Nonionic photoacid generator, photoresist composition, and pattern forming method

Abstract

Provided are a nonionic photoacid generator, a photoresist composition, and a patterning method. 【Solution means】 A nonionic photoacid generator compound represented by formula (1) or (2). TIFF2026137059000028.tif63166 (In the formula, ring A 1 is a monocyclic C 3~60 aromatic group, a polycyclic C 3~60 aromatic group, a C 3~15 monocyclic alicyclic group, or a C 3~15 polycyclic alicyclic group; each L 1 is a single bond or one or more linking groups, L 1 does not contain fluorine; each L 2 is a single bond or one or more divalent linking groups; P is a polymerizable group.)

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefits and priority of U.S. Provisional Patent Application No. 63 / 758,577, filed with the U.S. Patent and Trademark Office on 14 February 2025, the entire contents of which application are incorporated herein by reference.

[0002] The present invention relates to a nonionic photoacid generator compound, a photoresist composition, and a patterning method using such a photoresist composition. The present invention finds particular applicability to lithography applications in the semiconductor manufacturing industry. [Background technology]

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

Patent Document

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] [[ID=zo]] The properties of a photoresist composition that can directly affect semiconductor manufacturing costs are photosensitivity, that is, sensitivity to actinic radiation generated by an exposure tool, and higher sensitivity corresponds to higher process throughput for a given shape. To increase photosensitivity, it is desirable for the PAG to generate an acid of sufficiently high strength to cleave acid-labile groups on the polymer. It would be desirable to have a photoresist composition containing a nonionic photoacid generator compound that generates a sulfonic acid group of sufficient strength that does not rely on fluorine substitution due to increased acidity.

Means for Solving the Problems

[0006] One aspect is formula (1) or (2):

Chemical Formula

[0007] Another embodiment provides a photoresist composition comprising a nonionic photoacid generator compound, or a polymer containing repeating units derived from a nonionic photoacid generator compound, and a solvent.

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

[0009] References to exemplary embodiments will be made in detail below, and examples of such embodiments are illustrated in this description. In this regard, these exemplary embodiments may take different forms and should not be construed as being limited to the descriptions herein. Accordingly, exemplary embodiments are described below only for the purpose of illustrating aspects of this description. As used herein, the terms “and / or” encompass any and all combinations of one or more of the enumerated items relating to them. Expressions such as “at least one of” qualify the entire list of elements, but not the individual elements of the list, when preceding a list of elements.

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

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

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

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

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

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

[0016] Each of the aforementioned substituents may be optionally substituted unless otherwise explicitly specified. The term “optionally substituted” means either substituted or unsubstituted. “Substituted” means that at least one hydrogen atom of the chemical structure or group is replaced by another terminal substituent, typically monovalent, provided that the valency does not exceed the normal valency of the specified atom. When the substituent is oxo (i.e., O), two geminal hydrogen atoms on the carbon atom are replaced by a terminal oxo group. It is further noted that the oxo group is bonded to the carbon atom via a double bond to form a carbonyl (C=O), and the carbonyl group is represented herein as -C(O)-. Combinations of substituents or variables are permitted. Exemplary substituents that may be present in a “substituted” position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di-(C) 1~6 ) Alkylamino, alkanoyl (acyl, etc.) 2~6 Alkanoyl groups, for example, formyl (-C(O)H), carboxylic acids or alkali metal or ammonium salts thereof; C 2~6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl) and C 7~13 Esters such as aryl esters (-C(O)O-aryl or -OC(O)-aryl) (including acrylates, methacrylates, and lactones); amides (-C(O)NR2 (wherein R is hydrogen or C) 1~6 Alkyl carboxamide (-CH2C(O)NR2 (wherein R is hydrogen or C) 1~6 Alkyl, halogen, thiol (-SH), C 1~6 Alkylthio(-S-alkyl), thiocyano(-SCN), C 1~6 Alkyl, C 2~6 Alkenil, C 2~6 Alkinyl, C1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, C having at least one aromatic ring 6~12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring being either a substituted aromatic or an unsubstituted aromatic), C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms 7~19 Arylalkyl, aryloxy having 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-), but not limited thereto.

[0017] As used herein, when not otherwise defined, a "divalent linking group" is -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 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylene, or a divalent group containing one or more of combinations thereof, where each R ’ is independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted 1~20 Heteroalkyl, substituted or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30It is heteroaryl. Typically, the divalent linking group includes -O-, -S-, -C(O)-, -C(O)O-, -N(R’)-, -C(O)N(R ’ )-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 alkylene, substituted or unsubstituted C 3~30 cycloalkylene, substituted or unsubstituted C 3~30 heterocycloalkylene, substituted or unsubstituted C 6~30 arylene, substituted or unsubstituted C 3~30 heteroarylene, or one or more combinations thereof, wherein R’ is hydrogen, substituted or unsubstituted C 1~20 alkyl, substituted or unsubstituted C 1~20 heteroalkyl, substituted or unsubstituted C 6~30 aryl, or substituted or unsubstituted C 3~30 heteroarylene. More typically, the divalent linking group includes -O-, -C(O)-, -C(O)O-, -N(R ’ )-, -C(O)N(R’)-, substituted or unsubstituted C 1~10 alkylene, substituted or unsubstituted C 3~10 cycloalkylene, substituted or unsubstituted C 3~10 heterocycloalkylene, substituted or unsubstituted C 6~10 arylene, substituted or unsubstituted C 3~10 heteroarylene, or at least one combination thereof, wherein R’ is hydrogen, substituted or unsubstituted C 1~10 alkyl, substituted or unsubstituted C 1~10 heteroalkyl, substituted or unsubstituted C 6~10 aryl, or substituted or unsubstituted C 3~10 heteroarylene.

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

[0019] The sensitivity of a photoresist often correlates with the final device manufacturing throughput. High-resolution lithography techniques, particularly 193nm lithography (ArF), tend to struggle with photoresists possessing optimal sensitivity. To achieve good sensitivity, many photoresists utilize photoacid generators (PAGs) that contain or induce anions, belonging to the class of sulfonates linked to polymers containing low-activation-energy leaving groups (e.g., ester acetals or acetal-esters). Over the past decade or so, numerous sulfonate derivatives (and their nonionic precursors) have been developed for this purpose, with fluorinated sulfonates being one example. These compounds, excelling in lithography thanks to their remarkably high acidity, are being considered for replacement worldwide in favor of more sustainable alternatives. However, there is still a continuing need for nonionic PAG compounds with good acidity and better sustainability.

