Photoactive compounds, photoresist compositions comprising the same, and pattern forming methods

Abstract

Disclosed is a photoactive compound comprising an organic cation; and an anion represented by formula (1): wherein X is an organic group; Y 1 and Y 2 are each independently a non-hydrogen substituent; Y 1 and Y 2 together optionally form a ring; Z 2 is hydrogen, halogen, substituted or unsubstituted C 1‑30 alkyl, substituted or unsubstituted C 3‑30 cycloalkyl, substituted or unsubstituted C 3‑30 heterocycloalkyl, substituted or unsubstituted C 6‑50 aryl, substituted or unsubstituted C 7‑50 arylalkyl, substituted or unsubstituted C 7‑50 alkylaryl, substituted or unsubstituted C 6‑50 aryloxy, substituted or unsubstituted C 3‑30 heteroaryl, substituted or unsubstituted C 4‑30 alkylheteroaryl, substituted or unsubstituted C 4‑30 heteroarylalkyl, or substituted or unsubstituted C 3‑30 heteroaryloxy; Z 2 optionally further comprising one or more divalent linking groups as part of its structure; Z 2 and Y 1 or Y 2 together optionally form a ring; X and Z 2 together optionally form a ring; and X and Y 1 or Y 2 together optionally form a ring.

Description

Technical Field

[0001] This invention relates to photoactive compounds for use in photoresist compositions and to a method for patterning using such photoresist compositions. The invention has found applicability in photolithography applications within the semiconductor manufacturing industry. Background Technology

[0002] Photoresist materials are typically used to transfer images onto one or more underlying layers, such as metals, semiconductors, or dielectric layers, disposed on a semiconductor substrate. To increase the integration density of semiconductor devices and allow the formation of structures with dimensions in the nanometer range, photoresists and lithography tools with high-resolution capabilities have been and continue to be developed.

[0003] Chemically enhanced photoresists are commonly used for high-resolution processing. These resists typically employ a polymer with acid-indestabilized groups, a photoacid generator, and an acid quencher. Patterning exposure to activating radiation via a photomask causes the acid generator to form acid, which, during post-exposure baking, cleaves the acid-indestabilized groups in the exposed regions of the polymer. An acid quencher is typically added to the photoresist composition to control acid diffusion into unexposed areas, thereby improving contrast. The photolithography process results in a difference in solubility properties between exposed and unexposed areas of the resist in the developer solution. During positive development (PTD), the exposed areas of the photoresist layer dissolve in the developer and are removed from the substrate surface, while the unexposed areas, insoluble in the developer, are retained after development to form a positive image. The resulting embossed image allows for selective processing of the substrate.

[0004] Non-photoactive acid quenching materials commonly used in chemically reinforced resists include straight-chain aliphatic amines, cyclic aliphatic amines, aromatic amines, straight-chain and cyclic amides and their derivatives. Another commonly used class of acid quenching materials is photoactive quenchers, also known as photodegradable quenchers or photodegradable quenchers. Photoactive quenchers have also been used in chemically reinforced resist compositions. Photodegradable quenchers are typically salts containing a photoactive ononium cation and anion, where the anion is the conjugate base of a weak acid. Before exposure, the salt acts as a base or acid quencher. After exposure, the anionic portion of the photodegradable quencher becomes protonated and thus becomes more acidic. Therefore, when a chemically reinforced resist containing a photodegradable quencher is irradiated, the concentration of the acid quencher in the exposed area decreases sharply. On the other hand, intact photodegradable quenchers in the unexposed areas can capture acid molecules diffused from the exposed areas during photolithography, thereby improving photolithography performance.

[0005] Photoresist compositions comprising photodegradable quenchers and their uses have been described in the art. There is a need for novel photoresists that can provide high-resolution line-space features with superior contrast and / or contact holes (CH) with improved critical size uniformity (CDU). Summary of the Invention

[0006] A photoactive compound is provided, comprising an organic cation and an anion represented by formula (1): (1) Where X is an organic group; Y 1 and Y 2 Each is an independent non-hydrogen substituent; Y 1 and Y 2 Together they can form a ring at will; Z 2 It is hydrogen, halogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted C 7-50 arylalkyl, substituted or unsubstituted C 7-50 alkylaryl, substituted or unsubstituted C 6-50 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; Z 2 Optionally, it further comprises one or more divalent linking groups as part of its structure; Z 2 and Y 1 Or Y 2 One of them can optionally form a ring together; X and Z 2 Together they can arbitrarily form a ring; and X and Y 1 Or Y 2 One of them can be chosen to form a ring together.

[0007] A photoresist composition comprising the photoactive compound and a polymer is also provided.

[0008] A patterning method is also provided, comprising applying a layer of the photoresist composition described in this application onto a substrate to provide a photoresist composition layer; exposing the photoresist composition layer in a patterned manner to activation radiation to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer. Detailed Implementation

[0009] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this respect, these exemplary embodiments may take different forms and should not be construed as limiting to the description shown herein. Therefore, the following description of exemplary embodiments is intended to explain various aspects of this specification only. As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. When a statement such as “at least one of…” precedes the list of elements, it modifies the entire list of elements and does not modify any individual element in the list.

[0010] As used herein, the terms “a / an” and “the” do not indicate a limitation of quantity and are to be construed as including both the singular and plural unless otherwise indicated herein or clearly contradicted by the context. Unless otherwise explicitly stated, “or” means “and / or”. The modifier “about” used in conjunction with quantity includes the stated value and has the meaning specified by the context (e.g., including the degree of error associated with a particular quantity of measurement). The full scope disclosed herein includes endpoints, and these endpoints can be independently combined with each other. The suffix “(s)” is intended to include both the singular and plural of the term it modifies, thereby including at least one of the terms. “Optional” or “optionally” means that an event or situation subsequently described may or may not occur, and the description includes both the occurrence and non-occurrence of the event. The terms “first,” “second,” and similar terms herein do not indicate order, quantity, or importance, but are used to distinguish one element from another. When an element is referred to as being “on” another element, it may be in direct contact with or interposed to that other element, or the element may exist therein. In contrast, when an element is described as being "directly on" another element, there is no inserted element. It should be understood that the components, elements / features, limitations, and / or characteristics of the described aspects can be combined in any suitable manner within the aspects.

[0011] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It will be further understood that terms (such as those defined in common dictionaries) shall be interpreted as having the same meaning as they have in the relevant field and in the context of this disclosure, and shall not be construed as having an idealized or overly formal meaning unless expressly defined herein.

