (non-immersion lithography techniques). The exposure energy is typically 1 to 200 millijoules per square centimeter (mJ / cm²). 2 ), preferably 10 to 100 mJ / cm² 2 and preferably 20 to 50 mJ / cm² 2 depending on the exposure tool and the components of the photoresist composition.

[0129] After exposure of the photoresist layer, a post-exposure bake (PEB) is performed. The PEB can be carried out, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for the PEB depend, for example, on the photoresist composition and the layer thickness. The PEB is typically performed at a temperature of 70 to 150 °C, preferably 75 to 120 °C, and for a time of 30 to 120 seconds. A latent image is formed in the photoresist, defined by the polarity-switched regions (exposed areas) and the non-switched regions (unexposed areas).

[0130] The exposed photoresist layer is then developed with a suitable developer to selectively remove those areas of the layer that are soluble in the developer, while the remaining insoluble areas form the resulting photoresist structure relief image. In a positive-tone development (PTD) process, the exposed areas of the photoresist layer are removed during development, leaving unexposed areas behind. Conversely, in a negative-tone development (NTD) process, the exposed areas of the photoresist layer remain, and unexposed areas are removed during development. The developer can be applied by any suitable method, as described above for the application of the photoresist composition, with spin coating being typical.Development takes place over a period of time that is effective in removing the soluble regions of the photoresist, with a typical time of 5 to 60 seconds. Development is typically carried out at room temperature.

[0131] Examples of suitable developers for a PTD process are aqueous basic developers, for example, solutions of quaternary ammonium hydroxide such as tetramethylammonium hydroxide (TMAH), preferably 0.26-normal (N)TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. Suitable developers for an NTD process are organic solvent-based, i.e., the cumulative organic solvent content in the developer is 50 wt.% or more, typically 95 wt.% or more, 98 wt.% or more, or 100 wt.%, based on the total weight of the developer. Suitable organic solvents for the NTD developer are, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0132] A coated substrate can be formed from the photoresist compositions according to the invention. Such a coated substrate comprises: (a) a substrate with one or more layers to be structured on a surface thereof; and (b) a layer of the photoresist composition over the one or more layers to be structured.

[0133] The photoresist structure can, for example, be used as an etching mask, enabling the transfer of the structure to one or more sequentially underlying layers using known etching techniques, typically dry etching such as reactive ion etching. The photoresist structure can, for example, be used to transfer the structure to an underlying hard mask layer, which in turn can be used as an etching mask for transferring the structure to one or more layers below the hard mask layer. If the photoresist structure is not consumed during the structure transfer, it can be removed from the substrate using known techniques, such as oxygen plasma ashing.When used in one or more such structuring processes, the photoresist compositions can be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0134] The invention is further explained with reference to the following non-limiting examples. EXAMPLES

[0135] All reactions were carried out under ambient conditions. All chemicals were used directly in their supplied form. Unless otherwise stated, nuclear magnetic resonance (NMR) spectra were obtained for all compounds on a 400 MHz spectrometer. Chemical shifts are given in δ values ​​(parts per million, ppm) relative to the internal residual signal of deuterated chloroform. Multiplicities are indicated by s (singlet), d (doublet), t (triplet), m (multiplet), dd (doublet of doublets), dt (doublet of triplets), tt (triplet of triplets), br (wide singlet). Synthesis of potassium 4-carboxy-2-hydroxybenzenesulfonate.

[0136] 3-Hydroxybenzoic acid (50 grams (g)) was dissolved in sulfuric acid (100 milliliters (ml)) and heated to 90 °C, after which 30% SO3 solution in H2SO4 (20 ml) was added dropwise. The reaction mixture was held at 90 °C for 16 hours (h), cooled to room temperature, and quenched with the addition of ice water (120 ml). After adding 25 wt% KOH solution in water (150 ml), the resulting solid was filtered off, distilled with toluene (3 x 100 ml), washed with acetone (2 x 100 ml), and dried at 50 °C for 8 h, yielding potassium 4-carboxy-2-hydroxybenzenesulfonate as a light brown solid (68 g, 73%). 1 ¹H NMR (400 MHz, dimethyl sulfoxide-d6 (DMSO-d6)): δ 10.6 ppm (wide singlet, ¹H), 7.54 ppm (d, J = 8.4 Hz, ¹H), 7.37 ppm (dd, J = 8.0, 1.6 Hz, ¹H), and 7.28 ppm (d, J = 1.6 Hz, ¹H); Electrospray ionization mass spectrometry (ESI-MS): [MK] - : 217.16. Synthesis of potassium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate.

[0137] 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) using a Dean-Stark water separator. The resulting mixture was then heated under reflux at 100 °C for 48 h. The reaction mixture was cooled to room temperature, after which the solid was filtered off. The filtrate was concentrated under reduced pressure, dissolved in ethyl acetate (300 mL), washed with water (3 x 100 mL), washed with sodium chloride solution (100 mL), dried over Na₂SO₄, and then concentrated under reduced pressure. The crude product was purified by washing with n-pentane (50 ml), followed by acetonitrile (50 ml) and concentrated under reduced pressure, yielding potassium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate in the form of a pale yellow solid (6.0 g, 33%). 1H-NMR (400 MHz, DMSO-d6): δ 10.6 ppm (s, 1H), 7.57 ppm (d, J = 8.0 Hz, 1H), 7.39 ppm (dd, J = 8.0, 1.6 Hz, 1H), 7.30 ppm (d, J = 1.6 Hz, 1H), 4.25 ppm (t, J = 6.4 Hz, 2H), 1.72-1.65 ppm (m, 2H), 1.44-1.38 ppm (m, 2H), and 0.93 ppm (t, J = 7.6 Hz, 3H); ESI-MS: [MK] - : 273.22. Synthesis of triphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-1).

[0138] 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), after which the resulting mixture was stirred for 4 h at room temperature. The reaction mixture was then diluted with dichloromethane (200 mL) and washed with water (3 x 100 mL) followed by sodium chloride solution (100 mL), dried over Na₂SO₄, and concentrated under reduced pressure, yielding triphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-1) as a viscous oil (13.0 g, 83%). 1H-NMR (400 MHz, DMSO-d6): δ 10,65 ppm (s, 1H), 7,89-7,77 ppm (m, 15H), 7,58 ppm (d, J= 8,0 Hz, 1H), 7,39 ppm (dd, J = 8,0, 1,6 Hz, 1H), 7,30 ppm (d, J = 1,6 Hz, 1H), 4,25 ppm (t, J = 6,8 Hz, 2H), 1,71-1,64 ppm (m, 2H), 1,45-1,38 ppm (m, 2H), und 0,92 ppm (t, J= 7,6 Hz, 3H); ESI-MS: [M] - : 273,13 und [M] + : 263,25.

[0139] Synthese von Bis(4-(tert-butyl)phenyl)iodonium-4-(butoxycarbonyl)-2-hydroxybenzolsulfonat (PAG-2).

[0140] 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 h. The organic fraction was then washed with water (4 x 300 mL) and concentrated under reduced pressure to remove most of the volatile components. The remaining solution was then slowly poured into methyl tert-butyl ether (700 mL). A precipitate was collected and dried under vacuum, yielding bis(4-(tert-butyl)phenyl)iodonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-2) as a white solid (13.0 g, 59%). 1H NMR (499 MHz, Aceton-d6) δ 10,70 ppm (s, 1H), 8,26 - 8,15 ppm (m, 4H), 7,64 - 7,57 ppm (m, 4H), 7,56 - 7,51 ppm (m, 1H), 7,41 - 7,31 ppm (m, 2H), 4,29 ppm (t, J = 6,5 Hz, 2H), 1,75 ppm (dd, J = 9,0, 7,8, 6,5 Hz, 2H), 1,57 - 1,45 ppm (m, 2H), 1,32 ppm (s, 18H), und 0,99 ppm (t, J= 7,4 Hz, 3H).

[0141] Synthese von Kalium-4-((heptyloxy)carbonyl)-2-hydroxybenzolsulfonat.

[0142] 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) using a Dean-Stark water separator. The mixture was then heated under reflux at 100 °C for 32 h. The reaction mixture was cooled to room temperature, after which the resulting solid was filtered off. The filtrate was concentrated under reduced pressure, dissolved in ethyl acetate (600 mL), washed with water (3 x 150 mL), washed with sodium chloride solution (150 mL), dried over Na₂SO₄, and concentrated again under reduced pressure. The crude product was purified by washing with acetonitrile (40 ml) and concentrated under reduced pressure, yielding potassium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate in the form of an off-white solid (8.0 g, 58%). 1H-NMR (400 MHz, DMSO-d6): δ 10.64 ppm (s, 1H), 7.57 ppm (d, J = 8.0 Hz, 1H), 7.38 ppm (dd, J = 8.0, 1.6 Hz, 1H), 7.29 ppm (d, J = 1.2 Hz, 1H), 4.25 ppm (t, J = 6.8 Hz, 2H), 1.73-1.66 ppm (m, 2H), 1.40-1.27 ppm (m, 8H), and 0.86 ppm (t, J = 4.0 Hz, 3H); ESI-MS: [MK] - : 315.26. Synthesis of triphenylsulfonium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate (PAG-3).

[0143] 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), after which the mixture was stirred for 4 h at room temperature. The reaction mixture was then diluted with CH₂Cl₂ (200 mL), washed with water (5 x 75 mL), washed with sodium chloride solution (75 mL), dried over Na₂SO₄, and concentrated under reduced pressure, yielding triphenylsulfonium 4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate (PAG-3) as a viscous oil (5.5 g, 82%). 1H-NMR (400 MHz, DMSO-d6): δ 10,65 ppm (s, 1H), 7,88-7,77 ppm (m, 15H), 7,57 ppm (d, J = 8,0 Hz, 1H), 7,38 ppm (dd, J = 8,0, 1,6 Hz, 1H), 7,30 ppm (d, J = 1,6 Hz, 1H), 4,25 ppm (t, J = 6,8 Hz, 2H), 1,73-1,66 ppm (m, 2H), 1,39-1,27 ppm (m, 8H), und 0,86 ppm (t, J = 6,8 Hz, 3H); ESI-MS: [M] - : 315,26, [M] + : 263,21. Synthese von Adamantanmethanol.

[0144] 2 M lithium aluminum hydride in tetrahydrofuran (THF) (46 mL) was added dropwise under nitrogen at 0 °C to a solution of adamantane-1-carboxylic acid (5 g) in THF (100 mL), slowly warmed to room temperature, and stirred for 16 h. The reaction mixture was then cooled to 0 °C, washed with cold saturated Na₂SO₄ (50 mL), diluted with ethyl acetate (50 mL), and stirred for 15 min. The resulting solution was filtered through Celite and washed with ethyl acetate (20 mL). The filtrate was separated, and the ethyl acetate layer was washed with sodium chloride (30 mL), dried over Na₂SO₄, and concentrated under reduced pressure, yielding adamantane methanol as an off-white solid (4.1 g, 88.9%). 1 H-NMR (400 MHz, DMSO-d6): δ 4.27 ppm (t, J = 5.6 Hz, 1H), 2.95 ppm (dd, J = 5.6 Hz, 2H), 1.92 ppm (m, 3H), 1.68-1.65 ppm (m, 3H), 1.60-1.56 ppm (m, 3H), and 1.43 ppm (d, J = 2.4 Hz, 6H). Synthese von 4-(((Adamantan-1-yl)methoxy)carbonyl)-2-hydroxybenzolsulfonat (PAG-4).