[0020] According to one embodiment, formula (1) or (2): [ka] A nonionic photoacid generator compound represented by [formula] is provided.

[0021] In equations (1) and (2), ring A 1 This is a single ring C 3~60 Aromatic group, polycyclic C 3~60 Aromatic group, C 3~15 Monoalicyclic group, or C 3~15 It is a polyalicyclic group. For example, in some embodiments, ring A 1 This is a single ring C 3~60 Aromatic group or polycyclic carbon 3~60 It may be an aromatic group. In other embodiments, ring A 1 C 3~15 Monoalicyclic group or C 3~15 Possibly a polyalicyclic group. Ring A 1 X may optionally be used as described herein. 1 It contains a heteroatom group specified as such.

[0022] In some embodiments, ring A 1 This is a single ring C 3~60 Aromatic group or polycyclic carbon 6~60 It may be an aromatic group. The term "aromatic group" includes both aromatic and heteroaromatic groups. In one embodiment, a monocyclic C 3~60 Aromatic groups are monocyclic C 3~60 Arylene group or monocyclic C 3~60 Heteroarylene groups, typically monocyclic C 6~30 Arylene group or monocyclic C 3~30 It can be a heteroarylene group. 3~60 When an aromatic group is polycyclic, it should be understood that the number of carbon atoms is sufficient to make the group chemically feasible. For example, "polycyclic C 3~60 Aromatic group is a polycyclic carbon group. 10~60 Arylene group or polycyclic carbon 10~30 This can refer to an allerene group. Exemplary monocyclic or polycyclic carbons. 3~60 Aromatic groups include, but are not limited to, benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, and benzo[a]pyrene.

[0023] In some embodiments, ring A 1 C 3~15 Monoalicyclic group or C 3~15 It can be a polyalicyclic group. For example, ring A 1 C 3~15 Monoalicyclic group or C 6~15 It may be a polyalicyclic group. The alicyclic group can optionally be X in the structure of formula 1. 1 It should be understood that it may contain heteroatom groups as specified. For example, ring A 1 This is a single ring C 3~15 Cycloalkylene, monocyclic C 3~15 Cycloalkenylene, monocyclic C 3~15 Heterocycloalkylene, monocyclic C 3~15 Heterocycloalkenylene, polycyclic C 6~15Cycloalkylene, polycyclic C 6~15 Cycloalkenylene, polycyclic C 6~15 Heterocycloalkylene, or polycyclic C 6~15 It may be a heterocycloalkenylene. Ring A 1 Examples of alicyclic groups for this purpose include, but are not limited to, cyclopentane, cyclohexane, decalin, tetrahydrofuran, thiolane, thian, thian-1,1-dioxide, thian-1-oxide, tetrahydropyran, adamantyl, bicyclo[3.2.1]octane, bicyclo[4.3.0]nonane, bicyclo[3.3.1]nonane, etc.

[0024] In equations (1) and (2), each L 1 L is independently a single bond or one or more linking groups, where L 1 It does not contain fluorine. In other words, L 1 If L is one or more linking groups, 1 It does not contain fluorine. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups are, independently, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It can be a heteroaryl compound. Typically, L 1 C is a single bond or a substituted or unsubstituted C 1~20 Alkylene, preferably single bond or substituted or unsubstituted C 1~10It could be alkylene.

[0025] If b is 0, L 1 L can be a single bond or one or more divalent linking groups, where L 1 It should be understood that it does not contain fluorine.

[0026] In equations (1) and (2), each L 2 These are, independently, single bonds or one or more divalent linking groups. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups are, independently, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl. In some embodiments, L 2 is -O-, -N(R ’ )-,-C(O)N(R ’ )-, -S(O)-, -S(O)2-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 It comprises one or more divalent linking groups selected from heteroarylenes or combinations thereof, where each R ’ These are, independently, hydrogen, substituted or unsubstituted C1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It is a heteroaryl compound.

[0027] In formulas (1) and (2), P is a polymerizable group. Exemplary polymerizable groups include, but are not limited to, (meth)acrylate groups, vinyl groups, vinyl aromatic groups, vinyl ether groups, vinyl ketone groups, vinyl ester groups, epoxy groups, etc., or combinations thereof.

[0028] In equation (1), each R 1a and each R 1b R is an independent non-hydrogen substituent, where R 1a and R 1b Each of them optionally further includes one or more divalent linking groups as part of its structure, R 1a and R 1b These can optionally bond together to form aromatic or non-aromatic ring groups. For example, each R 1a and R 1b These are independently substituted or non-substituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, 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 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, or substituted or unsubstituted C 4~30 It may be a heteroarylalkyl. Typically, R 1a and R 1b These can bond together to form aromatic or non-aromatic ring groups.

[0029] In equation (2), each R 1c and R1d R is an independent non-hydrogen substituent, where R c and R 1d Each of them optionally further includes one or more divalent linking groups as part of its structure, R 1c and R 1d These can optionally bond together to form aromatic or non-aromatic ring groups. For example, each R 1c and R 1d These are independently cyano, substituted, or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, 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 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, or substituted or unsubstituted C 4~30 It may be a heteroarylalkyl. Typically, R 1c and R 1d These groups may bond together to form an aromatic or non-aromatic ring group. The ring group may be further substituted with one or more groups.

[0030] In some embodiments, R 1c and R 1d It may further include an electron-withdrawing group as part of its structure. In some embodiments, R 1c or R 1d R may be cyanopropyl alcohol. In one or more embodiments, R 1c and / or R 1d It may further include one or more halogens, for example, one or more iodine groups, as part of its structure.

[0031] In equations (1) and (2), each R 2 R is independently a monovalent nonhydrogen substituent; where each R 2It optionally further includes one or more divalent linking groups as part of its structure. For example, each R 2 These are, independently, halogens, hydroxyls, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It can be a heteroaryloxy. Typically, each R 2 These are independently hydroxyl, substituted, or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It may be a heteroaryloxy. In one or more embodiments, each R 2 It may independently further contain one or more halogens, such as one or more fluoro or iodo groups, as part of its structure.

[0032] In equations (1) and (2), each R 2 The compound optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It could be a heteroaryl.

[0033] In some embodiments, one or more R 2 Each of these may independently further contain an acid-unstable group, a lactone-containing group, a base-solubilizing group, or a combination thereof.