[0012] As used herein, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light, extreme ultraviolet light (EUV light), X-rays, particle rays (such as electron beams and ion beams), etc., represented by excimer lasers. Additionally, in this invention, "light" refers to photochemical rays or radiation. Krypton fluoride lasers (KrF lasers) are a special type of excimer laser, sometimes called excimer complex lasers. "Excimer" is an abbreviation for "excited dimer," and "excimer complex" is an abbreviation for "excited complex." Excimer lasers use a mixture of rare gases (argon, krypton, or xenon) and halogen gases (fluorine or chlorine), which, under appropriate electrical stimulation and high voltage conditions, emit coherent stimulated emission (laser) in the ultraviolet range. Furthermore, unless otherwise stated, "exposure" in this specification includes not only exposure through a mercury lamp, far-ultraviolet light, X-rays, extreme ultraviolet light (EUV light), etc., represented by excimer lasers, but also writing with particle rays (such as electron beams and ion beams).

[0013] As used herein, an "organic group" comprises one or more carbon atoms, for example, 1 to 60 carbon atoms. The term "hydrocarbon" refers to an organic compound or organic group having at least one carbon atom and at least one hydrogen atom. The term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group having a specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence of 2; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid group" refer to groups 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 atoms; "cycloalkylene" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of 2; "cycloalkenyl" refers to a group having at least three carbon atoms and a valence of at least 60 carbon atoms. A non-aromatic cyclic divalent hydrocarbon group with one less carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic ring system that satisfies Hückel's rule and includes a carbon atom in the ring, and optionally may include one or more heteroatoms selected from N, O, and S that replace the carbon atom in the ring; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which each ring member is carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocyclic alkyl ring; "arylene" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group that has been substituted with an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0014] The prefix "hetero" indicates that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) that replaces a carbon atom, wherein each of the one or more heteroatoms is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; "heteroalkyl" refers to an alkyl group having 1 to 4 or more heteroatoms that replace a carbon atom; "heterocyclic alkyl" refers to a cycloalkyl group having 1 to 4 or more heteroatoms that replace a carbon ring member; "heterocyclic alkylene" refers to a heterocyclic alkyl group having a valence of 2; "heteroaryl" refers to an aryl group having 1 to 4 or more heteroatoms that replace a carbon ring member; and "heteroarylene" refers to a heteroaryl group having a valence of 2.

[0015] Unless otherwise expressly provided, each of the foregoing substituent groups may be optionally substituted. For example, when a group is referenced without specifying whether it is substituted or unsubstituted, the group includes both unsubstituent and substituent groups. The term "optionally substituted" means either substituted or unsubstituted.

[0016] "Substituted" means that at least one hydrogen atom in a chemical structure is replaced by another terminal substituent group, typically monovalent, provided that the valence of the specified atom does not exceed its normal valence. When the substituent is oxo (i.e., =O), the two twin hydrogen atoms on the carbon atom are replaced by a terminal oxo group. Combinations of substituents or variations are permitted. Exemplary substituents that may exist at the "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C 1-6 )alkylamino, alkanoyl (such as C 2-6 Alkyl groups (such as acyl groups), formyl groups (-C(=O)H), carboxylic acids or their alkali metal salts or ammonium salts; 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-alkyl or -OC(=O)-aryl), amide groups (-C(=O)NR2, where R is hydrogen or C... 1-6 alkyl), formamido (-CH2C(=O)NR2, where R is hydrogen or C 1-6 Alkyl), halogen, mercapto (-SH), C 1-6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 1-6 Haloalkyl, C 1-9 Alkoxy, C1-6 Haloalkoxy, C 3-12 cycloalkyl, C 5-18 Cycloalkenyl, C 2-18 Heterocyclic alkenyl groups, having at least one aromatic ring, C 6-12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic), having 1 to 3 single or fused rings and 6 to 18 ring carbon atoms. 7-19 arylalkyl, having 1 to 3 single or fused rings and 6 to 18 cyclic carbon atoms, C 7-12 Alkyl aryl, C 3-12 Heterocyclic alkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(O)2-alkyl), C 6-12 Arylsulfonyl (-S(O)2-aryl) or toluenesulfonyl (CH3C6H4SO2-).

[0017] The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chloroinated), bromine (brominated), or iodine (iodinated). The prefix "halogenated" indicates a group containing one or more of the fluorine, chlorine, bromine, or iodine substituents that replace a hydrogen atom. Combinations of halogen groups (e.g., bromine and fluorine) or only fluorine groups may be present. For example, the term "halogenated alkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C" refers to an alkyl group substituted with one or more halogens. 1-8 "Halogenated alkyl" refers to a C that has been substituted with at least one halogen. 1-8 Alkyl groups, and further substituted by one or more other substituents that are not halogens.

[0018] As used herein, an "acid-indestructible group" refers to a group in which a bond is broken by the action of an acid (optionally and typically in conjunction with heat treatment), resulting in the formation of a polar group (such as a carboxylic acid or alcohol group, formed on the polymer) and, optionally and typically, the portion connected to the broken bond detaches from the polymer. In other systems, nonpolymeric compounds may include acid-indestructible groups that can be cleaved by the action of an acid, resulting in the formation of a polar group, such as a carboxylic acid or alcohol group, on the cleaved portion of the nonpolymeric compound. Such acids are typically photogenerated acids under conditions of bond cleavage during exposure-after baking (PEB); however, the examples are not limited thereto, and such acids may, for example, be thermally generated. Suitable acid-indestructible groups include, for example, 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. Acid-indestructible groups are also commonly referred to in the art as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-indestructible protecting groups," "acid-leaving groups," "acid-decomposable groups," and "acid-sensitive groups."

[0019] As used herein, unless otherwise defined, "divalent linker" means a divalent linker comprising one or more of the following: -O-, -S-, -Te-, -Se-, -C(O)-, -N(R)-. a -, -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 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R a It 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 groups. Typically, the divalent linking group includes one or more of the following: -O-, -S-, -C(O)-, -N(R-). a -, -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 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R a It 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 groups. More typically, the divalent linking group includes at least one of the following: -O-, -C(O)-, -C(O)O-, -N(R a )-、-C(O)N(R a -, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 heteroaryl, or combinations thereof, wherein R a It is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0020] This invention relates to photoactive compounds, such as photodegradable quencher compounds. In particular, the photoactive compounds of this invention are salts comprising a nitrogen anion directly bonded to an alkenyl group and optionally directly bonded to a second electron-withdrawing group. The photoactive compounds of this invention can be used in photoresist compositions to achieve improved contrast and improved local critical size uniformity (LCDU).