[0145] Adamantane methanol (3.1 g) in toluene (20 ml) followed by p-toluenesulfonic acid water (0.15 g) was added at room temperature to a stirred solution of triphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (2.0 g). The reaction mixture was then heated to 140 °C for 3 days with a Dean-Stark water separator attached to the reaction apparatus. 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 sodium chloride solution (10 ml), dried over Na2SO4, and concentrated again under reduced pressure. The crude product was washed with THF:petroleum ether (2 x 1:2, 20 ml : 40 ml) and concentrated under reduced pressure, yielding 4-(((adamantan-1-yl)methoxy)carbonyl)-2-hydroxybenzenesulfonate (PAG-4) in the form of an off-white solid (1.4 g, 59.8 %). 1H-NMR (400 MHz, DMSO-d6): δ 10.67 ppm (s, 1H), 7.88-7.76 ppm (m, 15H), 7.59 ppm (d, J = 8.0 Hz, 1H) 7.41 ppm (dd, J = 8.0, 1.6 Hz, 1H), 7.31 ppm (d, J = 1.6 Hz, 1H) 3.87 ppm (s, 2H), 1.97 ppm (m, 3H), 1.71-1.63 ppm (m, 6H), and 1.58 ppm (d, J = 2.4 Hz, 6H). LC-MS [M]+=263.21, [M]-=365.31. Synthesis of triphenylsulfonium 4-carboxy-2-hydroxybenzenesulfonate (PAG-5).

[0146] Triphenylsulfonium-4-((heptyloxy)carbonyl)-2-hydroxybenzenesulfonate (10 g) was dissolved in 6 N HCl (100 ml) and heated to 90 °C for 16 h with stirring. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, distilled together with toluene (2 x 50 ml), concentrated again under reduced pressure, washed with THF:hexane (1:2, 150 ml), filtered, and dried, yielding triphenylsulfonium-4-carboxy-2-hydroxybenzenesulfonate (PAG-5) as an off-white solid (7.5 g, 84%). 1H-NMR (400 MHz, DMSO-d6): δ 12.98 ppm (s, 1H), 10.61 ppm (s, 1H), 7.88-7.76 ppm (m, 15H), 7.54 ppm (d, J = 8.0 Hz, 1H), 7.36 ppm (dd, J = 8.0, 1.2 Hz, 1H), and 7.28 ppm (d, J= 1.2 Hz, 1H); ESI-MS: [M] - : 217.16, [M] + : 263.25. Synthesis of (3-chloropropyl)diphenylsulfonium tetrafluoroborate.

[0147] Silver tetrafluoroborate (4.18 g) was added to a solution of diphenyl sulfide (5.0 g) and 1-chloro-3-iodopropane (18.67 g) and nitromethane (10 mL), after which the resulting mixture was stirred at room temperature for 16 h. The reaction mixture was then diluted with dichloromethane (50 mL), filtered through a layer of Fluorosil, and washed with CH₂Cl₂ (25 mL). The filtrate was concentrated under reduced pressure and washed with diethyl ether (20 mL), petroleum ether (20 mL), and dried, yielding (3-chloropropyl)diphenylsulfonium tetrafluoroborate as an off-white solid (6.2 g, 66%). 1H-NMR (400 MHz, DMSO-d6): δ 8,12-8,09 ppm (m, 4H), 7,83-7,81 ppm (m, 2H), 7,79-7,73 ppm (m, 4H), 4,43 ppm (t, J = 7,6 Hz, 2H), 3,80 ppm (t, J = 6,4 Hz, 2H), und 2,17-2,11 ppm (m, 2H). ESI-MS: [M-BF4] + : 263,17. Synthese von Cyclopropyldiphenylsulfoniumtetrafluoroborat.

[0148] 60 wt% NaH (850 mg) was added at 0 °C to a solution of (3-chloropropyl)diphenylsulfonium tetrafluoroborate (6.2 g) in THF (124 ml), after which the reaction mixture was allowed to warm to room temperature and then stirred for a total of 16 h. Then, 48 wt% aqueous HBF4 (1.3 ml) followed by NaBF4 (0.78 g) in water (21 ml) was added, and the resulting mixture was stirred for another 30 minutes. The reaction mixture was diluted with dichloromethane (60 ml) and washed with water (2 x 30 ml), after which the aqueous layers were extracted with dichloromethane (30 ml), and 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, yielding cyclopropyldiphenylsulfonium tetrafluoroborate in the form of an off-white solid (2.7 g, 48%). 1H NMR (400 MHz, DMSO-d6): δ 8.05-8.03 ppm (m, 4H), 7.85-7.75 ppm (m, 6H), 3.89 ppm (m, 1H), 1.63-1.59 ppm (m, 2H), and 1.55-1.49 ppm (m, 2H). ESI-MS: [M-BF4] + : 227.21. Synthesis of cyclopropyldiphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-6).

[0149] 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), after which the reaction mixture was stirred for 4 h at room temperature. The reaction mixture was then diluted with dichloromethane (120 mL), washed with water (5 x 30 mL), washed with sodium chloride solution (30 mL), dried over sodium sulfate, and concentrated under reduced pressure, yielding cyclopropyldiphenylsulfonium 4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-6) as a light brown liquid (3.8 g, 95%). 1H-NMR (400 MHz, DMSO-d6): δ 10,65 ppm (s, 1H), 8,05-8,03 ppm (m, 4H), 7,84-7,75 ppm (m, 6H), 7,58 ppm (d, J = 8,0 Hz, 1H), 7,39 ppm (dd, J = 8,0, 1,6 Hz, 1H), 7,30 ppm (d, J = 1,6 Hz, 1H), 4,26 ppm (t, J = 6,8 Hz, 2H), 3,94-3,89 ppm (m, 1H), 1,71-1,59 ppm (m, 4H), 1,57-1,50 ppm (m, 2H), 1,48-1,42 ppm (m, 2H), und 0,93 ppm (t, J = 7,2 Hz, 3H). ESI-MS: [M] - : 273,36, [M] + : 227,26. Synthese von 2,4-Dihydroxybenzolsulfonsäure.

[0150] Chlorosulfonic acid (0.61 ml) was added dropwise at 0 °C to a solution of resorcinol (1.0 g) in nitrobenzene (10 ml). The reaction mixture was warmed to room temperature and stirred and filtered for 4 h. The solid was then 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, yielding 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. Synthesis of triphenylsulfonium 2,4-dihydroxybenzenesulfonate (PAG-7).

[0151] Silver oxide (0.74 g) was added to a solution of triphenylsulfonium bromide (1.0 g) in methanol (20 mL), after which the reaction mixture was stirred for 16 h at room temperature. The reaction mixture was then filtered through Celite and washed with methanol (10 mL). The combined methanol layers were treated with 2,4-dihydroxybenzenesulfonic acid (0.66 g), after which the mixture was stirred for 1 h at room temperature, concentrated under reduced pressure, washed with ethyl acetate (2 x 10 mL), and dried, yielding triphenylsulfonium 2,4-dihydroxybenzenesulfonate (PAG-7) as a gray solid (1.2 g, 91.6%). 1 H-NMR (400 MHz, DMSO-d6): δ 10.53 ppm (s, 1H), 9.48 ppm (s, 1H), 7.88-7.76 ppm (m, 15H), 7.21 ppm (d, J = 8.4 Hz, 1H), 6.19 ppm (dd, J = 8.4, 2.4 Hz, 1H), and 6.10 ppm (d, J = 2.0 Hz, 1H); ESI-MS: [M] - : 189.08 and [M] + : 263.25. Synthesis of potassium 1-hydroxynaphthalene 2-sulfonate.

[0152] 1-Hydroxynaphthalene (5.0 g) was dissolved in acetic acid (2.5 mL, AcOH) and heated to 55 °C for 10 minutes. H₂SO₄ (2.8 mL) was then added dropwise, and the reaction mixture was kept between 55 °C and 60 °C for 16 hours. Next, the reaction mixture was treated with potassium chloride (15 g) in water (50 mL) 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 x 50 mL), yielding potassium 1-hydroxynaphthalene-2-sulfonate as an off-white solid (1.7 g, 18.7%). 1 H-NMR (400 MHz, DMSO-d6): δ 11.60 ppm (s, 1H), 8.15-8.17 ppm (m, 1H), 7.82-7.80 ppm (m, 1H), 7.55-7.46 ppm (m, 3H), 7.31 ppm (d, J = 8.4 Hz, 1H), and 7.31 ppm (d, J = 8.4 Hz, 1H); ESI-MS: [MK] - : 223.16. Synthesis of triphenylsulfonium 1-hydroxynapthylene-2-sulfonate (PAG-8).

[0153] Triphenylsulfonium bromide (1.96 g) and potassium 1-hydroxynapthylene-2-sulfonate (1.5 g) were dissolved in dichloromethane (30 mL) and water (15 mL), after which the reaction mixture was stirred at room temperature for 16 h. After separation of the layers, the aqueous layer was extracted with dichloromethane (30 mL). The combined organic layers were washed with water (5 x 10 mL) and concentrated under reduced pressure. The resulting product was washed with ethyl acetate and petroleum ether (1:3, 40 mL) and dried, yielding triphenylsulfonium 1-hydroxynapthylene-2-sulfonate (PAG-8) as an off-white solid (2.8 g, 30.7%). 1 H-NMR (400 MHz, DMSO-d6): δ 11.61 ppm (s, 1H), 8.16 (d, J = 8.0 Hz, 1H), 7.88-7.76 ppm (m, 16H), 7.54-7.46 ppm (m, 3H), and 7.31 ppm (d, J = 8.8 Hz, 1H); ESI-MS: [M] - : 223.21 and [M] + : 263.25. Synthesis of potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate and potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate.

[0154] Chlorosulfonic acid (17.5 ml) was added to 4-hydroxyisobenzofuran-1,3-dione (3.5 g) at 0 °C, after which the reaction mixture was warmed to room temperature and stirred for 8 days at room temperature. The reaction mixture was then cooled to 0 °C, quenched with ice water (35 ml), and treated with 50% KOH solution in water (7.5 g, 15 ml), after which the mixture was stirred for 30 min. The resulting solid was filtered, washed with THF (20 ml), washed with petroleum ether (80 ml), and dried, yielding a mixture of potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate and potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate (4.8 g, 75%) as an off-white solid, which was used directly in the next step. Liquid chromatography-mass spectrometry (LC-MS): [MK] - =261.07, [MK] + =245.12. Synthesis of potassium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate.

[0155] para-Toluenesulfonic acid monohydrate (300 mg, PTSA) was added to a mixture of potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate and potassium 3,4-dicarboxy-2-hydroxybenzenesulfonate (3.5 g) in 1-butanol (40 mL), after which 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, yielding potassium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate (2.6 g, 54.1%) as an off-white solid, which was used directly in the next step. LC-MS: [MK] - =373.27. Synthesis of triphenylsulfonium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-9).

[0156] 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), after which the reaction mixture was stirred at room temperature for 16 h. The reaction mixture was then diluted with dichloromethane (50 mL), washed with 10 wt% aqueous sodium bicarbonate (2 x 30 mL), washed with water (5 x 30 mL), dried over Na₂SO₄, and concentrated under reduced pressure. The crude compound was suspended in THF (15 mL), stirred for 10 min, filtered, washed with additional THF (15 mL), and dried under reduced pressure, yielding triphenylsulfonium 3,4-bis(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-9) as an off-white solid (2.4 g, 67.6%). 1H-NMR (400 MHz, DMSO-d6): δ 10.36 ppm (s, 1H), 7.88-7.76 ppm (m, 15H), 7.65 ppm (d, J = 8.8 Hz, 1H), 6.90 ppm (d, J = 8.8 Hz, 1H), 4.12 ppm (t, J = 6.4 Hz, 2H), 4.02 ppm (t, J= 6.8 Hz, 2H), 1.61-1.53 ​​ppm (m, 4H), 1.41-1.31 ppm (m, 4H), and 0.91 ppm (m, 6H); LC-MS: [M] + = 263.23, [M] - =373.39. Synthesis of sodium 5-fluoro-2-hydroxybenzenesulfonate.