[0034] In equations (1) and (2), each X 1 These are independently -O-, -S-, and -N(R 2a )-, -C(O)-, -S(O)R 2a -, or -S(O2)R 2a -and here, R 2a These are independently substituted or non-substituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls. If n is 0, then X 1 is ring A 1It should be understood that it does not exist inside.

[0035] In equations (1) and (2), each Z 1 It independently contains an anion stabilizing group, where at least one Z 1 It is configured to form a ring having 5 to 8 ring atoms by forming an intramolecular non-covalent bond with an anion derived from the sulfonate group, Z 1 These are independently -OH, -C(O)OH, -SH, -C(O)SH, and -NHS(O)2R 3 -S(O)2R 3 ,-S(O)R 3 -S(O)2NHS(O)2R 3 -CH (=NOH), or -B (R 4 ) Selected from 2; each Z 1 It optionally further includes one or more divalent linking groups as part of its structure. Typically, each anion stabilizing group Z 1 This can be independently selected from -OH, C(O)OH, SH, or -B(OH)2, preferably at least one anionic stabilizing group Z 1 It contains -OH.

[0036] For example, each Z 1 It can be configured to form an intramolecular non-covalent bond with an anion derived from the sulfonate group to form a ring having 5 to 8 ring atoms, or typically 6 or 7 ring atoms. Ring A 1 two or more anionic stabilizing groups Z 1 If it contains an anionic stabilizing group Z 1 It should be understood that at least one of them is configured to form an intramolecular non-covalent bond with at least one anion derived from the sulfonate group to form a ring having 5 to 8 ring atoms. Similarly, L 1 two or more anionic stabilizing groups Z 1 If it contains an anionic stabilizing group Z 1 At least one of the components is configured to form an intramolecular non-covalent bond with at least one anion derived from the sulfonate group, thereby forming a ring having 5 to 8 ring atoms.

[0037] As used herein, “anion stabilizing group” refers to any suitable group capable of stabilizing an anionic group induced via an intramolecular non-covalent bond, as defined herein. Thus, anion stabilizing group is configured to form an intramolecular non-covalent bond with the induced anionic group, or, in other words, anion stabilizing group can form an intramolecular non-covalent bond with the induced anionic group of the sulfonate moiety. As used herein, “non-covalent bond” may refer to any non-covalent interaction between anion stabilizing group and the induced anionic group. As described above, non-covalent interactions are intramolecular, and the anion stabilizing group and the as-formed anionic group are on the same molecule. Exemplary non-covalent bonds include hydrogen bonds or ionic bonds. Anion stabilizing groups may include protic groups. For example, an intramolecular non-covalent bond may be an intramolecular hydrogen bond between a suitable hydrogen atom of the anion stabilizing group and the as-formed anionic group. For example, in some embodiments, the anion stabilizing group may be configured to form an intramolecular hydrogen bond with the as-formed anion group. In some embodiments, intramolecular non-covalent bonds include dipole-dipole interactions, ion-dipole interactions, or a combination thereof. As used herein, “non-covalent bond” does not include bonds based solely on van der Waals forces.

[0038] In equations (1) and (2), each R 3 These are independently trifluoromethyl, hydroxyl, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls.

[0039] In equations (1) and (2), each R 4 These are, independently, hydrogen, fluorine, hydroxyl, substituted or unsubstituted C 1~20Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Selected from heteroaryls.

[0040] In some embodiments, the anionic stabilizing group may have a pKa of 25 or less, typically 20 or less, or 18 or less, preferably 16 or less.

[0041] In equations (1) and (2), each Z 1 The compound optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It can be a heteroaryl compound. Typically, Z 1 These are, arbitrarily selected, -O-, -C(O)-, -C(O)O-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30It may further comprise one or more divalent linking groups selected from heteroarylenes or combinations thereof, where R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It could be a heteroaryl.

[0042] In equations (1) and (2), the two R 2 Together, optionally, ring A 1 A fused ring is formed, where the fused ring optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups is either substituted or unsubstituted, and the fused ring is either substituted or unsubstituted.

[0043] In equations (1) and (2), one Z 1 and one R 2 Together, optionally, ring A 1 Ring A forms a fused ring, where the fused ring optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups is either substituted or unsubstituted, where the fused ring is either substituted or unsubstituted. 1 The condensed ring formed may be aliphatic or aromatic.

[0044] In equations (1) and (2), a and b are independent integers between 0 and 2, provided that the sum of a and b is 1 or greater. Typically, a is 1 or 2 and b is 0.

[0045] In equations (1) and (2), c is an integer between 0 and 10. Typically, c is an integer between 0 and 2, and preferably c is 0 or 1.

[0046] In equations (1) and (2), d is an integer between 1 and 3. Typically, d is 1 or 2, preferably d is 1. For example, in some embodiments, a may be 1 or 2 and d may be 1. In some embodiments, d may be 1 and L 1 It is a single bond. 1 It should be understood that if it is a single bond, then b is 0.

[0047] In equations (1) and (2), e is either 0 or 1. Typically, e is 0.

[0048] In equations (1) and (2), n is an integer between 0 and 4. Typically, n is 0 or 1. Preferably, n is 0.

[0049] In some embodiments, the nonionic photoacid generator compound of formula (1) is formula (1a), (1b), (1c), or (1d): [ka] (In the formula, ring A 1 , X 1 , R 2 , Z 1 , L 1 , L 2 (P, a, b, c, d, e, and n are as defined for equation (1), respectively.) It can be represented by one of the following.

[0050] In equations (1a), (1b), (1c), and (1d), each R 1e R is independently a monovalent nonhydrogen substituent; where each R 1e It optionally further includes one or more divalent linking groups as part of its structure. For example, each R 1e These are, independently, halogens, hydroxyls, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It can be a heteroaryloxy. Typically, each R 1e These are independently hydroxyl, substituted, or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It may be a heteroaryloxy. In one or more embodiments, each R 1e It may independently further contain one or more halogens, such as one or more fluoro or iodo groups, as part of its structure.

[0051] In equations (1a), (1b), (1c), and (1d), each R 1e The compound optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, and -N(R ’)-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It could be a heteroaryl.

[0052] In some embodiments, one or more R 1e Each of these may independently further contain an acid-unstable group, a lactone-containing group, a base-solubilizing group, or a combination thereof.

[0053] In some embodiments, one or more R 1e Each of these may independently contain a polymerizable portion as all or part of its structure. For example, R 1e The structure may further include, in whole or in part, (meth)acrylate groups, vinyl aromatic groups, vinyl ether groups, vinyl ketone groups, and / or vinyl ester groups.