[0021] Photoactive compounds contain organic cations and anions represented by formula (1): (1) In formula (1), X is an organic group. For example, X may include substituted or unsubstituted C groups. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Heterocyclic alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, or substituted or unsubstituted C6-C 30 The aryloxy group, wherein X may optionally further comprise one or more divalent linking groups as part of its structure. In some embodiments, X may further comprise one or more divalent linking groups selected from the group consisting of -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' can be hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0022] X and Y 1 Or Y 2 Optionally, one of them can form a ring, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0023] In equation (1), Y 1 and Y 2 Each is independently a non-hydrogen substituent. In some respects, Y 1 and Y 2 Each group independently contains an electron-withdrawing group, such as a carbonyl group (-C(O)-) or a cyano group (-CN). Preferably, Y 1 and Y 2 Each is independently a halogen, cyano, substituted or unsubstituted C group. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Heterocyclic alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, or substituted or unsubstituted C6-C 30 aryloxy group, where Y 1 and Y 2 Each may optionally further comprise one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-20aryl, substituted or unsubstituted C 3-20 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds. Typically, Y 1 and Y 2 Each C is independently either cyano, substituted, or unsubstituted. 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, or substituted or unsubstituted C 3-10 Heterocyclic alkyl groups, wherein Y 1 and Y 2 Each may independently and optionally further comprise one or more divalent linking groups (e.g., -C(O)O-) as part of its structure. In some aspects, Y 1 and / or Y 2 It may contain acid-labile groups that are part of its structure. For example, Y 1 and Y 2 At least one of them contains an acid-indestructible group that is part of its structure.

[0024] In equation (1), Y 1 and Y 2 They can optionally form a ring. For example, Y 1 and Y 2 Optionally, a ring can be formed, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. In some aspects, Y 1 and Y 2 They can be linked together via divalent linking groups that may contain acid-indestructible groups as part of their structure.

[0025] In equation (1), Z 2 It is hydrogen, halogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted C 7-50 arylalkyl, substituted or unsubstituted C 7-50 alkylaryl, substituted or unsubstituted C 6-50 aryloxy, substituted or unsubstituted C 3-30heteroaryl, substituted or unsubstituted C 4-30 Alkyl heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, or substituted or unsubstituted C 3-30 Heteroaryloxy group. Preferably, Z 2 It can be hydrogen, halogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 6-20 aryloxy, substituted or unsubstituted C 3-10 heteroaryl, substituted or unsubstituted C 4-10 Alkyl heteroaryl, substituted or unsubstituted C 4-10 Heteroarylalkyl, or substituted or unsubstituted C 3-10 Heteroaryloxyl. Typically, Z 2 C can be substituted or unsubstituted. 1-10 Alkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 6-20 aryloxy, substituted or unsubstituted C 3-10 heteroaryl, substituted or unsubstituted C 4-10 Alkyl heteroaryl, substituted or unsubstituted C 4-10 Heteroarylalkyl, or substituted or unsubstituted C 3-10 heteroaryloxyl.

[0026] In equation (1), Z 2 Optionally, it further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds.

[0027] In equation (1), X and Z 2 Optionally, they can form a ring, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. Typically, X and Z 2 Together they form a ring, wherein the ring further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0028] Preferably, X comprises N directly attached or bonded to formula (1). – Electron-withdrawing groups. For example, electron-withdrawing groups can be bonded to the nitrogen anion in formula (1) (i.e., bonded to the anionic nitrogen atom in formula (1)).

[0029] In some respects, X can be a part represented by one of equations (2a) to (2c): (2a) (2b) (2c) in The expression N in equation (1) represents... – Attachment point.

[0030] In equation (2a), Z 1a It is hydrogen, halogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted C 7-50 arylalkyl, substituted or unsubstituted C 7-50 alkylaryl, substituted or unsubstituted C 6-50 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 group. Preferably, Z 1a It can be hydrogen, halogen, substituted or unsubstituted C1-10 Alkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 6-20 aryloxy, substituted or unsubstituted C 3-10 heteroaryl, substituted or unsubstituted C 4-10 Alkyl heteroaryl, substituted or unsubstituted C 4-10 Heteroarylalkyl, or substituted or unsubstituted C 3-10 Heteroaryloxyl. Typically, Z 1a C can be substituted or unsubstituted. 1-10 Alkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 6-20 aryloxy, substituted or unsubstituted C 3-10 heteroaryl, substituted or unsubstituted C 4-10 Alkyl heteroaryl, substituted or unsubstituted C 4-10 Heteroarylalkyl, or substituted or unsubstituted C 3-10 heteroaryloxyl.

[0031] In equation (2a), Z 1a Optionally, it further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds.

[0032] In equation (2a), Y3 and Y 4 Each is independently a non-hydrogen substituent. Preferably, Y 3 and Y 4 Each is independently a halogen, cyano, substituted or unsubstituted C group. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Heterocyclic alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, or substituted or unsubstituted C6-C 30 aryloxy group, where Y 3 and Y 4 Each may optionally further comprise one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 3-20 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds. Typically, Y 3 and Y 4 Each C is independently either cyano, substituted, or unsubstituted. 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, or substituted or unsubstituted C 3-10 Heterocyclic alkyl groups, wherein Y 3 and Y 4Each may independently and optionally further comprise one or more divalent linking groups (e.g., -C(O)O-) as part of its structure. In some aspects, Y 3 and / or Y 4 It may contain acid-labile groups that are part of its structure. For example, Y 3 and Y 4 At least one of them contains an acid-indestructible group that is part of its structure.

[0033] In equation (2a), Y 3 and Y 4 They can optionally form a ring. For example, Y 3 and Y 4 Optionally, a ring can be formed, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. In some aspects, Y 3 and Y 4 They can be linked together via divalent linking groups that may contain acid-indestructible groups as part of their structure.