[0157] Sulfuric acid (45.9 g) was added to 4-fluorophenol (15 g) at -10 °C. The reaction mixture was slowly warmed to room temperature, stirred for 16 h, and then diluted with cold water (30 mL). Aqueous NaOH (1.0 eq.) was then added, and the mixture was stirred for 30 minutes. The resulting solid was filtered and dried under reduced pressure, yielding sodium 5-fluoro-2-hydroxybenzenesulfonate as a white solid (26 g, 90%). 1H NMR (400 MHz, DMSO-d6): δ 7.12 ppm (dd, J= 8.8, 3.2 Hz, 1H), 6.79 ppm (td, J= 8.8, 3.6 Hz, 1H), and 6.63-6.60 ppm (m, 1H). ESI-MS: [M-Na] - : 191.23. Synthesis of triphenylsulfonium 5-fluoro-2-hydroxybenzenesulfonate (PAG-10).

[0158] Sodium 5-fluoro-2-hydroxybenzenesulfonate (10.0 g) and triphenylsulfonium chloride (12.5 g) were dissolved in dichloromethane (200 mL) and water (100 mL), after which the reaction mixture was stirred for 4 h at room temperature. The reaction mixture was then diluted with dichloromethane (400 mL), washed with water (5 x 100 mL), and concentrated under reduced pressure. The crude product was washed with hexane (50 mL), filtered, and dried under reduced pressure, yielding 7.5 g of a white solid, which, according to 1 H-NMR showed excess triphenylsulfonium cation.

[0159] Impure triphenylsulfonium 5-fluoro-2-hydroxybenzenesulfonate (21.0 g) and sodium 5-fluoro-2-hydroxybenzenesulfonate (9.89 g), synthesized according to the above procedure, were dissolved in dichloromethane (420 mL) and water (210 mL), after which the reaction mixture was stirred for 4 h at room temperature. The reaction mixture was then diluted with dichloromethane (400 mL) and washed with water (5 x 200 mL). The organic layer was concentrated under reduced pressure, washed with methyl tert-butyl ether (250 mL), filtered, dried, and dissolved in ethanol (40 mL), after which a hexane mixture (160 mL) was added with vigorous stirring. The resulting solid was filtered and dried, yielding triphenylsulfonium 5-fluoro-2-hydroxybenzenesulfonate (PAG-10) as a white solid (20.1 g). 1H-NMR (400 MHz, DMSO-d6): δ 10.2 ppm (s, 1H), 7.80-7.76 ppm (m, 15H), 7.14 ppm (dd, J = 8.4, 3.2 Hz, 1H), 7.09-7.04 ppm (m, 1H), and 6.78 ppm (dd, J = 9.2, 4.8Hz, 1H). ESI-MS: [M-Na] - : 191.21 and [M] + : 263.29. Synthesis of 3,5-dihydroxybenzoic acid butyl ester.

[0160] para-Toluenesulfonic acid monohydrate (2.5 g) was added to a solution of 3,5-dihydroxybenzoic acid (10.0 g) in 1-butanol (20 mL) and toluene (100 mL), after which the reaction mixture was heated to 120 °C for 16 h. The mixture was then cooled to room temperature, quenched with ice water, and extracted with ethyl acetate. The combined organic layers were washed with 10% aqueous NaHCO3 (2 x 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, yielding butyl 3,5-dihydroxybenzoate as a brown, viscous oil (10.1 g, 74%). 1 H-NMR (400 MHz, DMSO-d6): δ 9.60 ppm (s, 2H), 6.82 ppm (d, J = 2.4 Hz, 2H), 6.43 ppm (d, J = 2.4 Hz, 1H), 4.21 ppm (t, J = 6.8 Hz, 2H), 1.69-1.62 (m, 2H), 1.45-1.36 ppm (m, 2H), and 0.93 (t, J = 7.4 Hz, 3H). LC-MS [MH] -=209,25. Synthese von Natrium-4-(butoxycarbonyl)-2,6-dihydroxybenzolsulfonat.

[0161] Chlorosulfonic acid (7.6 ml) was added at 0 ± 5 °C to a solution of butyl 3,5-dihydroxybenzoate (20.0 g) in nitrobenzene (400 ml) and stirred at room temperature for 5 days. The reaction mixture was then cooled to 0 ± 5 °C, quenched with cold water (200 ml), and treated with aqueous sodium hydroxide (2 eq.). The product was then extracted with petroleum ether (4 x 200 ml) and the organic layers discarded. The aqueous layer was extracted with ethyl acetate and methanol (9:1, 3 x 200 ml), after which the combined organic layers were concentrated under reduced pressure. The crude product obtained was washed with ethyl acetate and petroleum ether (1:1, 200 ml) followed by ethyl acetate and methanol (19:1, 200 ml), yielding sodium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate in the form of an off-white solid (9.0 g, 30%). 1H NMR (400 MHz, DMSO-d6): δ 9.93 ppm (s, 2H), 6.84 ppm (s, 2H), 4.23 ppm (t, J = 6.4 Hz, 2H), 1.70-1.63 ppm (m, 2H), 1.45-1.35 ppm (m, 2H), and 0.93 ppm (t, J = 7.4 Hz, 3H). LC-MS [M-Na] - =289.26. Synthesis of triphenylsulfonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-11).

[0162] 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), after which the reaction mixture was stirred for 16 h at room temperature. The organic layer was then washed with water (3 x 100 ml) and concentrated under reduced pressure, yielding triphenylsulfonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-11) as a viscous brown oil (12.3 g, 95%). 1H-NMR (400 MHz, DMSO-d6): δ 9.92 ppm (s, 2H), 7.89 -7.76 ppm (m, 15H), 6.85 ppm (s, 2H), 4.23 ppm (t, J = 6.4 Hz, 2H), 1.70-1.63 ppm (m, 2H), 1.43-1.37 ppm (m, 2H), and 0.92 ppm (t, J = 7.6 Hz, 3H). LC-MS: [M] + =263.33, [M] - =289.26. Synthesis of 4-(4-(tert-butyl)phenyl)-1,4-oxathian-4-ium-4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-12).

[0163] 4-(4-(tert-Butyl)phenyl)-1,4-oxathian-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), after which the reaction mixture was stirred for 16 h at room temperature. The organic layer was then washed with water (7 x 400 ml) and concentrated under reduced pressure, yielding 4-(4-(tert-Butyl)phenyl)-1,4-oxathian-4-ium-4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-12) as a white solid (6.80 g, 81%). 1H-NMR (499 MHz, Aceton-d6): δ 10,13 - 9,87 ppm (m, 2H), 8,20 - 8,04 ppm (m, 2H), 7,93 - 7,75 ppm (m, 2H), 6,95 ppm (s, 2H), 4,54 - 4,42 ppm (m, 2H), 4,27 ppm (t, J = 6,6 Hz, 2H), 4,25 - 4,15 ppm (m, 2H), 4,14 - 3,95 ppm (m, 4H), 1,79 - 1,70 ppm (m, 2H), 1,55 - 1,43 ppm (m, 2H), 1,38 ppm (s, 9H), und 0,98 ppm (t, J = 7,4 Hz, 3H). Synthese von 3-(Butylthio)phenol.

[0164] 3-Mercaptophenol (10 g) in methanol (50 ml) was added dropwise to a solution of sodium hydroxide (3.3 g) in methanol (50 ml), after which the reaction mixture was stirred for 30 min at room temperature. Then 1-Bromobutane (8.8 ml) was added dropwise at room temperature, and the reaction mixture was heated to 70 °C and stirred for 2 h. The reaction mixture was then cooled to room temperature, concentrated under reduced pressure, dissolved in ethyl acetate (200 ml), washed with water (100 ml), concentrated under reduced pressure, and purified by flash column chromatography, yielding 3-(butylthio)phenol as a viscous brown oil (13.5 g, 93.5%). 1 H-NMR (400 MHz, DMSO-d6): δ 9.48 ppm (s, 1H), 7.08 ppm (t, J = 8 Hz, 1H), 6.71-6.68 ppm (m, 2H), 6.57-6.54 ppm (m, 1H), 2.89 ppm (t, J = 7.2 Hz, 2H), 1.58-1.51 ppm (m, 2H), 1.44-1.34 ppm (m, 2H), and 0.87 ppm (t, J = 7.2 Hz, 3H). LC-MS [M+H] + =183.28. Synthesis of 3-(Butylsulfonyl)phenol.

[0165] 30 wt% H₂O₂ in water (55 ml) was added to 3-(butylthio)phenol (11.0 g) in acetic acid (55 ml), after which 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 x 220 ml), washed with 10% aqueous NaHCO₃ (5 x 200 ml), washed with water (5 x 200 ml), dried over Na₂SO₄, and concentrated under reduced pressure, yielding 3-(butylsulfonyl)phenol as a viscous brown oil (11.5 g, 89%). 1 H-NMR (400 MHz, DMSO-d6): δ 10.21 ppm (s, 1H), 7.45 ppm (t, J = 8 Hz, 1H), 7.31-7.28 ppm (m, 1H), 7.23 ppm (t, J = 2.0 Hz, 1H), 7.12-7.09 ppm (m, 1H), 3.25 ppm (t, J = 8.0 Hz, 2H), 1.53-1.46 ppm (m, 2H), 1.37-1.33 ppm (m, 2H), and 0.82 ppm (t, J = 7.6 Hz, 3H). LC-MS [MH] - =213.25. Synthesis of sodium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate.

[0166] Fuming sulfuric acid (10 ml) was added at 50 °C to a solution of 3-(butylsulfonyl)phenol (9.0 g) in H₂SO₄ (5 ml), after which the reaction mixture was heated to 80 °C for 16 h. The mixture was then cooled to 0 °C, diluted with cold water (50 ml), titrated with sodium hydroxide to a pH of 7–8, and stirred for 30 minutes. The resulting solid was filtered, washed with THF (100 ml), washed with ethyl acetate (100 ml), and dried under reduced pressure, yielding sodium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate as an off-white solid (9.5 g, 72%). 1 H-NMR (400 MHz, DMSO-d6): δ 10.86 ppm (s, 1H), 7.69 ppm (d, J = 8.4 Hz, 1H), 7.30 ppm (dd, J = 8.0, 1.6 Hz, 1H), 7.24 ppm (t, J = 1.6 Hz, 1H), 3.28 ppm (t, J = 8.0, Hz, 2H), 1.50-1.47 ppm (m, 2H), 1.35-1.29 ppm (m, 2H), and 0.82 ppm (t, J = 7.2 Hz, 3H). LC-MS [M-Na] - =293.22. Synthesis of triphenylsulfonium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate (PAG-13).

[0167] Triphenylsulfonium bromide (8.2 g) and sodium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate (7.5 g) were dissolved in dichloromethane (160 ml) and water (160 ml), after which the reaction mixture was stirred at room temperature for 16 h. The organic layer was then separated and washed with water (3 x 150 ml), concentrated under reduced pressure, and stirred with hexane and ethanol (3:1, 100 ml), yielding triphenylsulfonium 4-(butylsulfonyl)-2-hydroxybenzenesulfonate (PAG-13) as a white solid (12.3 g, 94%). 1 H-NMR (400 MHz, DMSO-d6): δ 10.87 ppm (s, 1H), 7.88-7.76 ppm (m, 15H), 7.70 ppm (d, J= 8 Hz, 1H), 7.31 ppm (dd, J= 8.0, 2.0 Hz, 1H), 7.24 ppm (d, J= 2.0 Hz, 1H), 3.29 ppm (m, 2H), 1.52-1.44 ppm (m, 2H), 1.35-1.29 ppm (m, 2H), and 0.82 ppm (t, J = 7.2 Hz, 3H). LC-MS: [M] + 263.33, [M] - =293.22. Synthesis of 4-(4-(tert-butyl)phenyl)-1,4-oxathian-4-ium-4-(butylsulfonyl)-2-hydroxybenzenesulfonate (PAG-14).