[0054] In equation (1a), f is an integer between 0 and 4. Typically, f is an integer between 0 and 2, and preferably f is 0 or 1.

[0055] In equations (1b) and (1c), g is an integer between 0 and 6. Typically, g is an integer between 0 and 2, and preferably g is 0 or 1.

[0056] In equation (1d), h is an integer between 0 and 2. Typically, h is 0 or 1, preferably 0.

[0057] In some embodiments, the nonionic photoacid generator compound of formula (2) is formula (2a) or (2b): [ka] (In the formula, ring A 1 , X 1 , R 2 , Z 1 , L 1 , L 2 (P, a, b, c, d, e, and n are as defined for equation (2), respectively.) It can be represented by one of the following.

[0058] In equations (2a) and (2b), each R 1e R is independently a monovalent nonhydrogen substituent; where each R 1e It optionally further includes one or more divalent linking groups as part of its structure. For example, each R 1e These are, independently, halogens, hydroxyls, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It can be a heteroaryloxy. Typically, each R 1e These are independently hydroxyl, substituted, or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It may be a heteroaryloxy. In one or more embodiments, each R 1e It may independently further contain one or more halogens, such as one or more fluoro or iodo groups, as part of its structure.

[0059] In equations (2a) and (2b), each R 1e The structure optionally further includes one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylenes or combinations thereof may be selected, where R ’ C is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It could be a heteroaryl.

[0060] In some embodiments, one or more R 1eEach of these may independently further contain an acid-unstable group, a lactone-containing group, a base-solubilizing group, or a combination thereof.

[0061] In some embodiments, one or more R 1e Each of these may independently contain a polymerizable portion as all or part of its structure. For example, R 1e The structure may further include, in whole or in part, (meth)acrylate groups, vinyl aromatic groups, vinyl ether groups, vinyl ketone groups, and / or vinyl ester groups.

[0062] In equations (2a) and (2b), f is an integer between 0 and 4. Typically, f is an integer between 0 and 2, and preferably f is 0 or 1.

[0063] Exemplary nonionic photoacid-generating compounds of formulas (1) and (2) include the following: [ka] [ka] [ka]

[0064] In some embodiments, the nonionic photoacid generator compound may not contain trifluoromethyl and difluoromethylene groups. In other words, in some embodiments, the nonionic photoacid generator compound formulas (1) and (2) may not contain trifluoromethyl and difluoromethylene groups. For example, in some embodiments, the nonionic photoacid generator compound does not contain fluorine.

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

[0066] Another embodiment provides a photoresist composition comprising a nonionic photoacid generator compound, or a polymer containing repeating units derived from a nonionic photoacid generator compound (for example, in cases where the nonionic photoacid generator compound contains polymerizable groups as part of its structure); and a solvent. That is, the photoresist composition may comprise (i) a nonionic photoacid generator compound and a solvent; or (ii) a polymer containing repeating units derived from a nonionic photoacid generator compound and a solvent.

[0067] Nonionic photoacid generator compounds may be present in the photoresist composition in amounts of 1 to 99 weight percent (wt%), more typically 1 to 80 wt%, 2 to 75 wt%, or 2 to 60 wt%, based on the total solid content of the photoresist composition.

[0068] If the photoresist composition contains a polymer containing repeating units derived from a nonionic photoacid generator compound, the polymer may be present in the photoresist composition in an amount of 1 to 99 weight percent (wt%), more typically 1 to 80%, 2 to 75 weight%, or 2 to 60 weight%, based on the total solids content of the photoresist composition. The repeating units of the polymer containing units derived from the nonionic photoacid generator compound may typically be present in an amount of 1 to 35 mol%, typically 1 to 25 mol%, or more typically 2 to 15 mol%, based on the total repeating units of the polymer.

[0069] The photoresist composition may further contain additional photoacid generators different from nonionic photoacid generator compounds. The additional PAG may be in polymer or nonpolymer form. In polymer form, the additional PAG may exist as a portion of repeating units of a polymer derived from polymerizable PAG monomers.

[0070] Suitable additional PAGs can generate acids during post-exposure baking (PEB) that cause cleavage of acid-unstable groups present on the polymer of the photoresist composition. PAGs may be in non-polymeric or polymeric form, for example, they may be present in polymerized repeating units of a polymer. In some embodiments, PAGs may be included in the composition as non-polymerized PAG compounds, as repeating units of a polymer having PAG moieties derived from polymerizable PAG monomers, or as a combination thereof.

[0071] A suitable nonpolymer PAG compound is formula G + A - (In the formula, G + A is an organic cation selected from iodonium cations substituted with two alkyl groups, two aryl groups, or a combination of alkyl groups and aryl groups; and sulfonium cations substituted with three alkyl groups, three aryl groups, or a combination of alkyl groups and aryl groups. - These are nonpolymerizable organic anions. Particularly preferred nonpolymerizable organic anions include those whose conjugate acid has a pKa of -15 to 1. Particularly preferred anions are fluorinated alkyl sulfonates and fluorinated sulfonimides.

[0072] In some embodiments, the anions of the additional PAG do not contain -F, -CF3, or -CF2- groups. “Absent -F, -CF3, or -CF2- groups” should be understood as meaning that the anions of the additional PAG exclude groups such as -CH2CF3 and -CH2CF2CH3. In yet other embodiments, the anions of the additional PAG are fluorine-free (i.e., they do not contain a fluorine atom and are not substituted by a fluorine-containing group). In some embodiments, the additional PAG is fluorine-free (i.e., neither the photoactive cation nor the anion is fluorine-free).

[0073] Useful nonpolymeric PAG compounds are known in the art of chemically amplified photoresists and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Nonionic sulfonates and sulfonyl compounds, e.g., nitrobenzyl derivatives, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, e.g., , bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimodomethanesulfonic acid and N-hydroxysuccinimodotrifluoromethanesulfonic acid; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine are also known to function as photoacid generators. Suitable non-polymerizable acid generators are further described in Hashimoto et al. (Patent Document 1), column 37, rows 11-47 and columns 41-91.Other suitable sulfonate PAGs include sulfonated esters and sulfonyl oxyketones, nitrobenzyl esters, s-triazine derivatives, benzointosylates, t-butylphenyl α-(p-toluenesulfonyloxy)acetate, and t-butyl α-(p-toluenesulfonyloxy)acetate, as described in (Patent Document 2) and (Patent Document 1).