[0034] In equation (2a), Z 1a and Y 3 Or Y 4 Optionally, one of them forms a ring together. The ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0035] In equations (1) and (2a), Z 2 and Y 3 Or Y 4 Optionally, one of them forms a ring together. The ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0036] In equations (1) and (2a), Z 1a and Z 2 Optionally, they form a ring. The ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. Typically, Z 1a and Z 2Together they form a ring, wherein the ring further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0037] In equations (2b) and (2c), Z 1b and Z 1c Each is a substituted or unsubstituted C independently. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted C 7-50 arylalkyl, substituted or unsubstituted C 7-50 alkylaryl, substituted or unsubstituted C 6-50 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 group. Preferably, Z 1b and Z 1c Each can be either substituted or unsubstituted C independently. 1-10 Alkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 6-20 aryloxy, substituted or unsubstituted C 3-10 heteroaryl, substituted or unsubstituted C 4-10 Alkyl heteroaryl, substituted or unsubstituted C 4-10 Heteroarylalkyl, or substituted or unsubstituted C 3-10 Heteroaryloxyl. Typically, Z 1b and Z 1c Each can be either substituted or unsubstituted C independently. 1-10 Alkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 6-20 aryloxy, substituted or unsubstituted C 3-10heteroaryl, substituted or unsubstituted C 4-10 Alkyl heteroaryl, substituted or unsubstituted C 4-10 Heteroarylalkyl, or substituted or unsubstituted C 3-10 heteroaryloxyl.

[0038] In equations (2b) and (2c), Z 1b and Z 1c Each may independently and optionally further comprise one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds.

[0039] In equations (1) and (2b), Z 1b and Z 2 Optionally, they form a ring. The ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. Typically, Z 1b and Z 2 Together they form a ring, wherein the ring further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0040] In equations (1) and (2c), Z 1c and Z 2 Optionally, they form a ring. The ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. Typically, Z 1c and Z 2Together they form a ring, wherein the ring further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0041] In some respects, the anion represented by formula (1) does not include and is free from -F, -CF3, or -CF2- groups. It should be understood that "free from -F, -CF3, or -CF2- groups" means that the anion of the photoacid generator does not include groups such as -CH2CF3 and -CH2CF2CH3. In other respects, the anion represented by formula (1) is free from fluorine (i.e., it does not contain fluorine atoms and is not substituted by fluorine-containing groups). In some respects, the photoactive compound is free from fluorine (i.e., neither the organic cation nor the anion represented by formula (1) is fluorine-free).

[0042] For example, in equation (1), X and Y 1 Y 2 and Z 2 One or more of them are fluorine-free, and preferably X and Y. 1 Y 2 and Z 2 None of them contain fluorine. For example, in equations (1), (2a), (2b), and (2c), Y 1 Y 2 Y 3 Y 4 Z 1a Z 1b Z 1c and Z 2 One or more of them are fluorine-free, and preferably Y 1 Y 2 Y 3 Y 4 Z 1a Z 1b Z 1c and Z 2 None of them contain fluorine.

[0043] In some respects, as mentioned above, the anion represented by formula (1) may contain one or more acid-labile groups. For example, in formula (1), X, Y 1 Y 2 and Z 2 One or more of the groups in the formula contain acid-labile groups. For example, in formulas (1), (2a), (2b), and (2c), Y 1 Y 2 Y 3 Y 4 Z 1a Z 1b Z1c and Z 2 One or more of them contain acid-labile groups.

[0044] In some respects, photoactive compounds having formula (1) can be represented by one or more of formulas (3a) to (3c): (3a) (3b) (3c) In equations (3a) and (3b), Y 1 and Y 2 As in equation (1), for Y 1 and Y 2 Defined. In equation (3c), Y 1 and Y 2 As in equation (1), for Y 1 and Y 2 Defined, and Y 3 and Y 4 As in equation (2a), for Y 3 and Y 4 As defined.

[0045] In equations (3a) to (3c), R 1 and R 2 Each is a substituted or unsubstituted C independently. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, 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 heteroaryloxyl.

[0046] In equations (3a) to (3c), R 1 and R 2 Each may independently and optionally further comprise one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds.

[0047] In equations (3a) to (3c), R 1 and R 2 Optionally, a ring can be formed, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. Typically, R 1 and R 2 Together they form a ring, wherein the ring further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0048] The anions represented by formulas (3a) to (3c) may be fluorine-free. For example, in formulas (3a) and (3b), R 1 R 2 Y 1 and Y 2 One or more of them are fluorine-free, and preferably R 1 R 2 Y 1 and Y 2 None of them contain fluorine. For example, in formula (3c), R 1 R 2 Y 1 Y 2 Y 3 and Y 4 One or more of them are fluorine-free, and preferably R 1 R 2 Y 1 Y 2 Y 3 and Y 4 None of them contain fluorine.

[0049] The anions represented by formulas (3a) to (3c) may contain one or more acid-labile groups. For example, in formulas (3a) and (3b), R 1 R 2 Y 1 and Y 2 One or more of them contain acid-labile groups. For example, in formula (3c), R 1 R 2 Y 1 Y 2 Y 3 and Y 4 One or more of them contain acid-labile groups.

[0050] In some respects, photoactive compounds having formula (1) can be represented by one or more of formulas (4a) to (4c): (4a) (4b) (4c) In equations (4a) and (4b), Y 1 and Y 2 As in equation (1), for Y 1 and Y 2 Defined. In equation (4c), Y 1 and Y 2 As in equation (1), for Y 1 and Y 2 Defined, and Y 3 and Y 4 As in equation (2a), for Y 3 and Y 4 As defined.

[0051] In equations (4a) to (4c), R 3 Each is independently a halogen, cyano, substituted or unsubstituted C group. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, 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 heteroaryloxyl.

[0052] In equations (4a) to (4c), R 3 Each may independently and optionally further comprise one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds.

[0053] In equations (4a) to (4c), a is an integer from 0 to 4, preferably from 0 to 2, and typically 0 or 1.

[0054] In equations (4a) to (4c), when a is 2 or greater, two or more adjacent R 3 Optionally, a ring may be formed together, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0055] The anions represented by formulas (4a) to (4c) may be fluorine-free. For example, in formulas (4a) and (4b), R 3 Y 1 and Y 2 One or more of them are fluorine-free, and preferably R 3 Y 1 and Y 2 None of them contain fluorine. For example, in formula (4c), R 3 Y 1 Y 2 Y 3 and Y 4 One or more of them are fluorine-free, and preferably R 3 Y 1 Y 2 Y 3 and Y 4 None of them contain fluorine.