[0168] 4-(4-(tert-Butyl)phenyl)-1,4-oxathian-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), after which the reaction mixture was stirred for 16 h at room temperature. The organic layer was then separated and washed with water (3 x 250 ml) and concentrated under reduced pressure, yielding 4-(4-(tert-Butyl)phenyl)-1,4-oxathian-4-ium-4-(butylsulfonyl)-2-hydroxybenzenesulfonate (PAG-14) as a white solid (1.7 g, 20%). 1H-NMR (499 MHz, Aceton-d6) δ 11,28 ppm (s, 1H), 8,18 - 8,07 ppm (m, 2H), 7,89 - 7,84 ppm (m, 2H), 7,81 ppm (dd, J = 8,0, 1,2 Hz, 2H), 7,30 ppm (dd, J = 8,0, 1,8 Hz, 1H), 7,26 ppm (d, J = 1,8 Hz, 1H), 4,56 - 4,41 ppm (m, 2H), 4,25 - 4,18 ppm (m, 2H), 4,15 - 4,00 ppm (m, 4H), 3,22 - 3,16 ppm (m, 2H), 1,69 - 1,58 ppm (m, 2H), 1,44 ppm (dt, J = 14,8, 7,4 Hz, 2H), 1,39 ppm (s, 9H), und 0,90 ppm (t, J = 7,4 Hz, 3H). Synthese von Natrium-2,4,6-trihydroxybenzolsulfonat.

[0169] Fuming sulfuric acid (6 ml) was added at 0 °C to a solution of benzene-1,3,5-triol (10.0 g) in acetonitrile (200 ml). The reaction mixture was then heated to room temperature, stirred for 4 h, diluted with cold water (200 ml), and extracted with methyl tert-butyl ether (4 x 100 ml), after which the organic layers were discarded. The aqueous layer was adjusted to a pH of 7–8 with aqueous sodium hydroxide at 0 °C, after which the resulting solid was filtered and dried, yielding sodium 2,4,6-trihydroxybenzenesulfonate (13.6 g, 83%), which was used directly in the next step without further purification. Synthesis of triphenylsulfonium 2,4,6-trihydroxybenzenesulfonate (PAG-15).

[0170] Triphenylsulfonium bromide (8.0 g) and sodium 2,4,6-trihydroxybenzenesulfonate (10.0 g) were dissolved in dichloromethane (250 ml) and water (125 ml), after which the reaction mixture was stirred at room temperature for 16 h. The organic layer was then washed with water (3 x 125 ml) and concentrated under reduced pressure, yielding triphenylsulfonium 2,4,6-trihydroxybenzenesulfonate (PAG-15) as a viscous brown oil (5.2 g, 25%). Further purification was achieved by washing with a hexane-ethanol mixture (2:1). 1 H NMR (400 MHz, DMSO-d6) δ: 9.61 ppm (s, 2H), 9.46 ppm (s, 1H), 7.89-7.77 ppm (m, 15 H), and 5.70 ppm (s, 2H). LC-MS: [M] + = 263.33, [M] - = 205.21. Synthesis of triphenylsulfonium2-sulfobenzoic acid (PAG-16).

[0171] Triphenylsulfonium bromide (33.98 g) and ammonium 2-sulfobenzoic acid (23.87 g) were dissolved in dichloromethane (550 ml) and water (550 ml), after which the reaction mixture was stirred for 16 h at room temperature. The organic layer was washed with water (6 x 500 ml) and concentrated under reduced pressure, yielding triphenylsulfonium 2-sulfobenzoic acid (PAG-16) as a white solid (16.6 g, 36%). 1 H NMR (499 MHz, DMSO-d6) δ 14.21 ppm (s, 1H), 7.92 - 7.72 ppm (m, 17H), 7.56 ppm (td, J = 7.6, 1.5 Hz, 1H), and 7.50 ppm (td, J = 7.5, 1.5 Hz, 1H). Synthesis of 4-(tert-Butyl)phenyl)diphenylsulfonium-2-sulfobenzoic acid (PAG-17).

[0172] 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), after which the reaction mixture was stirred for 16 h at room temperature. The organic layer was washed with water (6 x 500 ml) and concentrated under reduced pressure, yielding 4-(tert-Butyl)phenyl)diphenylsulfonium 2-sulfobenzoic acid (PAG-17) as a rubbery solid (37.5 g, 60%). 1 H-NMR (499 MHz, acetone-d6) δ 15.09 ppm (s, 1H), 8.02 ppm (dd, J = 7.6, 1.5 Hz, 1H), 7.97 ppm (dd, J = 7.6, 1.6 Hz, 1H), 7.95 - 7.80 ppm (m, 14H), 7.52 ppm (td, J = 7.5, 1.6 Hz, 1H), 7.47 ppm (td, J = 7.5, 1.5 Hz, 1H), and 1.38 ppm (s, 9H). Synthesis of sodium 4-carboxy-2-hydroxybenzenesulfonate.

[0173] Sulfur trimethylamine trioxide (SO3.TMA, 5 g) was added to a solution of 3-hydroxybenzoic acid (50.2 g) in H2SO4 (100 mL), heated to 90 °C, and stirred for 16 h. The reaction mixture was then cooled to 0 °C and diluted with water (500 mL). After adding sodium hydroxide (29 g) in water (100 mL) at 0 °C, the resulting mixture was stirred for 30 min. The precipitate was washed with acetone (600 mL), ethyl acetate (200 mL), and petroleum ether (500 mL) in the order indicated and then dried, yielding sodium 4-carboxy-2-hydroxybenzenesulfonate (82.5 g, 94.9%) as an off-white solid. 1 H NMR (400 MHz, DMSO-d6): δ 12.93 (1H, broad singlet), 10.58 (1H, S), 7.55 (d, J= 8 Hz, 1H), 7.37 (dd, J= 8, 1.6 Hz, 1H), 7.29 (d, J= 1.6 Hz, 1H). Synthesis of sodium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate.

[0174] 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 then concentrated to half its volume, cooled to 0 °C, and stirred for 30 min. The resulting solid was filtered, washed with methanol (200 ml) and petroleum ether (500 ml), and then dried, yielding sodium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (37.0 g, 70%) as an off-white solid. 1 H NMR (400 MHz, DMSO-d6): δ 10.63 (1H, S) 7.57 (d, J = 8.0 Hz, 1H), 7.39 (dd, J = 8.0, 2.0 Hz, 1H), 7.30 (d, J = 1.6 Hz, 1H), 3.83 (3H, S). Synthesis of triphenylsulfonium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (PAG-18).

[0175] 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), after which the mixture was stirred at room temperature for 16 h. The organic layer was then washed with 10% NaHCO3 in water (100 ml), followed by five 100 ml washes with water. The organic layer was concentrated under reduced pressure, washed with THF:petroleum ether (1:3, 100 ml), and dried, yielding triphenylsulfonium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (18 g, 92.5%) as an off-white solid. 1 H NMR (400 MHz, DMSO-d6): δ 10.64 (1H, S), 7.88-7.76 (m, 15H), 7.57 (d, J = 8.0 Hz, 1H), 7.39 (dd, J = 8.0, 2.0 Hz, 1H), 7.30 (d, J = 1.6 Hz, 1H), 3.83 (3H, S). Synthesis of bis(4-(tert-butyl)phenyl)iodonium 2-hydroxy-4-(methoxycarbonyl)benzenesulfonate (PAG-19).

[0176] 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), after which the resulting mixture was stirred at room temperature for 16 h. The organic fraction was then washed with water (5 x 500 ml) and concentrated under reduced pressure to remove the solvent. The remaining solution was then slowly poured into methyl tert-butyl ether (700 ml). A precipitate was collected and dried under vacuum, yielding bis(4-(tert-butyl)phenyl)iodonium 4-(methoxycarbonyl)-2-hydroxybenzenesulfonate as a white solid (28.5 g, 69%). 1 H NMR (499 MHz, 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, 1.7 Hz, 1H), 7.32 (d, J = 1.7 Hz, 1H), 3.84 (s, 2H), 1.26 (s, 14H). Synthesis of 4-(4-(tert-butyl)phenyl)-1,4-oxathian-4-ium-4-(butoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-20).

[0177] 4-(4-(tert-Butyl)phenyl)-1,4-oxathian-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), after which the reaction mixture was stirred for 16 h at room temperature. The organic layer was then washed with water (7 x 500 ml) and concentrated under reduced pressure to remove the solvent. The remaining solution was then slowly poured into methyl tert-butyl ether (700 ml). The precipitate was collected and dried under vacuum, yielding 4-(4-(tert-Butyl)phenyl)-1,4-oxathian-4-ium-4-(butoxycarbonyl)-2-hydroxybenzenesulfonate as a white solid (39.1 g, 78%). 1H NMR (499 MHz, Aceton-d6) δ 8,17 - 8,11 (m, 2H), 7,89 - 7,82 (m, 2H), 7,70 (dd, J = 8,0, 1,1 Hz, 1H), 7,45 - 7,37 (m, 2H), 4,49 (dt, J = 14,0, 3,8 Hz, 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 = 7,4 Hz, 3H). Synthese von Natrium-4-(ethoxycarbonyl)-2-hydroxybenzolsulfonat.

[0178] Concentrated hydrochloric acid (200 ml) was added to a solution of sodium 4-carboxy-2-hydroxybenzenesulfonate (100 g) in ethanol (2 l), after which the resulting mixture was heated under reflux for 32 h. The reaction mixture was then cooled to room temperature, concentrated under reduced pressure, dissolved in water (300 ml), extracted with 5% methanol in ethyl acetate (2 x 500 ml), and concentrated under reduced pressure. The crude product obtained was further purified by washing with acetonitrile and dried, yielding sodium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate as an off-white solid (50.0 g, 45%). 1 H NMR (400 MHz, DMSO-d6): δ 10.6 (s, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.39 (dd, J = 8.0, 1.6 Hz, 1H), 7.31 (d, J = 1.6 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 1.31 (t, J = 7.2 Hz, 3H). Synthesis of triphenylsulfonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-21).

[0179] Sodium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (15.0 g) and triphenylsulfonium bromide (15.3 g) were dissolved in water (150 ml) and DCM (300 ml), after which the resulting mixture was stirred at room temperature for 16 h. The organic layer was then washed with saturated sodium bicarbonate in water (100 ml) followed by water (3 x 100 ml) and then concentrated under reduced pressure, yielding triphenylsulfonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate as a light brown oil (14 g, 49%). 1 H NMR (400 MHz, DMSO-d6): δ 10.64 (s, 1H), 7.88-7.63 (m, 15H), 7.57 (d, J = 8.0 Hz, 1H), 7.39 (dd, J = 8.0, 1.6 Hz, 1H), 7.30 (d, J = 1.6 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 1.31 (t, J = 7.2 Hz, 3H). Synthesis of bis(4-(tert-butyl)phenyl)iodonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate (PAG-22).

[0180] 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), after which the resulting mixture was stirred at room temperature for 16 h. The organic fraction was then washed with water (6 x 700 mL) and concentrated under reduced pressure to remove the solvent. The remaining solution was then slowly poured into methyl tert-butyl ether (700 mL). The resulting precipitate was collected and dried under reduced pressure, yielding bis(4-(tert-butyl)phenyl)iodonium 4-(butoxycarbonyl)-2,6-dihydroxybenzenesulfonate as a white solid (69.4 g, 82.2%). 1 H NMR (400 MHz, acetone-d6) δ 8.31 - 8.24 (m, 2H), 7.71 - 7.65 (m, 2H), 6.94 (s, 1H), 4.27 (t, J = 6.5 Hz, 1H), 2.85 - 2.78 (m, 4H), 1.79 - 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 = 7.4 Hz, 2H). Synthesis of bis(4-(tert-butyl)phenyl)iodonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-23).

[0181] 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), after which the resulting mixture was stirred at room temperature for 16 h. The organic fraction was then washed with water (7 × 500 mL) and concentrated under reduced pressure to remove the solvent. The remaining solution was then slowly poured into methyl tert-butyl ether (700 mL). A precipitate was collected and dried under reduced pressure, yielding bis(4-(tert-butyl)phenyl)iodonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate as a white solid (67.0 g, 77%). 1H NMR (400 MHz, Aceton-d6) δ 7,97 - 7,82 (m, 6H), 7,44 - 7,36 (m, 1H), 4,28 (t, J = 6,5 Hz, 1H), 3,14 (s, 1H), 2,80 (t, J = 1,0 Hz, 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 = 7,4 Hz, 1H). Synthese von (4-(tert-Butyl)phenyl)diphenylsulfonium-4-(butoxycarbonyl)-2-hydroxybenzolsulfonat (PAG-24).