[0074] In some embodiments, G + This can be a sulfonium cation of formula (3) or an iodonium cation of formula (4): [ka]

[0075] In equations (3) and (4), each R aa These are independently substituted or non-substituted C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 7~20 Arylalkyl, or substituted or unsubstituted C 4~20 It is a heteroarylalkyl. Each R aa These are either individual or connected to another group R via a single bond or divalent linking group. aa It may either bond with each other to form a ring. Each R aa Each R may optionally include a divalent linking group as part of its structure. aa This may independently and optionally include an acid-unstable group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group.

[0076] The exemplary sulfonium cations in formula (3) include the following: [ka] [ka] (In the formula, R d This includes hydrogen, halogens (e.g., F, Cl, Br, I), and substituted or unsubstituted C. 1~6 Alkyl, or substituted or unsubstituted C 3~6 (It is cycloalkyl) It may include one or more of the following.

[0077] The exemplary iodonium cations in formula (4) may include one or more of the following: [ka]

[0078] Additional PAGs, which are onium salts, typically contain an organic anion having a sulfonate group or a non-sulfonate type group such as a sulfonamide, sulfonimidate, methide, or borate.

[0079] Exemplary organic anions having a sulfonate group may include one or more of the following: [ka] [ka] [ka]

[0080] Examples of non-sulfonated anions include one or more of the following: [ka]

[0081] Typically, when a photoresist composition contains additional PAGs, the additional PAGs are present in the photoresist composition in an amount of 0.1 to 55% by weight, more typically 1 to 25% by weight, based on the total solids content of the photoresist composition. When present in polymer form, the additional PAGs are typically present in the polymer in an amount of 1 to 25 mol%, more typically 1 to 8 mol%, or 2 to 6 mol%, based on the total repeating units in the polymer.

[0082] The photoresist composition may also contain one or more non-solvent alkali-insoluble substrates, which typically exist in a total amount of more than 50 weight percent based on the total solids content of the photoresist composition. The one or more non-solvent alkali-insoluble substrates, which may also be referred to herein as matrix materials, may be polymers or nonpolymers. Suitable alkali-insoluble substrates will be apparent to those skilled in the art and will be based on the descriptions provided herein. In some embodiments, the alkali-insoluble substrate does not contain phenolic hydroxyl groups, such as phenolic hydroxyl group-containing novolac resins. In some embodiments, the alkali-insoluble substrate does not contain carboxylic acid groups. In some embodiments, the alkali-insoluble substrate may contain phenolic hydroxyl groups and / or carboxylic acid groups, provided that the alkali-insolubility of the substrate is maintained.

[0083] To determine whether a particular substrate is alkali-insoluble, the substrate can be subjected to a solubility test in 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 substrate can be applied to the surface of a Si substrate by spin coating, and the initial film thickness can be measured. The film of the substrate is immersed in a 0.26 N TMAH aqueous solution for 60 seconds at room temperature under typical developing conditions, followed by a DI water rinse and air drying, and then 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.

[0084] In some embodiments, the substrate may include polymers, metal-containing materials, or combinations thereof. It should be understood that “substrate” does not define the material as basic (for example, the substrate is not necessarily basic according to the definition of acid / base chemistry).

[0085] The polymer in the photoresist composition may be a homopolymer or a copolymer containing two or more structurally different repeating units. For example, the polymer may contain one or more repeating units containing functional groups selected from hydroxyaryl groups, acid-unstable groups, base-solubilizing groups, lactone-containing groups, sultone-containing groups, polar groups, crosslinkable groups, crosslinking groups, etc., or combinations thereof.

[0086] In one or more embodiments, the polymer may comprise repeating units formed from monomers containing acid-unstable groups. Suitable acid-unstable groups include, for example, tertiary esters, acetals, ketals, and tertiary ether groups. [ka] [ka] In the formula, R d This includes hydrogen, halogens (e.g., F, Cl, Br, I), and substituted or unsubstituted C. 1~6 Alkyl, or substituted or unsubstituted C 3~6 It is a cycloalkyl group.

[0087] When repeating units with acid-unstable groups are present in a polymer, they typically exist in amounts of 25–75 mol%, more typically 25–50 mol%, and even more typically 30–50 mol%, relative to the total repeating units in the polymer.

[0088] In some embodiments, the polymer may comprise repeating units derived from one or more lactone-containing monomers. Suitable lactone-containing monomers include, for example: [ka] (where R d is hydrogen, halogen (e.g., F, Cl, Br, I), substituted or unsubstituted C 1~6 alkyl, or substituted or unsubstituted C 3~6 cycloalkyl). is included.

[0089] When repeating units derived from one or more lactone-containing monomers are present in the polymer, they are typically present in an amount of 0.5 to 75 mol%, more typically 1 to 50 mol%, and even more typically 5 to 50 mol% based on the total repeating units in the polymer.

[0090] In some embodiments, the polymer may contain repeating units having a base-solubilizing group and / or having a pKa of 12 or less. Exemplary base-solubilizing groups may include a fluoroalcohol group, a carboxylic acid group, a carboxyimide group, a sulfonamide group, or a sulfonimide group.

[0091] Non-limiting examples of monomers containing a base-solubilizing group include the following:

Chemical formula

Chemical formula

Chemical formula

[0092] When repeating units having a base solubilizing group and / or having a pKa of 12 or less are present in the polymer, they are typically present in an amount of 0.5 to 30 mol%, more typically 15 to 25 mol%, and even more typically 5 to ten mol%, based on the total repeating units in the polymer.

[0093] The polymer may optionally further contain one or more aromatic group-containing repeating units. For example, such repeating units include the following:

Chemical formula

[0094] When present, the polymer typically contains aromatic group-containing repeating units in an amount of 1 to 80 mol%, more typically 5 to 75 mol%, and even more typically 5 to 50 mol%, based on the total repeating units in the polymer.

[0095] In some embodiments, the polymer may optionally contain an acetal monomer without an ester acetal, such as a monomer having the following structure:

Chemical formula

[0096] When present, the polymer typically contains repeating units having an acetal monomer without an ester acetal in an amount of 1 to 80 mol%, more typically 5 to 75 mol%, and even more typically 5 to 50 mol%, based on the total repeating units in the polymer.

[0097] The polymer may optionally further contain one or more additional repeating units. These additional repeating units may be one or more units for modifying the properties of the photoresist composition, such as etch rate and solubility. Exemplary additional units may include those derived from one or more (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. If present in the polymer, the one or more additional repeating units may be used in an amount of 50 mol% or less, typically 3 to 50 mol%, based on the total repeating units of the polymer.