[0056] The anions represented by formulas (4a) to (4c) may contain one or more acid-labile groups. For example, in formulas (4a) and (4b), R 3 Y 1 and Y 2 One or more of them contain acid-labile groups. For example, in formula (4c), R 3 Y 1 Y 2 Y 3 and Y 4 One or more of them contain acid-labile groups.

[0057] In some respects, photoactive compounds having formula (1) can be represented by one or more of formulas (5a) to (5c): (5a) (5b) (5c) In equations (5a) to (5c), R 3 And a are respectively as in equations (4a) to (4c) for R 3 And as defined by a.

[0058] In equations (5a) and (5b), R 4 and R 5 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, 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 heteroaryloxyl.

[0059] In equations (5a) and (5b), R 4 and R 5Each may independently and optionally further comprise one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds.

[0060] In equations (5a) and (5b), R 4 and R 5 Optionally, a ring may be formed together, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0061] In equation (5c), R 4 To R 7 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, 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 heteroaryloxyl.

[0062] In equation (5c), R 4 To R 7Each may independently and optionally further comprise one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' can be 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 Mixed aromatic compounds.

[0063] In equation (5c), R 4 and R 5 Optionally, a ring may be formed together, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or R 6 and R 7 Optionally, a ring may be formed together, wherein the ring optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0064] The anions represented by formulas (5a) to (5c) may be fluorine-free. For example, in formulas (5a) and (5b), R 3 R 4 and R 5 One or more of them are fluorine-free, and preferably R 3 R 4 and R 5 None of them contain fluorine. For example, in formula (5c), R 3 To R 7 One or more of them are fluorine-free, and preferably R 3 To R 7 None of them contain fluorine.

[0065] The anions represented by formulas (5a) to (5c) may contain one or more acid-labile groups. For example, in formulas (5a) and (5b), R 3 R4 and R 5 One or more of them contain acid-labile groups. For example, in formula (5c), R 3 To R 7 One or more of them contain acid-labile groups.

[0066] In some respects, photoactive compounds having formula (1) can be represented by one or more of formulas (6a) to (6c): (6a) (6b) (6c) Where Y 1 and Y 2 As in equation (1), for Y 1 and Y 2 As defined, Y 3 and Y 4 As in equation (2a), for Y 3 and Y 4 Defined, and R 3 And a is as in equations (4a) to (4c) for R 3 And as defined by a.

[0067] Exemplary anions represented by equation (1) include the following:

[0068] The photoactive compound also contains an organic cation. For example, the organic cation may be a sulfonium cation or an iodonium cation. In some embodiments, the organic cation may be a sulfonium cation having formula (7a) or an iodonium cation having formula (7b): (7a) (7b) In equations (7a) and (7b), R 8 To R 12 Each is a substituted or unsubstituted C independently. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C 6-30 Iodoaryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 Heteroaryl alkyl groups, or combinations thereof. R 8 To R 10 Each can be attached to R individually or via a single bond or a divalent linker. 8 To R 10 Another group in it forms a ring. R 11 and R 12 They can be individual or linked together via single or divalent connecting groups to form a ring. R 8 To R 12 Each may optionally contain a divalent linker as part of its structure. R 8 To R 12 Each group may independently and optionally contain an acid-instable group selected from, for example, the following: tertiary alkyl ester group, secondary or tertiary aryl ester group, secondary or tertiary ester group having a combination of alkyl and aryl groups, tertiary alkoxy group, acetal group or ketal group.

[0069] Exemplary sulfonium cations having formula (7a) include one or more of the following:

[0070] An exemplary iodonium cation having formula (7b) may include one or more of the following:

[0071] Photoactive compounds can be prepared using any suitable method in the art, including those described in the examples herein.

[0072] The present invention further relates to photoresist compositions comprising a photoactive compound and a polymer and may contain additional optional components. Typically, the photoresist composition will further comprise one or more solvents, photoacid generators (PAGs), or combinations thereof.

[0073] The polymer may contain one or more repeating units. These repeating units may be one or more units for purposes such as modulating the properties of the photoresist composition (e.g., etching rate and solubility). Exemplary repeating units may include those derived from one or more of (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. The polymer of 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, acid-labile, base-solubilizing, lactone-containing, sulfonyl-containing, polar, crosslinkable, crosslinking, etc., or combinations thereof.

[0074] In one or more embodiments, the polymer may comprise repeating units formed from monomers containing acid-labile groups. Suitable acid-labile groups include, for example, tertiary ester groups, acetal groups, ketal groups, and tertiary ether groups.

[0075]

[0076] Where R d It is hydrogen, halogen, substituted or unsubstituted C 1-6 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0077] When repeating units with acid-labile groups are present in a polymer, they are typically present in amounts 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.

[0078] In some embodiments, the polymer may comprise repeating units derived from one or more lactone-containing monomers. Suitable lactone-containing monomers include one or more of, for example, the following:

[0079] Where R d It is hydrogen, halogen, substituted or unsubstituted C 1-6 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0080] In some embodiments, the polymer may comprise repeating units having a base-solubilizing group and / or having a pKa of less than or equal to 12. Exemplary base-solubilizing groups may include fluorohydrin groups, carboxylic acid groups, carboximide groups, sulfonamide groups, or sulfonimide groups.

[0081] Non-limiting examples of monomers containing a base-solubilizing group include one or more of the following:

[0082] Where R i Each is independently hydrogen, halogen, substituted or unsubstituted C. 1-6 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0083] The polymer may optionally further include one or more additional repeating units. These additional repeating units may be, for example, units used to modulate the properties of the photoresist composition, such as etching rate and solubility. Exemplary additional units may include those derived from one or more of (meth)acrylates, vinyl aromatic compounds, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. These one or more additional repeating units (if present in the first and / or second polymer) may be used in amounts up to 50 mol% of the total repeating units of the polymer, typically 3 to 50 mol%.