[0182] 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), after which the resulting mixture was stirred at room temperature for 16 h. The reaction mixture was then diluted with DCM (200 mL), washed with water (7 x 500 mL), and concentrated under reduced pressure to remove the solvent. The remaining solution was then slowly poured into methyl tert-butyl ether (700 mL). A gel was collected and dried under reduced pressure, yielding (4-(tert-butyl)phenyl)diphenylsulfonium-4-(butoxycarbonyl)-2-hydroxybenzenesulfonate as a viscous oil (57.8 g, 66%). 1 H-NMR (400 MHz, acetone-d6): δ 7.97 - 7.82 (m, 6H), 7.44 - 7.36 (m, 1H), 4.28 (t, J = 6.6 Hz, 1H), 3.14 (s, 1H), 2.80 (t, J = 1.0 Hz, 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 = 7.4 Hz, 1H). Synthesis of (4-(tert-butyl)phenyl)diphenylsulfonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate (PAG-25).

[0183] 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), after which the resulting mixture was stirred at room temperature for 16 h. The reaction mixture was then diluted with DCM (200 mL), washed with water (7 x 500 mL), and concentrated under reduced pressure to remove the solvent. The remaining solution was then slowly poured into methyl tert-butyl ether (700 mL), yielding the product as a gel. The gel was collected and dried under reduced pressure, giving (4-(tert-butyl)phenyl)diphenylsulfonium 4-(ethoxycarbonyl)-2-hydroxybenzenesulfonate as a viscous oil (7180 g, 93%). 1H NMR (400 MHz, acetone-d6) δ 8.29 - 8.22 (m, 1H), 7.64 (dd, J = 15.9, 8.3 Hz, 1H), 4.33 (q, J = 7.1 Hz, 1H), 3.14 (s, 1H), 2.82 - 2.78 (m, 3H), 2.10 (s, 1H), 1.37 (t, J = 7.1 Hz, 1H), 1.34 (s, 5H), 1.14 (s, 4H); ESI-MS: [M] - : 245.01 and [M] + : 319.15. Production of photoresist polymer

[0184] The chemical structures of the polymers and quenchers used in the examples and comparison examples are shown below. Polymer P1 was prepared using generally available industrial processes, and polymer P2 and quencher Q1 were obtained from commercial sources. Solubility test for base material (polymer P1)

[0185] A 3 wt% solution of polymer P1 in propylene glycol methyl ether acetate (PGMEA) was shaken in a 20 mL glass vial on a mechanical shaker and filtered through a PTFE disc filter with a pore size of 0.20 µm. Si wafers were primed with hexamethyldisilazane (HMDS) at a curing temperature of 120 °C for 30 seconds. The polymer films were applied to the primed Si wafers by spin coating using a TEL Clean Track ACT 8 coating tool and pre-annealed at 90 °C for 60 seconds. The initial thickness (t0) was determined using a KLA Therma-Wave Opti-Probe 7341. The wafers were then treated with 0.26 N aqueous TMAH solution (MF™-CD26, DuPont Electronics & Industrial) for 60 seconds at room temperature. The wafers were then rinsed with deionized water and centrifugally dried. After treatment, the thickness (t1) was measured again and the thickness change (Δt) was calculated according to Equation 1: Δt=t1−t0

[0186] The results are shown in Table 1. Table 1 polymer Thickness before alkali treatment t0(Å) Thickness after alkali treatment t1(Å) Thickness change Δt(Å) P1 833 833 0 PHS (cf.) 874 15 859 PHS = Poly(hydroxystyrene) Production and processing of photoresist compositions

[0187] ArF photoresist compositions. Positive tone photoresist compositions were prepared by dissolving solid components (PAG, quencher, first polymer, and second polymer) in solvents using the materials and amounts specified in Table 2A, the amounts being expressed in wt% based on 100 wt% of the total weight of the solids. The total solids content for the photoresist compositions was 3.10%. The solvent system contained propylene glycol methyl ether acetate (S1) (35 wt%) and methyl 2-hydroxyisobutyrate (S2) (65 wt%). Each mixture was shaken in a 100 mL glass vial on a mechanical shaker and filtered through a PTFE disc filter with a pore size of 0.20 micrometers. Table 2A Photoresist composition PAG Quencher First polymer Second polymer solvent PR1 PAG-1[8,68] Q1[3,10] P1[85,22] P2[3,001 S1 / S2[35:65 w / w] PR2 PAG-9[10,29] Q1[3.10] P1[83,61] P2[3,001 S1 / S2[35:65 w / w] PR3 PAG-3[9,36] Q1[3,10] P1[84,551 P2[3,00] S1 / S2[35:65 w / w] PR4 PAG-4[10,16] Q1[3,10] P1[83,74] P2[3,001 S1 / S2[35:65 w / w] PR5 PAG-5[7,77] Q1[3,10] P1[86,13] P2[3,00] S1 / S2[35:65 w / w] PR6 PAG-6[8,09] Q1[3,10] P1[85,81] P2[3,001 S1 / S2[35:65 w / w] PR7 PAG-8[7,87] Q1[3,10] P1[86,03] P2[3,00] S1 / S2[35:65 w / w] PRS PAG-10[7,35] Q1[3,10] P1[86,55] P2[3,001 S1 / S2[35:65 w / w] PR9 PAG-11[8,93] Q1[3,10] P1[84,97] P2[3,00] S1 / S2[35:65 w / w] PR10 PAG-13[9,00] Q1[3,10] P1[84,90] P2[3,00] S1 / S2[35:65 w / w] PR11 PAG-12[8,51] Q1[3,10] P1[85,39] P2[3,00] S1 / S2[35:65 w / w] PR12 PAG-17[8,42] Q1[3,10] P1[85,48] P2[3,00] S1 / S2[35:65 w / w] See PR1 TPS-PFBuS [9,09] Q1[3,10] P1[84,81] P2[3,00] S1 / S2[35:65 w / w] See PR2 TPS-CSA[10,67] Q1[2,32] P1[84,01] P2[3,00] S1 / S2[35:65 w / w] See PR3 TPS tosylate [7.02] Q1[3,10] P1[86,88] P2[3,00] S1 / S2[35:65 w / w] TPS-PFBuS: Triphenylsulfonium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate TPS tosylate: Triphenylsulfonium tosylate TPS-CSA: Triphenylsulfonium camphorsulfonate

[0188] KrF photoresist compositions. Positive tone photoresist compositions were compared by dissolving solid components (PAG, Q2, P3, and SLA1) in solvents using the materials and amounts listed in Table 2B, where the amounts are expressed in wt% based on 100 wt% 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) wt ratio 70 / 20 / 10; and SLA1: SILWET™ L-7604 (silicone surfactant, Momentive Performance Materials). The total solids content for the photoresist compositions was 3.10%. Ethyl lactate (S3) was used as the solvent. Each mixture was shaken in a 100 ml glass vial on a mechanical shaker and filtered through a PTFE disc filter with a pore size of 0.20 micrometers. Table 2B Photoresist composition PAG Quencher First polymer Second polymer solvent PR13 PAG-1[2,17] Q2[0,24] P3[97,06] SLA1[0,53] S3 PR14 PAG-10[1,84] Q2[0,24] P3[97,39] SLA1[0.53] S3 PR15 PAG-11[2,24] Q2[0,24] P3[97,00] SLA1[0.53] S3 PR16 PAG-13[2,25] Q2[0,24] P3[96,98] SLA1[0.53] S3 PR17 PAG-12[2,13] Q2[0,24] P3[97,10] SLA1[0.53] S3 PR18 PAG-16[1,88] Q2[0,24] P3[97,35] SLA1[0.53] S3 PR19 PAG-14[2,15] Q2[0,24] P3[97,09] SLA1[0.53] S3 PR20 PAG-4[2,55] Q2[0,24] P3[96,69] SLA1[0.53] S3 PR21 PAG-18[2.00] Q2[0,24] P3[97,23] SLA1[0.53] S3 PR22 PAG-17[2,11] Q2[0,24] P3[97,13] SLA1[0.53] S3 PR23 PAG-2[2,70] Q2[0,24] P3[96,54] SLA1[0.53] S3 PR24 PAG-19[2,53] Q2[0,24] P3[96,71] SLA1[0.53] S3 PR25 PAG-20[2,07] Q2[0,24] P3[97,17] SLA1[0.53] S3 PR26 PAG-21[2,06] Q2[0,24] P3P3[97,18] SLA1SLA1[0.53] S3 PR27 PAG-22[2,76] Q2[0,24] P3[96,47] SLA1[0.53] S3 PR28 PAG-23[2,59] Q2[0,24] P3[96,65] SLA1[0.53] S3 PR29 PAG-24[2,40] Q2[0,24] P3[96,83] SLA1[0.53] S3 PR30 PAG-25[2,29] Q2[0,24] P3[96,95] SLA1[0.53] S3 VGL. PR4 TPS-TFMBS [2,50] Q2[0,24] P3[96,73] SLA1[0.53] S3 VGL. PR5 TPS-AdOH-DFMS [2,44] Q2[0,24] P3[96,79] SLA1[0.53] S3 VGL. PR 6 TPS-PFBuS [2,28] Q2[0,24] P3[96,96] SLA1[0.53] S3 TPS-TFMBS: Triphenylsulfonium-2-(trifluoromethyl)benzenesulfonate TPS-AdOH-DFMS: Triphenylsulfonium-1,1-difluoro-2-(((1r,3s,5R,7S)-3-hydroxyadamantan-1-yl)methoxy)-2-oxoethane-1-sulfonate TPS-PFBuS: Triphenylsulfonium-perfluorobutane sulfonate Lithographic Examination - Examples 1-9

[0189] Evaluation of E size, EL% and LWR. Antireflection agent AR™ 40A (DuPont Electronics & Industrial) was spin-deposited onto 300 mm silicon wafers using a curing temperature of 205 °C for 60 seconds, forming a first BARC layer 800 Å thick. Antireflection agent AR™ 104 (DuPont Electronics & Industrial) was then spin-deposited onto the wafers using a curing temperature of 175 °C for 60 seconds, forming a second BARC layer 400 Å thick. A photoresist composition from Table 1 was then spin-deposited onto the wafers, after which the wafers were pre-annealed at 90 °C for 60 seconds, resulting in a photoresist layer 900 Å thick. The BARC and photoresist layers were applied using a TEL Clean Track Lithius coating tool.Wafers were exposed using an ASML 1900i immersion scanner (1.35 NA, 0.988 / 0.90 inner / outer sigma, dipole illumination with 35Y polarization) with a 1:1 line-spacing mask (38 nm linewidth / 76 nm pitch) at various doses of activating 193 mm radiation. After exposure, the wafers were annealed for 60 seconds at 95 °C and developed for 12 seconds with 0.26 N aqueous tetramethylammonium hydroxide (TMAH) solution (MF™-CD26, DuPont Electronics & Industrial). The wafers were then rinsed with deionized water and centrifugally dried, yielding photoresist structures. CD linewidth measurements of the formed structures were performed using a Hitachi High Technologies Co. CG4000 CD-SEM.

[0190] Line-space structures in nanometers (mm) were analyzed for the critical dimension (CD), where the dimensional energy “E size“The irradiation energy is such that the CD of the formed line-distance structure equals the CD of the mask structure.” size is measured in units of millijoules per square centimeter (mJ / cm²). 2 The exposure margin (EL%) is the difference in exposure energy required to print the line-spacing structures at plus and minus 10% of the target diameter, normalized by the dimensioning energy. Linewidth roughness (LWR) is expressed in nanometers (nm) and was determined as a 3-sigma value from the distribution of 100 random linewidth measurement points and subsequent removal of metrological noise. size EL% and LWR data are shown in Table 3.