[0098] Examples of non-limiting polymers of the present invention include: [ka] (In the formula, a, b, and c represent the mole fractions for each repeating unit of the polymer, and a + b + c = 1) It includes one or more of the following. It should be understood that the mole fractions of a, b, and c are selected so that the polymer is alkali-insoluble.

[0099] In some embodiments, the non-solvent alkali-insoluble substrate may include chain-severable polymers, unclipping polymers, or combinations thereof.

[0100] Chain-severable polymers can undergo chain-severing reactions under suitable conditions. Any suitable chain-severable polymer can be used. Exemplary direct photolysis, chain-severable polymers include, for example, copolymers of α-substituted styrene and substituted α-halogenated acrylates, such as α-methylstyrene / methyl-α-chloroacrylate copolymer, 2-trifluoroethyl-α-chloroacrylate / α-methyl-4-fluorostyrene copolymer, etc., or combinations thereof.

[0101] Unzipping polymers include polymers that have unczipping polymer end groups when triggered by a suitable stimulus (photo-induced or chemically induced stimulus) that causes the polymer backbone to decompose into smaller parts. Typically, unczipping polymers are selected so that the stimulus of a first chemical modification or decomposition event triggers an unczipping effect, whether partial or complete. Any suitable unczipping polymer may be used.

[0102] The polymer typically has a weight-average molecular weight (M) of 1,000 to 200,000 Datons (Da), preferably 10,000 to 150,000 Da, more preferably 15,000 to 150,000 Da, and even more preferably 25,000 to 150,000 Da or 50,000 to 150,000 Da. w ) has M w Logarithmic mean molecular weight (M n The polydispersity index (PDI) of the first polymer, which is the ratio of ), is typically 1.1–3, more typically 1.1–2. The molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.

[0103] Polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined or supplied separately and polymerized in a reactor using a suitable solvent and initiator. For example, polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with a chemical beam at an effective wavelength, or a combination thereof.

[0104] In some embodiments, one or more non-solvent alkali-insoluble substrates may be metal-containing materials. Exemplary metal-containing materials include metal-organic resists (e.g., photo-induced crosslinkable metal-organic resists), metal oxide resists, etc., or combinations thereof. In some embodiments, the metal-containing material may include Sn, Zr, Hf, Si, Ge, Se, Cr, Mo, W, V, Nb, Ta, P, Sb, Ti, Ce, Ru, Sb, Y, Ga, Cr, Fe, Co, Ru, Al, In, Sc, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zn, Co, Ni, Mn, Mg, Ca, Sr, Ba, or combinations thereof. Typically, the metal-containing material may include Sn, Zr, Hf, Si, Ge, Se, or combinations thereof.

[0105] One or more non-solvent alkali-insoluble substrates are present in a total amount of more than 50% by weight based on the total solids content of the photoresist composition. For example, one or more non-solvent alkali-insoluble substrates may be present in a total amount of 50% to 99% by weight, typically 60% to 95% by weight, or 70% to 90% by weight, based on the total solids content of the photoresist composition.

[0106] The photoresist composition further comprises a solvent for dissolving the components of the composition and for facilitating its coating on a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, iso-propanol, 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); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone These solvents include ketones such as n, 2-heptanone, and cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and acetate acetate; lactones such as gamma-butyrolactone (GBL) and epsilon-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or acyclic carbonate esters such as dimethyl carbonate, ethylene carbonate, propylene carbonate, and diphenyl carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; or combinations thereof. Of these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, DAA, or combinations thereof.

[0107] The total solvent content in a photoresist composition (i.e., the cumulative solvent content for all solvents) is typically 40–99% by weight, for example, 60–99% by weight, or 85–99% by weight, based on the total solids content of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the photoresist layer to be coated and the coating conditions.

[0108] In some embodiments, the photoresist composition may further comprise a substance containing one or more base-labile groups (a "base-labile substance"). As referred to herein, a base-labile group is a functional group that, after the exposure step and the post-exposure baking step, can undergo a cleavage reaction in the presence of an aqueous alkaline developer to provide polar groups such as hydroxyl, carboxylic acid, sulfonic acid, etc. The base-labile group will not significantly react (e.g., will not undergo a bond cleavage reaction) prior to the development step of the photoresist composition containing the base-labile group. Thus, for example, the base-labile group will be substantially inert during pre-exposure soft bake, exposure, and post-exposure bake steps. "Substantially inert" means that 5% or less, typically 1% or less, of the base-labile group (or moiety) decomposes, cleaves, or reacts during pre-exposure soft bake, exposure, and post-exposure bake steps. The base-labile group reacts under typical photoresist development conditions using an aqueous alkaline photoresist developer such as, for example, an aqueous solution of 0.26 normal (N) tetramethylammonium hydroxide (TMAH). For example, a 0.26N aqueous solution of TMAH can be used for single paddle development or dynamic development, in which case, for example, the 0.26N TMAH developer is preferably dispensed over the imaged photoresist layer for a time such as 10 to 120 seconds (s). Exemplary base-labile groups are ester groups, typically fluorinated ester groups. Preferably, the base-labile substance is substantially immiscible with the first and / or second polymer and other solid components of the photoresist composition and has a lower surface energy than them. When coated on a substrate, the base-labile substance can thereby separate from the other solid components of the photoresist composition to the topmost surface of the formed photoresist layer.

[0109] In some embodiments, the base-unstable material may be a polymer material, also referred to herein as a base-unstable polymer, and may comprise one or more repeating units comprising one or more base-unstable groups. For example, a base-unstable polymer may comprise repeating units comprising two or more identical or different base-unstable groups. A preferred base-unstable polymer comprises at least one repeating unit comprising two or more base-unstable groups, for example, a repeating unit comprising two or three base-unstable groups.

[0110] Base-unstable polymers can be prepared using any suitable method in the art, including those described herein for the first and second polymers. For example, base-unstable polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with a chemical beam at an effective wavelength, or a combination thereof. In addition, or alternatively, one or more base-unstable groups can be grafted onto the polymer backbone using a suitable method.

[0111] In some embodiments, the base-unstable substance is a single molecule comprising one or more base-unstable ester groups, preferably one or more fluorinated ester groups. The base-unstable substance, being a single molecule, typically has a molecular weight in the range of 50 to 1,500 Da. W It has.