[0084] Non-limiting exemplary polymers of the present invention include one or more of the following:

[0085] Where x, y, and z are each the mole fraction of the relevant repeating unit, the sum of the mole fractions of each polymer is 1, and R d Each is independently hydrogen, halogen, substituted or unsubstituted C. 1-6 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0086] Other non-limiting exemplary polymers of the present invention include one or more of the following:

[0087] Where x, y, and z are each the mole fraction of the relevant repeating unit, the sum of the mole fractions of each polymer is 1, and R dEach is independently hydrogen, halogen, substituted or unsubstituted C. 1-6 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0088] The polymer typically has a weight-average molecular weight (Mn) of 1,000 to 50,000 Daltons (Da), preferably 2,000 to 30,000 Da, more preferably 3,000 to 20,000 Da, and even more preferably 4,000 to 15,000 Da. w The first polymer's polydispersity index (PDI) (which is M) w Number-average molecular weight (M n The ratio of 1 / 3 to 1 / 2 is typically 1.1 to 3, and more typically 1.1 to 2. Molecular weight values ​​are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0089] In the photoresist compositions of the present invention, the polymer is typically present in the photoresist composition in an amount of 10 to 99.9 wt%, typically 25 to 99 wt%, and more typically 50 to 95 wt% based on the total solids of the photoresist composition. It will be understood that the total solids include one or more polymers, PAG, and other non-solvent components.

[0090] Polymers can be prepared using any suitable method or one method in the art. For example, one or more monomers corresponding to the repeating units described herein can be fed together or separately using suitable solvents or initiators and polymerized in a reactor. For example, polymers can be obtained by polymerizing the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiating with photochemical radiation at an effective wavelength, or a combination thereof.

[0091] The photoresist composition may further comprise a photoacid generator (PAG). PAG can be in ionic or nonionic form. PAG can be in polymeric or nonpolymeric form. When in polymeric form, PAG can exist as part of a repeating unit of a polymer derived from a polymerizable PAG monomer.

[0092] Suitable PAG compounds can have the formula G + A - G + It is a photoactive cation and A -These are anions capable of producing photoactive acids. The photoactive cations are preferably selected from ononium cations, more preferably iodonium or sulfonium cations, as described above regarding the photoactive compounds of the present invention (e.g., those having formulas (7a) and / or (7b)). Particularly suitable anions include those whose conjugate acid has a pKa of -15 to 10. Anions are typically organic anions having a sulfonate group or non-sulfonate groups such as sulfonamidate, sulfonimidate, methylate, or borate.

[0093] In some respects, the anions of PAG do not include and are free from -F, -CF3, or -CF2- groups. It should be understood that "free from -F, -CF3, or -CF2- groups" means that the anions of PAG do not include groups such as -CH2CF3 and -CH2CF2CH3. In other respects, the anions of PAG are fluorine-free (i.e., they do not contain fluorine atoms and are not substituted by fluorine-containing groups). In some respects, the photoacid generator is fluorine-free (i.e., neither the photoactive cation nor the anion is fluorine-free).

[0094] Exemplary organic anions having a sulfonate group include one or more of the following:

[0095] Exemplary nonsulfonated anions include one or more of the following:

[0096] Commonly used onium salts may include, for example, triphenylsulfonium trifluoromethane sulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethane sulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethane sulfonate, triphenylsulfonium p-toluene sulfonate; di-tert-butylphenyliodomonium perfluorobutane sulfonate and di-tert-butylphenyliodomonium camphor sulfonate. Other useful PAG compounds are known in the field 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; sulfonates, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; and diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane and bis(p-toluenesulfonyl)diazomethane. Diazomethane; dioxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethyldioxime and bis-O-(n-butanesulfonyl)-α-dimethyldioxime; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate; and halogenated 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. Suitable photoacid generators are further described in U.S. Patent Nos. 8,431,325 and 4,189,323.

[0097] Typically, when the photoresist composition contains additional non-polymeric PAG, the PAG is present in the photoresist composition in an amount of 0.1 to 55 wt%, more typically 1 to 25 wt%, based on the total solids of the photoresist composition. When present in polymeric form, the additional PAG is typically contained 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.

[0098] The photoresist composition further comprises a solvent for dissolving the components of the composition and promoting its coating on a substrate. Preferably, the solvent is an organic solvent commonly 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); 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 acetoacetate; lactones, such as γ-butyrolactone (GBL) and ε-caprolactone; lactams, such as N-methylpyrrolidone; nitriles, such as acetonitrile and propionitrile; cyclic or acyclic carbonates, 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; and combinations thereof. Among these, preferred solvents include one or more of PGME, PGMEA, EL, GBL, HBM, CHO, DAA, or combinations thereof.

[0099] The total solvent content (i.e., the cumulative solvent content of all solvents) in the photoresist composition 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 will depend, for example, on the desired thickness of the photoresist layer being coated and the coating conditions.

[0100] In some aspects, the photoresist composition may further comprise a material containing one or more base-indestructible groups (“base-indestructible material”). As mentioned herein, a base-indestructible group is a functional group that can undergo a cleavage reaction in the presence of an aqueous base developer after the exposure step and the post-exposure baking step to provide a polar group (such as a hydroxyl, carboxylic acid, sulfonic acid, etc.). The base-indestructible group will not react significantly prior to the development step of the photoresist composition containing the base-indestructible group (e.g., will not undergo a bond-breaking reaction). Therefore, for example, the base-indestructible group will be substantially inert during the pre-exposure soft baking step, the exposure step, and the post-exposure baking step. “Substantially inert” means that ≤5%, typically ≤1%, of the base-indestructible group (or a portion thereof) will decompose, cleave, or react during the pre-exposure soft baking step, the exposure step, and the post-exposure baking step. The base-indestructible group is reactive under typical photoresist development conditions using, for example, an aqueous base photoresist developer (such as an aqueous solution of 0.26 standard (N) tetramethylammonium hydroxide (TMAH)). For example, a 0.26 N aqueous solution of TMAH can be used for single-immersion development or dynamic development, where, for example, 0.26 N TMAH developer is dispensed onto the imaged photoresist layer for a suitable duration (e.g., 10 to 120 seconds). Exemplary base-insecure groups are ester groups, typically fluorinated ester groups. Preferably, the base-insecure material is substantially immiscible with the first and / or second polymers of the photoresist composition and other solid components and has a lower surface energy than them. Thus, when coated onto a substrate, the base-insecure material can separate from the other solid components of the photoresist composition and reach the top surface of the formed photoresist layer.

[0101] In some respects, an alkali-insecure material can be a polymeric material that may contain one or more repeating units having one or more alkali-insecure groups (also referred to herein as an alkali-insecure polymer). For example, an alkali-insecure polymer may contain repeating units having two or more identical or different alkali-insecure groups. Preferred alkali-insecure polymers contain at least one repeating unit having two or more alkali-insecure groups, such as repeating units having two or three alkali-insecure groups.