[0191] Evaluation of E0. Antireflection agent AR™40A (DuPont Electronics & Industrial) was spin-deposited onto 200 mm silicon wafers using a curing temperature of 205 °C for 60 seconds, forming a BARC layer 800 Å thick. A photoresist composition from Table 1 was then spin-deposited onto the wafers, after which the wafers were pre-annealed at 90 °C for 60 seconds, resulting in a photoresist layer 900 Å thick. The BARC and photoresist layers were deposited using a TEL Clean Track ACT 8 coating tool. The wafers were exposed to activating 193 mm radiation at various doses using an ASML 1100 scanner (0.75 NA, 0.89 / 0.64 inner / outer sigma, with Quadrapole-30). The exposed wafers were annealed for 60 seconds at 95 °C after exposure and developed for 60 seconds with 0.26 N aqueous TMAH solution (MF™-CD26, DuPont Electronics & Industrial).The wafers were then rinsed with deionized water and centrifugally dried. The film thickness was calculated for each exposed area using a KLA Therma-Wave Opti-Probe 7341 device and plotted against the dose. E0 values ​​(mJ / cm²). 2 The E0 values ​​were determined as the first dose value at which the remaining film thickness was less than 7% of the original application thickness. The E0 data are shown in Table 3. Table 3 Example Composition E0 38 nm / 76 p E size EL% LWR 1 PR1 7,2 22,3 16,6 2,8 2 PR2 14,6 55,7 23,4 2,3 3 PR3 9,0 24,4 19,8 2,7 4 PR4 8,6 30,3 24,0 2,4 5 PR5 6,6 23,8 17,2 2,8 6 PR6 8,2 27,7 16,1 2,8 7 PR7 8,0 24,9 14,4 3,4 8 (Cf.) VGL. PR1 5,8 16,3 19,2 2,7 9 (Cf.) VGL. PR2 34,0 NZ NZ NZ NZ = not tested due to low sensitivity based on E0 Lithographic testing - Examples 10-43ArF photolithography

[0192] Evaluation of E0, E size, EL% and LWR. Antireflection agent AR™ 40A (DuPont Electronics & Industrial) was spin-deposited onto 200 mm silicon wafers using a curing temperature of 205 °C for 60 seconds, forming a BARC layer 800 Å thick. A photoresist composition from Table 1 was then spin-deposited onto the wafers, after which the wafers were pre-annealed at 90 °C for 60 seconds, resulting in a photoresist layer 900 Å thick. The BARC and photoresist layers were applied using a TEL Clean Track ACT 8 coating tool. The wafers were exposed using an ASML 1100 scanner (0.75 NA, 0.89 / 0.64 inner / outer sigma, dipole illumination with 35Y polarization) using a mask with 1:1 line spacing structures (90 nm line width / 180 nm pitch) with activating 193 mm radiation.The exposed wafers were annealed for 60 seconds at 95 °C after exposure and developed for 60 seconds with 0.26 N aqueous TMAH solution (MF™-CD26, DuPont Electronics & Industrial). The wafers were then rinsed with deionized water and centrifuged, resulting in photoresist structures. CD linewidth measurements of the formed structures were performed using a Hitachi High Technologies Corp. CG9380 CD SEM. The E0, E. size EL% and LWR values ​​were determined as described above, and the results are shown in Table 4. Example Composition E0 90 nm / 180 p E size EL% LWR 10 PR1 7,2 25,4 14,9 4,3 11 PR3 7,4 26,1 12,9 4,4 12 PR4 8,6 31,0 14,4 4,5 13 PR5 8,6 30,1 12,2 4,3 14 PR6 6,6 23,4 13,5 5,0 15 PR7 8,0 26,3 12,3 5,0 16 PR8 6,2 21,0 9,0 4,8 17 PR9 6,6 23,4 17,0 4,5 18 PR10 6,8 25,1 28,0 4,1 19 PR11 9,0 34,0 18,0 5,0 20 PR12 8,4 29,7 14,0 4,3 21 (Cf.) VGL. PR1 5,8 19,8 15,3 4,7 22 (Cf.) VGL. PR3 15,0 63,6 5,0 11,7 KrF photolithography

[0193] Evaluation of E0, E sizeEL% and LWR. A bottom antireflective coating, AR™ 3 (DuPont Electronics & Industrial), was spin-deposited onto 200 mm silicon wafers using a curing temperature of 205 °C for 60 seconds, forming a BARC layer 600 Å thick. A KrF photoresist was then spin-deposited onto the wafers, after which they were pre-annealed at 130 °C for 60 seconds, resulting in a photoresist layer 6035 Å thick. The BARC and photoresist layers were applied using a TEL CLEAN TRACK™ ACT™ 8 coating tool. The wafers were exposed using a CANON FPA 5000 ES4 DUV Stepper (conventional illumination 0.63 NA, 0.8 partial coherence) using a mask with 1:1 line spacing structures (250 nm line width / 500 nm pitch) with activating 248 nm radiation.The exposed wafers were annealed for 90 seconds at 130 °C after exposure and developed for 45 seconds with 0.26 N aqueous TMAH solution (DuPont MF™-CD26, DuPont Electronics & Industrial). The wafers were then rinsed with deionized water and centrifuged dry, yielding photoresist structures. CD linewidth measurements of the formed structures were performed using a Hitachi High Technologies Corp. CG9380 CD-SEM. The E0, E. size -, EL% and LWR values ​​were determined as described above, and the results are shown in Table 5. Table 5 Example composition E0 250 nm / 500 p E size EL% LWR 23 PR13 74 164 18 7,3 24 PR14 62 125 13 8,2 25 PR15 54 131 25 8,7 26 PR16 61 151 23 8,6 27 PR17 108 208 22 8,3 28 PR18 53 117 20 7,0 29 PR19 126 235 14 7,7 30 PR20 86 215 26 7,7 31 PR21 73 154 7 8,1 32 PR22 77 188 22 6,5 33 PR23 53 130 23 7,1 34 PR24 56 126 15 7,8 35 PR25 126 35 14 7,7 36 PR26 86 193 23 7,7 37 PR27 72 180 23 7,3 38 PR28 72 173 20 6,7 39 PR29 94 259 14 - 40 PR30 94 284 11 - 41 (cf.) See PR4 64 144 24 7,4 42 (cf.) See PR5 68 173 28 7,9 43 (cf.) See PR6 59 154 23 8,4

[0194] The following photoacid generators were prepared in the following synthesis examples for use in the photolithography examples in Tables 6 and 7 below. Synthesis of tetraethylammonium 2-hydroxy-4-((4-iodophenoxy)carbonyl)benzenesulfonate

[0195] A mixture of potassium 4-carboxy-2-hydroxybenzenesulfonate (6.41 grams (g), 25 millimoles (mmol)), 4-iodophenol (8.25 g, 37.5 mmol), tetraethylammonium chloride (8.29 g, 50 mmol), and 4-pyrrolidinopyridine (185 milligrams (mg), 1.25 mmol) in N,N-dimethylformamide (DMF, 75 mL) was mixed with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (5.75 g, 30 mmol) at room temperature. The mixture was stirred for 3 hours. Then, the mixture was quenched by pouring it into aqueous tetramethylammonium chloride solution (20% w / v, 500 mL). The resulting mixture was extracted with dichloromethane (DCM, 4 × 100 ml), after which the combined organic layers were washed with aqueous tetraethylammonium chloride (20% w / v, 3 × 50 ml) and water (3 × 100 ml). The organic layer was dried over 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 oily precipitate was isolated by decanting the mother liquor and washed with an excess of methyl tert-butyl ether. The residual solvent was removed by overnight storage in a vacuum oven at 3 °C, yielding the product as a colorless oil (6.08 g, 44%). 1 H NMR (499 MHz, DMSO-d6) δ 10.71 (s, 1H), 7.81 (d, J = 8.9 Hz, 2H), 7.66 (d, J = 8.0 Hz, 1H), 7.56 (dd, J = 8.0, 1.7 Hz, 1H), 7.47 (d, J = 1.6 Hz, 1H), 7.15 (d, J = 8.7 Hz, 2H), 3.19 (q, J = 7.3 Hz, 8H), 1.15 (tt, J = 7.3, 1.7 Hz, 12H). Synthesis of phenyl(3-(trifluoromethyl)phenyl)iodonium-2-hydroxy-4-((4-iodophenoxy)carbonyl)benzenesulfonate (D1):

[0196] 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 stirred vigorously in a two-phase mixture of DCM (50 mL) and water (50 mL) at room temperature for 3 h. The stirrer was then stopped, and the two-phase mixture was separated into individual layers. The organic layer was treated with n-heptane to a final n-heptane:DCM ratio of 1:3. The organic layer was washed with water (5 x 20 mL), dried over filter paper, and concentrated under reduced pressure. The resulting residue was resuspended in acetone (20 mL) and then added to a stirred solution of n-heptane (500 mL), resulting in a precipitate. The precipitate was isolated by decanting the mother liquor and washed with an excess of n-heptane.The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding product D1 in the form of an amorphous, colorless solid (1.76 g, 63%). 1 H NMR (499 MHz, DMSO-d6) δ 10.71 (s, 1H), 8.75 (s, 1H), 8.55 (d, J = 8.1 Hz, 1H), 8.31 (d, J = 7.7 Hz, 2H), 8.02 (d, J = 7.9 Hz, 1H), 7.80 (d, J = 8.7 Hz, 2H), 7.75 (t, J = 8.0 Hz, 1H), 7.67 (t, J = 7.9 Hz, 2H), 7.59 - 7.51 (m, 3H), 7.49 (d, J = 1.7 Hz, 1H), 7.17 - 7.12 (m, 2H). 19 F NMR (470 MHz, DMSO) δ -61.22. Synthesis of tris(4-fluorophenyl)sulfonium-2-hydroxy-4-((4-iodophenoxy)carbonyl)benzenesulfonate (D2):

[0197] 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 in a two-phase mixture of DCM (50 mL) and water (50 mL) at room temperature for 3 h. The stirrer was then stopped, and the two-phase mixture was separated into individual layers. The organic layer was treated with n-heptane to a final n-heptane:DCM ratio of 1:3. The organic layer was washed with water (5 x 20 mL), dried over 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), resulting in a precipitate. The precipitate was isolated by vacuum filtration and washed with an excess of n-heptane.The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding product D2 in the form of a white solid (1.53 g, 57%). 1 H NMR (499 MHz, DMSO-d6) δ 10.70 (s, 1H), 7.97 - 7.89 (m, 6H), 7.81 (dt, J = 8.7, 2.0 Hz, 2H), 7.66 (t, J = 8.1 Hz, 7H), 7.55 (dd, J = 8.0, 1.7 Hz, 1H), 7.46 (d, J = 1.7 Hz, 1H), 7.18 - 7.12 (m, 2H). 19 F NMR (470 MHz, DMSO) δ -103.50. Synthesis of tetraethylammonium 4-((2-fluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate:

[0198] A mixture of 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) in DMF (30 mL) was treated at room temperature with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (3.59 g, 18.2 mmol). The mixture was stirred overnight at room temperature. The mixture was then quenched by pouring it into aqueous tetramethylammonium chloride solution (20% w / v, 500 mL). The resulting mixture was extracted with DCM (4 x 100 mL), after which the combined organic layers were washed with aqueous tetraethylammonium chloride (20% w / v, 3 x 50 mL) and water (3 x 100 mL). The organic layer was dried over filter paper and concentrated under reduced pressure. The resulting residue was resuspended in acetone (50 ml) and added dropwise to a stirred solution of methyl tert-butyl ether (500 ml), resulting in a precipitate.The oily precipitate was isolated by decanting the mother liquor and washing with an excess of methyl tert-butyl ether. The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding the product as a colorless oil (3.20 g, 46%). 1 H NMR (499 MHz, DMSO-d6) δ 7.71 (d, J = 8.0 Hz, 1H), 7.61 (dd, J = 8.1, 1.7 Hz, 1H), 7.51 (d, J = 1.7 Hz, 1H), 7.50 - 7.36 (m, 3H), 7.31 (td, J = 7.6, 1.7 Hz, 1H), 3.20 (q, J = 7.3 Hz, 8H), 1.27 - 1.12 (t, 12H). Synthesis of Bis(4-(tert-butyl)phenyl)iodonium-4-((2-fluorphenoxy)carbonyl)-2 hydroxybenzenesulfonate (D3):