[0112] If present, the base-unstable substance is typically present in the photoresist composition in an amount of 0.01 to 10% by weight or 2 to 7% by weight, typically 1 to 5% by weight, based on the total solid content of the photoresist composition.

[0113] In addition to, or instead of, the base-unstable polymer, the photoresist composition may further comprise one or more polymers in addition to and different from the non-solvent, alkali-insoluble substrates described above. For example, the photoresist composition may comprise additional polymers, such as those described above, but with different compositions. In addition to, or instead of, the one or more additional polymers may include those well known in the photoresist art, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene polymers, polyvinyl alcohols, or combinations thereof.

[0114] The photoresist composition may further contain one or more additional, optional additives. For example, optional additives may include chemical laser dyes and contrast agents, striation inhibitors, plasticizers, rate accelerators, sensitizers, photodegradable deactivators (PDQ) (also known as photodegradable bases), basic deactivators, thermoacid generators, surfactants, etc., or combinations thereof. If present, the optional additives are typically present in the photoresist composition in an amount of 0.01 to 10% by weight, based on the total solids content of the photoresist composition.

[0115] PDQ generates a weak acid upon irradiation. The acid generated from the photodegradable deactivator is not strong enough to react rapidly with the acid-unstable groups present in the resist matrix. Exemplary photodegradable deactivators include, for example, photodegradable cations, preferably, for example, C 1~20 Carboxylic acid or C 1~20This includes compounds useful for preparing strong acid-generating compounds paired with anions of weak acids (pKa>1), such as sulfonic acid anions. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In preferred embodiments, the photodegradable deactivator is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0116] The photodegradable inactivator may be in a non-polymeric form or in a polymer-bound form. When in a polymeric form, the photodegradable inactivator is present in polymerization units on the first or second polymer. Polymerization units containing the photodegradable inactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0117] Examples of basic deactivators 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-diyrbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2''-nitrilotriethanol; 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidine carboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, and di-tert-butyl Cyclic aliphatic amines such as piperazine-1,4-dicarboxylate and N-(2-acetoxy-ethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3This includes linear and cyclic amides and their derivatives such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines such as primary and secondary aldimines and ketimines; diazines such as optionally substituted pyrazines, piperazines, and phenazines; diazoles such as optionally substituted pyrazoles, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0118] Basic deactivators can exist in non-polymeric or polymer-bound forms. If in polymeric form, the deactivator may be present in the repeating units of the polymer. Repeating units containing the deactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0119] Exemplary surfactants include fluorinated and non-fluorinated surfactants, and can be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In some embodiments, the photoresist composition further comprises a surfactant polymer containing fluorine-containing repeating units.

[0120] A method for forming patterns using the photoresist composition of the present invention is described herein. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates, such as semiconductor wafers, polycrystalline silicon substrates, packaging substrates such as multi-chip modules, flat panel display substrates, substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), etc., can be used in the present invention, with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), but wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that optionally contain the effective or operable portion of the device to be formed.

[0121] Typically, one or more lithography layers, such as a hard mask layer (e.g., spin-on carbon (SOC), amorphous carbon, or a metallic hard mask layer), a CVD layer (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer), an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of the substrate before coating with the photoresist composition of the present invention. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0122] Optionally, a layer of adhesion promoter may be applied to the substrate surface before coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, and hexamethyldisilazane, or aminosilane couplers such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from DuPont Electronics & Industrial (Marlborough, Massachusetts) under the names AP® 3000, AP® 8000, and AP® 9000S.

[0123] The photoresist composition can be coated onto a substrate by any preferred method, such as spin coating, spray coating, dip coating, doctor blading, etc. For example, the application of a photoresist layer can be achieved by spin coating the photoresist in a solvent using a coating track, in which case the photoresist is distributed onto a rotating wafer. During distribution, the wafer is rotated for 15 to 120 seconds at a speed typically of 4,000 revolutions per minute (rpm) or less, for example, 200 to 3,000 rpm, for example, 1,000 to 2,500 rpm, to obtain a layer of the photoresist composition on the substrate. It will be well understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and / or the total solid content of the composition. The photoresist composition layer formed from the composition of the present invention typically has a dry layer thickness of 1 nanometer (nm) to 120 micrometers (μm), preferably more than 5 nm to 110 μm, more preferably 6 to 100 μm. In some embodiments, the photoresist composition layer formed from the composition may have a dry layer thickness of 10 nm to 5 μm, or 3 to 20 μm.

[0124] The photoresist composition is typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft-bake temperature and time will depend, for example, on the photoresist composition and thickness. The soft-bake temperature is typically 80–170°C, more typically 90–150°C. The soft-bake time is typically 10 seconds–20 minutes, more typically 1–10 minutes, and even more typically 1–2 minutes. The heating time can be easily determined by those skilled in the art based on the composition's components.

[0125] The photoresist layer is then pattern-exposed to activating radiation to create a difference in solubility between exposed and unexposed areas. The reference herein to exposing a photoresist composition to activating radiation indicates that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions, respectively, corresponding to the exposed and unexposed areas of the resist layer. Such exposure may instead be performed without a photomask using a direct writing method, typically used for e-beam lithography. Activating radiation typically has wavelengths less than 400 nm, less than 300 nm, or less than 200 nm, with 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV) wavelengths or e-beam lithography being preferred. This method is used in immersion or dry (non-immersion) lithography techniques. The exposure energy depends on the components of the exposure tool and photoresist composition, and is typically 1 to 200 millijoules (mJ / cm²) per square centimeter. 2 ), preferably 10 to 100 mJ / cm² 2 More preferably 20-50 mJ / cm² 2 That is the case.

[0126] After exposure of the photoresist layer, post-exposure baking (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for PEB will depend, for example, on the photoresist composition and layer thickness. PEB is typically performed at a temperature of 70-150°C, preferably 75-120°C, for a time of 30-120 seconds. A latent image is formed in the photoresist, defined by polarity switching regions (exposed regions) and non-switching regions (unexposed regions).

[0127] The exposed photoresist layer is then developed with a suitable developer to selectively remove the soluble regions of the layer, while the remaining insoluble regions form the resulting photoresist pattern relief image. In a positive development (PTD) process, the exposed regions of the photoresist layer are removed during development, leaving the unexposed regions. Conversely, in a negative development (NTD) process, the exposed regions of the photoresist layer remain, and the unexposed regions are removed during development. The application of the developer can be achieved by any preferred method as described above for coating the photoresist composition, with spin coating being a typical example. The development time is an effective time for removing the soluble regions of the photoresist, typically 5 to 60 seconds. Development is typically carried out at room temperature.