[0102] Alkali-instable polymers can be prepared using any suitable method in the art. For example, alkali-instable polymers can be obtained by polymerizing the corresponding monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with photochemical radiation at an effective wavelength, or a combination thereof. Alternatively or additionally, suitable methods can be used to graft one or more alkali-instable groups onto the polymer backbone.

[0103] In some respects, alkali-instable materials are single molecules comprising one or more alkali-instable ester groups, preferably one or more fluorinated ester groups. Alkali-instable materials that are single molecules typically have an M value in the range of 50 to 1,500 Da. w .

[0104] When present, alkali-instable materials are typically present in the photoresist composition in an amount of 0.01 to 10 wt%, typically 1 to 5 wt%, based on the total solids of the photoresist composition.

[0105] In addition, or alternatively, besides alkali-instable polymers, the photoresist composition may further comprise one or more polymers other than and different from the polymers described above. For example, the photoresist composition may comprise additional polymers as described above but with different compositions. Furthermore, or alternatively, these one or more additional polymers may include those well-known in the field of photoresists, such as those selected from: polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycol, polyamides, polyacrylamide, polyphenols, phenolic varnishes, styrene polymers, polyvinyl alcohol, or combinations thereof.

[0106] The photoresist composition may further comprise one or more additional optional additives. For example, optional additives may include photochemical dyes and contrast dyes, anti-stripping agents, plasticizers, accelerators, sensitizers, photodegradable quenchers (PDQ) (and also referred to as photodegradable bases), alkaline quenchers, hot acid generators, surfactants, etc., or combinations thereof. If present, optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 wt% based on the total solids of the photoresist composition.

[0107] PDQ produces a weak acid upon irradiation. The acid produced by the photodegradable quencher is not strong enough to react rapidly with the acid-indegradable groups present in the resist matrix. Exemplary photodegradable quenchers include, for example, anions of weak acids (pKa > 1) such as Cp. 1-20 Carboxylic acid or C 1-20 The photodegradable quencher is a photodegradable cation paired with the anion of a sulfonic acid, and preferably also those that can be used to prepare strong acid generating compounds. 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 a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound, such as diphenyliodonium-2-carboxylic acid ester.

[0108] PDQ can be in non-polymeric or polymeric forms. Polymer units containing photodegradable quenchers are typically present in amounts of 0.1 to 30 mol%, typically 1 to 10 mol%, and more typically 1 to 2 mol%, based on the total repeating units in the polymer.

[0109] Exemplary basic quenchers include, for example, straight-chain aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetra(2-hydroxypropyl)ethylenediamine, N-tert-butyldiethanolamine, tris(2-acetoxy-ethyl)amine, 2,2',2'',2'''-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2''-nitrotriethanol; cyclic aliphatic amines, Examples include 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazolium-1-carboxylate, di-tert-butyl piperazine-1,4-dicarboxylate, and N-(2-acetoxy-ethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; linear and cyclic amides and their derivatives, such as N,N-bis(2-hydroxyethyl)palmitamide, N,N-diethylacetamide, and N... 1 N 1 N 3 N 3 -Tetrabutylmalonamide, 1-methylazacycloheptan-2-one, 1-allylazacycloheptan-2-one and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propyl-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, aminosulfonates, carboxylates and phosphonates; imines, such as primary and secondary aldehyde imines 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.

[0110] The alkaline quencher can be in non-polymeric or polymeric form. When in polymeric form, the quencher 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 repeating units in the polymer.

[0111] Exemplary surfactants include fluorinated and nonfluorinated surfactants and can be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluorinated C4 surfactants, such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorinated glycols, such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorinated surfactants from Omnova. In this aspect, the photoresist composition further comprises a surfactant polymer containing fluorinated repeating units.

[0112] A patterning method using the photoresist composition of the present invention will now be described. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates can be used in the present invention, such as: semiconductor wafers; polycrystalline silicon substrates; packaging substrates, such as multi-chip modules; flat panel display substrates; substrates for light-emitting diodes (LEDs) including organic light-emitting diodes (OLEDs); etc., wherein semiconductor wafers are typical. Such substrates are typically composed of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanide, 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 for manufacturing 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 millimeters (mm), although 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 may optionally include active or operable portions of the formed device.

[0113] Typically, prior to coating the photoresist composition of the present invention, one or more photolithographic layers, such as hard mask layers (e.g., spin-coated carbon (SOC), amorphous carbon, or metal hard mask layers), CVD layers (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layers), organic or inorganic underlayers, or combinations thereof, are provided on the upper surface of the substrate. These layers, together with the externally coated photoresist layer, form a photolithographic material stack.

[0114] Optionally, an adhesion promoter layer may be applied to the substrate surface prior to 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 like trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents like γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold from DuPont Electronics & Industrial (Marlborough, Massachusetts) under the names AP™ 3000, AP™ 8000, and AP™ 9000S.

[0115] Photoresist compositions can be coated onto a substrate by any suitable method, including spin coating, spraying, dip coating, blade coating, etc. For example, applying a photoresist layer can be accomplished by spin coating the photoresist in a solvent using a coating track, wherein the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically rotated at speeds up to 4,000 rpm, for example 200 to 3,000 rpm, or for example 1,000 to 2,500 rpm, for a period of 15 to 120 seconds to obtain a photoresist composition layer on the substrate. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by varying the rotation speed and / or the total solids of the composition. Photoresist composition layers formed from the compositions of the present invention typically have a dry layer thickness of 3 to 30 micrometers (µm), preferably greater than 5 to 30 µm, and more preferably 6 to 25 µm.

[0116] Next, the photoresist composition is typically soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the layer's adhesion to the substrate. Soft baking is typically performed, for example, on a heated plate or in an oven, with a heated plate being typical. The soft baking temperature and time will depend, for example, on the photoresist composition and thickness. Soft baking temperatures are typically 80°C to 170°C, and more typically 90°C to 150°C. Soft baking times are typically 10 seconds to 20 minutes, more typically 1 to 10 minutes, and even more typically 1 to 2 minutes. Those skilled in the art can readily determine the heating time based on the composition's components.