[0199] Tetraethylammonium 4-((2-fluorphenoxy)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 in a two-phase mixture of DCM (70 mL) and water (70 mL) at room temperature for 3 h. The stirrer was then stopped, and the two-phase mixture was separated into individual layers. The organic layer was washed with water (5 x 20 mL), dried over 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), yielding a precipitate. The precipitate was isolated by vacuum filtration and washed with an excess of n-heptane. The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding product D3 in the form of a white solid (2.60 g, 50%). 1H NMR (499 MHz, DMSO-d6) δ 10,80 (s, 1H), 8,20 - 8,14 (m, 4H), 7,71 (d, J = 8,0 Hz, 1H), 7,59 (dd, J = 8,0, 1,7 Hz, 1H), 7,56 -7,49 (m, 5H), 7,48 - 7,33 (m, 3H), 7,29 (td, J = 7,7, 1,8 Hz, 1H), 1,26 (s, 18H). 19 F NMR (470 MHz, DMSO) δ 129,50. Synthese von Tetraethylammonium-4-((2,6-difluorphenoxy)carbonyl)-2-hydroxybenzolsulfonat:

[0200] A mixture of 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) in DMF (30 mL) was treated with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (3.59 g, 18.2 mmol) at room temperature. The mixture was stirred overnight at room temperature. The reaction was then quenched by pouring it into aqueous tetramethylammonium chloride solution (20% w / v, 500 mL). The resulting mixture was extracted with DCM (4 x 100 ml), after which the combined organic layers were washed with aqueous tetraethylammonium chloride (20% w / v, 3 x 50 ml) and water (3 x 100 ml). The organic layer was dried over filter paper and concentrated under reduced pressure. The resulting residue was resuspended in acetone (50 ml) and added dropwise to a stirred solution of methyl tert-butyl ether (500 ml), resulting in a precipitate.The oily precipitate was isolated by decanting the mother liquor, washing with an excess of methyl tert-butyl ether. The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding the product as a colorless oil (4.20 g, 59%). 1 H NMR (499 MHz, acetone-d6) δ 7.84 (d, J = 8.1 Hz, 1H), 7.66 (dd, J = 8.0, 1.8 Hz, 1H), 7.61 (d, J = 1.7 Hz, 1H), 7.44 (tt, J = 8.5, 6.1 Hz, 1H), 7.25 (t, J = 8.3 Hz, 2H), 3.45 (q, J = 7.3 Hz, 8H), 1.36 (t, J = 9.1, 5.5, 1.9 Hz, 12H). Synthesis of bis(4-(tert-butyl)phenyl)iodonium-4-((2,6-difluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate (D4):

[0201] Tetraethylammonium-4-((2,6-difluorphenoxy)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 in a two-phase mixture of DCM (70 mL) and water (70 mL) at room temperature for 3 h. The stirrer was then stopped, and the two-phase mixture was separated into individual layers. The organic layer was washed with water (5 x 20 mL), dried over 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), yielding a precipitate. The precipitate was isolated by vacuum filtration and washed with an excess of n-heptane. The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding product D4 in the form of a white solid (3.43 g, 58%). 1H NMR (499 MHz, CDCl3) δ 7,85 - 7,83 (m, 4H), 7,51 (t, J = 1,1 Hz, 1H), 7,42 (d, J = 1,0 Hz, 2H), 7,29 - 7,26 (m, 4H), 7,14-7,12 (m, J = 8,5, 5,9 Hz, 1H), 6,97 - 6,92 (m, 2H), 1,18 (s, 18H). 19 F NMR (470 MHz, DMSO-d6) δ 126,06. Synthese von Tetraethylammonium-2-hydroxy-4-((2,4,6-triiodphenoxy)carbonyl)benzolsulfonat:

[0202] A mixture of 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) in DMF (150 ml) was treated at room temperature with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (18.40 g, 96 mmol). The mixture was stirred for 3 h. Then, the mixture was quenched by pouring it into aqueous tetramethylammonium chloride solution (20% w / v, 750 ml). The resulting mixture was extracted with DCM (4 x 200 ml), after which the combined organic layers were washed with aqueous tetraethylammonium chloride (20% w / v, 3 x 100 ml) and water (3 x 200 ml). The organic layer was dried over 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), resulting in a precipitate.The oily precipitate was isolated by decanting the mother liquor, washing with an excess of methyl tert-butyl ether. The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding the product as a white solid (28.50 g, 44%). 1 H NMR (499 MHz, DMSO-d6) δ 10.77 (s, 1H), 8.24 (s, 2H), 7.72 (d, J = 8.1 Hz, 1H), 7.63 (dd, J = 8.1, 1.8 Hz, 1H), 7.52 (d, J = 1.7 Hz, 1H), 3.19 (q, J = 7.3 Hz, 8H), 1.19 - 1.12 (m, 12H). Synthesis of tri-p-tolylsulfonium-2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate (DS):

[0203] Tetraethylammonium-2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate (4.0 g, 5 mmol) and trip-p-tolylsulfonium bromide (1.93 g, 5 mmol) were vigorously stirred in a two-phase mixture of DCM (50 mL) and water (50 mL) at room temperature for 3 h. The stirrer was then stopped, and the two-phase mixture was separated into individual layers. The organic layer was treated with n-heptane to a final n-heptane:DCM ratio of 1:3. The organic layer was washed with water (5 x 20 mL), dried over 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), yielding a precipitate. The precipitate was isolated by vacuum filtration and washed with an excess of n-heptane.The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding product D5 in the form of a white solid (4.61 g, 94%). 1 H NMR (499 MHz, DMSO-d6) δ 10.78 (s, 1H), 8.23 ​​(s, 2H), 7.71 (d, J = 8.0 Hz, 1H), 7.67 (d, J = 8.5 Hz, 6H), 7.61 (dd, J = 8.1, 1.7 Hz, 1H), 7.57 (d, J = 8.2 Hz, 6H), 7.51 (d, J = 1.7 Hz, 1H), 2.43 (s, 9H). Synthesis of 5-phenyl-5H-dibenzo[b,d]thiophene-5-ium-2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate (D6):

[0204] 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 stirred vigorously in a two-phase mixture of DCM (50 mL) and water (50 mL) at room temperature for 3 h. The stirrer was then stopped, and the two-phase mixture was separated into individual layers. The organic layer was treated with n-heptane to a final n-heptane:DCM ratio of 1:3. The organic layer was washed with water (5 x 20 mL), dried over 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), resulting in a precipitate. The precipitate was isolated by vacuum filtration and washed with an excess of n-heptane.The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding product D6 in the form of a white solid (3.53 g, 76%). 1 H NMR (499 MHz, DMSO-d6) δ 10.77 (s, 1H), 8.52 (d, J = 7.9 Hz, 2H), 8.38 (d, J = 7.9 Hz, 2H), 8.23 ​​(s, 2H), 7.95 (td, J = 7.6, 1.1 Hz, 2H), 7.79 - 7.66 (m, 4H), 7.64 - 7.55 (m, 5H), 7.52 (d, J = 1.7 Hz, 1H). Synthesis of phenyl(3-(trifluoromethyl)phenyl)iodonium 2-hydroxy-4-((2,4,6-triiodophenoxy)carbonyl)benzenesulfonate (D7):

[0205] 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 in a two-phase mixture of DCM (60 mL) and water (60 mL) at room temperature for 3 h. After the addition of acetone (50 mL), stirring continued overnight. The stirrer was then stopped, and the two-phase mixture was separated into individual layers. The aqueous layer was back-extracted with DCM (3 x 50 mL), after which the combined organic layers were washed with water (5 x 50 mL), dried over filter paper, and concentrated under reduced pressure. The obtained precipitate was resuspended in acetone (100 ml) and added to a stirred solution of n-heptane and methyl tert-butyl ether (1:1, 900 ml), resulting in a precipitate. The precipitate was isolated by vacuum filtration and washed with an excess of n-heptane.The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding product D7 in the form of a white solid (2.58 g, 30%). 1 H NMR (499 MHz, DMSO-d6) δ 10.76 (s, 1H), 8.75 (s, 1H), 8.55 (d, J = 8.1 Hz, 1H), 8.31 (d, J = 7.6 Hz, 2H), 8.24 (s, 2H), 8.05 (d, J = 7.9 Hz, 1H), 7.76 (t, J = 8.0 Hz, 1H), 7.73 - 7.66 (m, 2H), 7.62 (dd, J = 8.1, 1.7 Hz, 1H), 7.56 (t, J = 7.8 Hz, 2H), 7.52 (d, J = 1.7 Hz, 1H). 19 F NMR (470 MHz, DMSO-d6) δ -61.19. Synthesis of 2-(4-iodophenoxy)ethan-1-ol:

[0206] 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. After the addition of 2-bromoethanol (15 g, 120 mmol) to the reaction mixture, the mixture was stirred for 3 hours. The mixture was then quenched by pouring it into water (500 ml). After adding methyl tert-butyl ether (300 ml), the mixture was stirred for 15 minutes. The two-phase mixture was separated into individual layers, after which the aqueous layer was extracted with methyl tert-butyl ether (2 x 100 ml). The combined organic layers were washed with aqueous potassium hydroxide solution (1 M, 3 x 100 ml) and water (3 x 100 ml), dried over filter paper and concentrated under reduced pressure, yielding the product in the form of a white solid (5.82 g, 55%). 1H NMR (499 MHz, DMSOd6) δ 7,57 (dt, J = 9,0, 2,3 Hz, 2H), 6,78 (dt, J = 9,0, 2,2 Hz, 2H), 4,87 (t, J = 5,3 Hz, 1H), 3,95 (dd, J = 5,4, 4,6 Hz, 2H), 3,70 (q, J = 4,8 Hz, 2H). Synthese von Tetraethylammonium-2-hydroxy-4-((2-(4-iodphenoxy)ethoxy)carbonyl)benzolsulfonat:

[0207] A mixture of potassium 4-carboxy-2-hydroxybenzenesulfonate (5.82 g, 22.7 mmol), 2-(4-iodophenoxy)ethan-1-ol (9.00 g, 34.1 mmol), tetraethylammonium chloride (7.52 g, 45.4 mmol), and 4-pyrrolidinopyridine (170 mg, 1.1 mmol) in DMF (50 ml) was treated at room temperature with N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (5.21 g, 27.2 mmol). The mixture was stirred for 3 h and then quenched by pouring it into aqueous tetramethylammonium chloride solution (20% w / v, 300 ml). The resulting mixture was extracted with DCM (4 × 50 ml), after which the combined organic layers were washed with aqueous tetraethylammonium chloride (20% w / v, 3 × 50 ml) and water (3 × 50 ml). The organic layer was dried over 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), resulting in a precipitate.The precipitate was isolated by vacuum filtration and washed with an excess of methyl tert-butyl ether. The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding the product as a white solid (2.80 g, 21%). 1 H NMR (499 MHz, DMSO-d6) δ 10.65 (s, 1H), 7.63 - 7.56 (m, 3H), 7.38 (dd, J = 8.1, 1.7 Hz, 1H), 7.31 (d, J = 1.7 Hz, 1H), 6.85 (dt, J = 8.8, 2.0 Hz, 2H), 4.56 (t, J = 4.6 Hz, 2H), 4.32 (t, J = 4.5 Hz, 2H), 3.19 (q, J = 7.2 Hz, 8H), 1.15 (tt, J = 7.2, 1.8 Hz, 12H). Synthesis of tri-p-tolylsulfonium-2-hydroxy-4-((2-(4-iodophenoxy)ethoxy)carbonyl)benzenesulfonate (D8):