[0128] Suitable developers for the PTD process include aqueous base developers, such as tetramethylammonium hydroxide (TMAH), preferably 0.26 N (N) TMAH, quaternary ammonium hydroxide solutions such as tetraethylammonium hydroxide and tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent systems, meaning that the cumulative content of organic solvents in the developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0129] A coated substrate may be formed from the photoresist composition of the present invention. Such a coated substrate comprises (a) a substrate having one or more layers patterned on its surface; and (b) a layer of the photoresist composition on one or more patterned layers.

[0130] A photoresist pattern can be used, for example, as an etch mask, thereby enabling the transfer of the pattern to one or more consecutive underlying layers by known etching techniques, typically dry etching such as reactive ion etching. A photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, and it can subsequently be used as an etch mask for pattern transfer to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such patterning processes, photoresist compositions can be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0131] While this disclosure has been described in relation to what is currently considered to be a practical and exemplary embodiment, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to encompass various modifications and equivalent arrangements that fall within the spirit and scope of the appended claims.

Claims

1. Formula (1) or (2): 【Chemistry 1】 [In equations (1) and (2), Ring A １ This is a single ring C ３～６０ Aromatic group, polycyclic C ３～６０ aromatic group, C ３～１５ Monoalicyclic group, or C ３～１５ It is a polyalicyclic group, Each L １ L is independently a single bond or one or more linking groups, where L １ It does not contain fluorine. Each L ２ These are independently single bonds or one or more divalent linking groups; P is a polymerizable group; Each R １ａ 、R １ｂ 、R １ｃ 、and R １ｄ are, independently, non-hydrogen substituents, where each of R １ａ 、R １ｂ 、R １ｃ 、and R １ｄ optionally further includes, as part of its structure, one or more divalent linking groups, and R １ａ and R １ｂ optionally combine together to form an aromatic or non-aromatic ring group, and R １ｃ and R １ｄ optionally combine together to form an aromatic or non-aromatic ring group, Each R ２ R is independently a monovalent nonhydrogen substituent; where each R ２ It optionally further includes one or more divalent linking groups as part of its structure, Each X １ These are independently -O-, -S-, and -N(R ２ａ )-, -C(O)-, -S(O)R ２ａ -, or -S(O ２ ) R ２ａ - and here, R ２ａ These are independently substituted or non-substituted C １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl, or substituted or unsubstituted C ３～３０ Selected from heteroaryls, Each Z １ It independently contains an anion stabilizing group, where at least one Z １ It is configured to form a ring having 5 to 8 ring atoms by forming an intramolecular non-covalent bond with an anion derived from a sulfonate group, Z １ These are independently -OH, -C(O)OH, -SH, -C(O)SH, -NHS(O) ２ R ３ , -S(O) ２ R ３ , -S(O)R ３ , -S(O) ２ NHS (O) ２ R ３ -CH (=NOH), or -B (R ４ ) ２ Selected from; each Z １ It optionally further includes one or more divalent linking groups as part of its structure, Each R ３ These are independently trifluoromethyl, hydroxyl, substituted or unsubstituted C １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl, or substituted or unsubstituted C ３～３０ Selected from heteroaryls, Each R ４ These are, independently, hydrogen, fluorine, hydroxyl, substituted or unsubstituted C １～２０ Alkyl, substituted, or unsubstituted C １～２０ Heteroalkyl, substituted, or unsubstituted C ６～３０ Aryl, or substituted or unsubstituted C ３～３０ Selected from heteroaryls, Two R's ２ Together, optionally, ring A １ A fused ring is formed, where the fused ring optionally further includes one or more divalent linking groups as part of its structure. One Z １ and one R ２ Together, optionally, ring A １ A fused ring is formed, where the fused ring optionally further includes one or more divalent linking groups as part of its structure. Each of a and b is an independent integer between 0 and 2, provided that the sum of a and b is 1 or greater. c is an integer between 0 and 10. d is an integer between 1 and 3. e is either 0 or 1, n is an integer between 0 and 4. A nonionic photoacid-generating compound represented by [formula].

2. Equation (1) is the same as equations (1a), (1b), (1c), or (1d): 【Chemistry 2】 (In equations (1a), (1b), (1c), and (1d), Each R １ｅ R is independently a monovalent nonhydrogen substituent; where each R １ｅ It optionally further includes one or more divalent linking groups as part of its structure, f is an integer between 0 and 4. g is an integer from 0 to 6, (h is an integer between 0 and 2) A nonionic photoacid generating compound according to claim 1, represented by one of the following.

3. Equation (2) is equation (2a) or (2b): 【Transformation 3】 (In equations (2a) and (2b), Each R １ｅ is a monovalent nonhydrogen substituent; where each R １ｅ It optionally further includes one or more divalent linking groups as part of its structure, f is an integer between 0 and 4. A nonionic photoacid generating compound according to claim 1, represented by one of the following.

4. Ring A １ This is a single ring C ３～６０ Aromatic group, or polycyclic carbon ６～６０ A nonionic photoacid generator compound according to any one of claims 1 to 3, wherein the compound is an aromatic group.

5. Ring A １ C ３～１５ Monoalicyclic group, or C ６～１５ A nonionic photoacid generator compound according to any one of claims 1 to 3, wherein the compound is a polyalicyclic group.

6. L １ The nonionic photoacid generator compound according to any one of claims 1 to 5, wherein the bond is a single bond.

7. A nonionic photoacid generator compound according to any one of claims 1 to 6, wherein at least one anion-stabilizing group comprises -OH.

8. A nonionic photoacid generator compound according to any one of claims 1 to 7, which does not contain a trifluoromethyl group or a difluoromethylene group.

9. A nonionic photoacid generator compound according to any one of claims 1 to 8, wherein e is 1.

10. A polymer comprising a nonionic photoacid generator compound according to any one of claims 1 to 9, or a polymer comprising repeating units derived from the nonionic photoacid generator compound according to any one of claims 1 to 9; solvent and A photoresist composition containing [a specific compound / component].

11. The photoresist composition according to claim 10, further comprising a non-solvent alkali-insoluble substrate.

12. A pattern forming method, wherein the method is To provide a photoresist composition layer by coating a layer of the photoresist composition according to claim 10 or 11 onto a substrate; To provide a photoresist composition layer exposed by pattern exposure with activating radiation; The exposed photoresist composition layer is developed to provide a resist relief image. A method that includes this.

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