[0208] Tetraethylammonium-2-hydroxy-4-((2-(4-iodophenoxy)ethoxy)carbonyl)benzenesulfonate (2.80 g, 4.72 mmol) and trip-p-tolylsulfonium bromide (1.82 mg, 4.72 mmol) were stirred vigorously in a two-phase mixture of DCM (50 mL) and water (50 mL) at room temperature for 3 h. The stirrer was then stopped, and the two-phase mixture was separated into individual layers. The organic layer was treated with n-heptane to a final n-heptane:DCM ratio of 1:3. The organic layer was washed with water (5 x 20 mL), dried over 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), yielding a precipitate. The precipitate was isolated by vacuum filtration and washed with an excess of n-heptane.The residual solvent was removed by overnight storage in a vacuum oven at 35 °C, yielding product D8 in the form of a colorless oil (2.48 g, 69%). 1 H NMR (499 MHz, DMSOd6) δ 10.67 (s, 1H), 7.67 (d, J = 8.5 Hz, 6H), 7.62 - 7.54 (m, 9H), 7.38 (dd, J = 8.0, 1.7 Hz, 1H), 7.31 (d, J = 1.7 Hz, 1H), 6.85 (dt, J = 8.9, 1.9 Hz, 2H), 4.57 (t, J = 4.5 Hz, 2H), 4.32 (t, J = 4.6 Hz, 2H), 2.43 (s, 9H). Production of photoresist polymer

[0209] The chemical structures of the polymer (P4), the quencher (Q3), and the reference photoacid generator (cD1) used in the examples and reference examples are shown below. Polymer P4 was prepared using generally available industrial processes, and quencher Q3 and reference PAG cD1 were obtained from commercial sources. Production and processing of photoresist compositions

[0210] KrF photoresist compositions. Photoresist compositions were prepared by dissolving solid components in solvents using the materials and amounts specified in Tables 6 and 7, the amounts being expressed in wt% based on 100 wt% of the total weight of the solids. The total solids content for the photoresist compositions was 2.1 wt%. The solvent system contained propylene glycol monomethyl ether acetate (50 wt%) and 4-hydroxy-4-methyl-2-pentanone (50 wt%). Each mixture was shaken with a mechanical shaker and then filtered through a PTFE disc filter with a pore size of 0.2 microns.

[0211] Photolithography evaluation was performed using a CLEAN TRAC ACT8 wafer line (TEL, Tokyo Electron Co.). 200 nm wafers for photolithographic testing were coated with AR™-3 BARC (DuPont Electronics & Industrial) and pre-annealed for 60 seconds at 205 °C, resulting in a 70 nm film. A coating of AR™-40A BARC (DuPont Electronics & Industrial) was then deposited onto the AR™-3 layer and pre-annealed for 60 seconds at 215 °C, resulting in a second BARC layer approximately 80 nm thick. Finally, a photoresist composition was applied to the double BARC stack and pre-annealed for 60 seconds at 110 °C, resulting in a photoresist film layer approximately 50 nm thick.

[0212] The wafers were exposed to 248 nm radiation on a CANON FPA-5000 ES4 scanner (NA=0.8, outer sigma = 0.85, inner sigma = 0.57) using a mask with selected features. After exposure, the wafers were annealed for 60 seconds at 100 °C, developed for 60 seconds with MF™ CD26 TMAH (DuPont Electronics & Industrial) developer, washed with demineralized water, and dried. CD linewidth measurements (CD = critical dimension) of the formed structures were performed using a HITACHI S-9380 CD-SEM. The line width roughness (LWR) values ​​were determined by top-down SEM at an accelerating voltage of 800 volts (V) and a sample current of 8.0 picoamperes (pA) using 200,000x magnification with a digital zoom of 1.0, with the number of frames set to 64.The LWR was measured over a line length of 2 µm in 40 nm steps and reported as the average LWR for the measured area. Based on the CD measurements, the design energy (E. size ) and the LWR of the lines is determined. The pseudo-Z-factor is given below and was determined according to Equation 1: Pseudo Z factor=(Esize)×(LWR)2 where E size in millijoules per square centimeter (mJ / cm²) 2 ) is specified, LWR is specified in nanometers (nm) and the pseudo-Z factor is specified in mJ × 10 -11The pseudo-Z factor (Z' factor) is a modified measure of photoresist performance based on the Z factor, which is a well-known parameter indicative of the RLS performance of photoresists (RLS = Resolution, Line Edge Roughness, Sensitivity; see, e.g., Wallow, T. et al., Proc. SPIE 6921, 69211F, 2008). The pseudo-Z factor is calculated at constant resolution (CD size). Table 6 Photoresist example polymer PAG Quencher E size (mJ / cm 2 LWR(nm) Pseudo-Z factor Structuring quality PR31 P4[75,23%] D1[21,76%] Q3[3,01 %] 74,29 5,33 2114 Good PR32 P4[75,91%] D2[21,05%] Q3[3,04 %] 99,03 5,51 3010 Good PR33 P4[71,04%] D5[26,12%] Q3[2,84 %] 130,46 5,59 4082 Good PR34 P4[71,89%] D6[25,24%] Q3[2,88 %] 90,89 5,63 2885 Good PR35 P4[70,22%] D7[26,97%] Q3[2,81 %] 80,52 5,91 2815 Good PR36 P4[75,22%] D8[21,77%] Q3[3,01 %] 85,81 5,03 2169 Good PR37 P4[69,41%] D9[27,81%] Q3[2,78 %] 62,18 5,89 2157 Good Table 7 PR38 P3[76,61 %] D3 [20,33%] Q3[3,06 %] 86,39 4,80 1990 Good PR39 P3[76,21 %] D4 [20,74%] Q3[3,05 %] 88,24 4,88 2100 Good See PR7 P3[76,88 %] cD1[20.04%] Q3[3,08 %] 92,54 4,98 2294 Good

[0213] As shown in Tables 6 and 7, each of the photoresist examples PR31 to PR39 produced structures with good profiles (structuring quality). As shown in Table 7, the comparison photoresist example PR7 contains the comparison photoacid generator cD1, which contains the anion perfluorobutanesulfonate and the cation bis(4-(tert-butyl)phenyl)iodonium. By direct comparison, the photoresist examples PR38 and PR39 can be directly compared with PR7, since PR38 and PR39 each have the same polymer and quencher components as PR7. The photoacid generators in the photoresist compositions PR38 and PR39 contain the anions 4-((2-fluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate and 4-(2,6-difluorophenoxy)carbonyl)-2-hydroxybenzenesulfonate, respectively. The photoresists of examples PR38 and PR39 showed better lithographic performance, as evidenced by the higher quality images with less LWR and a lower Z-factor compared to VGL.PR7 emerges.

[0214] Although the present disclosure has been described in connection with what is currently considered to be practical embodiments, it is understood that the invention is not limited to the disclosed embodiments, but on the contrary is intended to cover various modifications and equivalent arrangements which are included in the nature and scope of protection of the attached claims. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] US 2024 / 042626

[0001] US 65 / 533,270

[0001] US 8,431,325

[0077] US 4,189,323

[0077] Cited non-patent literature

[0000] Wallow, T. et al Proc. SPIE 6921, 69211F, 2008

[0212]

Claims

[1] Photoresist composition, comprising: one or more alkali-insoluble, non-solvent base materials present in a combined amount of more than 50% by weight, based on the total solids of the photoresist composition; a non-polymeric ionic photoacid generator compound with an anion and an iodonium or sulfonium cation, wherein the anion is represented by formula (1): where in formula (1) Ar 1 for a monocyclic or polycyclic aromatic C 3-60 -group stands L 1 L represents a single bond or one or more binary linkage groups. 1 is free of fluorine R 1 each independently for 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 -Alkyl heteroaryl, substituted or unsubstituted C 4-30 -Heteroarylalkyl or substituted or unsubstituted C 3-30 -Heteroaryloxy stands; R 1 each may further comprise one or more binary linking groups as part of its structure, Z 1 an anion-stabilizing group, wherein Z 1 is designed in such a way that it forms an intramolecular non-covalent bond with the sulfonate anion group, forming a ring with 5 to 8 atoms, and wherein Z1 from -OH, -C(O)OH, -SH, -C(O)SH, -NHS(O)2R 2 , -S(O)2R 2 , -S(O)2NHS(O)2R 2 , -CH(=NOH) or -B(R 3 )2 is selected and where Z 1 optionally also includes one or more binary linking groups as part of its structure, R 2 each independently from 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 -Heteroaryl is selected R 3 each independently from 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 -Heteroaryl is selected two R1 together possibly with Ar 1 form an fused ring, the fused ring optionally further comprising one or more divalent linkage groups as part of its structure, Z 1 and an R 1 together possibly with Ar 1 form an fused ring, the fused ring optionally comprising one or more divalent linkage groups as part of its structure, and b represents an integer from 0 to 4; a photodegradable quencher, a basic quencher, or a combination thereof, and a solvent. [2] Photoresist composition according to claim 1, wherein R 1 each independently for substituted or unsubstituted C 1-30 -Alkyl, substituted or unsubstituted C 3-30 -Cycloalkyl, substituted or unsubstituted C 3-30 -Cycloalkene, substituted or unsubstituted C3-30 -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 -Heteroaryloxy stands and R 1 Each may also include one or more binary linking groups as part of its structure. [3] Photoresist composition according to claim 1, wherein Z 1 is designed in such a way that it forms an intramolecular non-covalent bond with the sulfonate anion group, forming a ring with 6 or 7 atoms. [4] Photoresist composition according to claim 1, wherein the anion stabilizing group has a pKa value of 25 or less. [5] Photoresist composition according to claim 1, wherein the anion-stabilizing group comprises a group which is protic. [6] Photoresist composition according to claim 1, wherein the anion-stabilizing group comprises -OH. [7] Photoresist composition according to claim 1, wherein the anion is free of trifluoromethyl groups and difluoromethylene groups. [8] Photoresist composition according to claim 7, wherein the anion does not comprise fluorine. [9] Photoresist composition according to claim 1, wherein Ar 1 for a monocyclic aromatic C 3-6 -Group stands and Z 1 in an ortho position to that defined by -L'-SO3 - The group shown is present. [10] Photoresist composition according to claim 1, wherein Ar 1 for a polycyclic aromatic C6-60 -Group is standing. [11] Photoresist composition according to claim 10, wherein Z 1 to a ring carbon atom of Ar 1 , which is in an ortho position on the same ring as the one defined by -L 1 -SO3 - The group shown is bound. [12] Photoresist composition according to claim 11, wherein Z 1 in the ortho position stands for -OH and where L 1 stands for a single binding. [13] Photoresist composition according to claim 10, wherein Ar 1 for an fused polycyclic aromatic C 6-60 -Group stands, Z 1 to a ring carbon atom of Ar 1 , which is in a beta position to a ring carbon atom, to the -L 1 -SO3 - is bound, stands, is bound and Z 1 and -L 1 -SO3 - to different rings of the fused polycyclic aromatic C 6-60 are bound to the -group. [14] Photoresist composition according to claim 1, wherein a conjugated acid of the nonpolymeric ionic photoacid generator compound has a pKa value of 0 or less. [15] Photoresist composition according to claim 1, wherein the alkali-insoluble, non-solvent base material comprises a polymer. [16] Photoresist composition according to claim 15, wherein the alkali-insoluble non-solvent base material comprises a chain-cleavable polymer, an unzipping polymer or a combination thereof. [17] Photoresist composition according to claim 1, wherein the alkali-insoluble non-solvent base material comprises a metal-containing material. [18] Photoresist composition according to claim 1, wherein at least one R 1 for a substituted C 6-30 -Aryl or a substituted C 7-30 -Arylalkyl, which may further include one or more divalent linking groups as part of its structure. [19] Photoresist composition according to claim 1, wherein L 1 stands for a single binding. [20] Structuring procedure, the procedure comprising the following: the application of a layer of the photoresist composition according to claim 1 to a substrate to provide a photoresist composition layer; the structural exposure of the photoresist composition layer with activating radiation to provide an exposed photoresist composition layer and the development of the exposed photoresist composition layer to provide a resist relief image.