[0117] Next, the photoresist layer is patterned and exposed to activating radiation to create a solubility difference between the exposed and unexposed areas. The exposure of the photoresist composition to radiation that activates the composition, as described herein, indicates that radiation can form a latent image in the photoresist composition. Exposure is typically performed using a patterned photomask with optically transparent and optically opaque regions corresponding to the areas of the photoresist layer to be exposed and the areas of the unexposed photoresist layer, respectively. Alternatively, this exposure can be performed without a photomask in a direct-write method, typically used in electron beam lithography. The activating radiation typically has wavelengths 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 radiation. This method can be used in immersion or dry (non-immersion) lithography techniques. The energy exposed is typically 1 to 200 millijoules per square centimeter (mJ / cm²). 2 ), preferably 10 to 100 mJ / cm 2 And more preferably 20 to 50 mJ / cm 2 This depends on the composition of the exposed tool and the photoresist composition.

[0118] After the photoresist layer is exposed, post-exposure baking (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a heated plate or in an oven, with a heated plate being typical. The conditions of PEB will depend, for example, on the photoresist composition and the layer thickness. PEB is typically performed at a temperature of 70°C to 150°C, preferably 75°C to 120°C, for a time of 30 to 120 seconds. A latent image is formed in the photoresist, defined by polarity-converted regions (exposed regions) and polarity-unconverted regions (unexposed regions).

[0119] The exposed photoresist layer is then developed with a suitable developer to selectively remove areas of the layer that are soluble in the developer while retaining insoluble areas, forming the resulting photoresist pattern relief image. In the case of a positive development (PTD) process, the exposed areas of the photoresist layer are removed during development, while the unexposed areas are retained. Conversely, in a negative development (NTD) process, the exposed areas of the photoresist layer are retained during development, while the unexposed areas are removed. The application of the developer can be accomplished by any suitable method, as described above regarding the application of the photoresist composition, with spin coating being typical. The development time is the period of time during which the soluble areas of the photoresist are effectively removed, typically 5 to 60 seconds. Development is typically performed at room temperature.

[0120] Suitable developers for PTD processes include aqueous alkaline developers, such as quaternary ammonium hydroxide solutions, such as TMAH (preferably 0.26 N TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for NTD processes are based on organic solvents, meaning that the cumulative content of organic solvents 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 NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. Typical developers are 2-heptanone or n-butyl acetate.

[0121] The coated substrate can be formed from the photoresist composition of the present invention. Such a coated substrate comprises: (a) a substrate having one or more layers to be patterned on its surface; and (b) a photoresist composition layer on the one or more layers to be patterned.

[0122] Photoresist patterns can be used, for example, as an etching mask to transfer the pattern to one or more sequentially arranged underlying layers using known etching techniques, typically dry etching (such as reactive ion etching). Photoresist patterns can also be used, for example, to transfer a pattern to an underlying hard mask layer, which in turn serves as an etching mask for transferring the pattern to one or more layers below the hard mask layer. If the photoresist pattern is not lost during pattern transfer, it can be removed from the substrate using 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.

[0123] The invention is further illustrated by the following non-limiting examples.

[0124] Example

[0125] Synthetic examples. The synthetic reactions were carried out under a nitrogen atmosphere. All chemicals were used as is, without further purification, from the commercial supplier. Proton NMR (Nuclear Magnetic Resonance) spectra of all compounds were obtained. 1 H-NMR spectra were obtained on a 500 MHz NMR spectrometer. Chemical shifts relative to the internal standard tetramethylsilane are reported in δ (parts per million, ppm). Multiplicity is indicated by singlet (s), doublet (d), triplet (t), multiplet (m), double doublet (dd), double triplet (dt), triple triplet (tt), or broad singlet (br).

[0126] Synthesis of Q1

[0127] Compound B (0.68 g, 2 mmol) and 10 mL of deionized (DI) water were added to a solution of compound A (0.66 g, 1.99 mmol) in 10 mL of dichloromethane (DCM). The resulting biphasic reaction mixture was stirred at room temperature for one hour. The organic layer was then separated and washed with 5 mL of DI water. After washing, the organic layer was separated again, and the solvent was removed under reduced pressure to give product Q1 as a pale yellow solid, 1.1 g (96%). 1 ¹H-NMR (δ, dimethyl sulfoxide-d6(DMSO-d6)) 7.92–7.75 ppm (17H, m), 7.64–7.56 ppm (2H, m), and 1.64 ppm (6H, m).

[0128] Synthesis of Q2

[0129] Compound C (0.9 g, 2 mmol) and 10 mL of DI water were added to a solution of compound A (0.66 g, 1.99 mmol) in 10 mL of DCM. Following a similar procedure to the synthesis of Q1, product Q2 was obtained as a 1.3 g (93%) white-orange solid. 1 H-NMR (δ, DMSO-d6) 8.14 ppm (d, 4H), 7.89 ppm (dd, 2H), 7.64-7.58 ppm (2H,m), 7.53 ppm (d, 4H), 1.64 ppm (6H, s), and 1.26 ppm (18H, s).

[0130] Q3 Synthesis

[0131] Compound B (0.6 g, 3 mmol) and 10 mL of DI water were added to a solution of compound D (0.5 g, 1.55 mmol) in 10 mL of DCM. Following a similar procedure to the synthesis of Q1, 0.75 g (80%) of product Q3, a pale yellow oil, was obtained. 1 H-NMR (δ, DMSO-d6) 8.32 ppm (1H, d), 7.89-7.76 ppm (15H, m), 7.62 ppm (1H,d), 7.48 ppm (2H, m), and 1.43 ppm (18H, s).

[0132] Q4 Synthesis

[0133] Compound B (2.0 g, 5.82 mmol) and 20 mL of DI water were added to a solution of compound E (2.0 g, 6.26 mmol) in 20 mL of DCM. The resulting biphasic reaction mixture was then stirred at room temperature for four hours. The organic layer was separated and washed five times each with 15 mL of DI water. The organic layer was separated again, and the solvent was removed under reduced pressure to give Q4 as a white solid. 1 H-NMR (δ, DMSO-d6) 7.69-7.59 ppm (17H, m), 7.64-7.42 ppm (2H, m), and 2.6 ppm (6H, s).

[0134] Q5 Synthesis

[0135] Compound C (1.4 g, 3.9 mmol) and 20 mL of DI water were added to a solution of compound E (1.0 g, 3.13 mmol) in 20 mL of DCM. Following a similar procedure to the synthesis of Q4, Q5 was obtained as a white solid. 1 H-NMR (δ, DMSO-d6)6.87 ppm (4H, d), 7.81 ppm (2H, m), 4.55 ppm (2H, M), 6.39 ppm (4H, d), and 1.29 ppm (18H, s).

[0136] Contrast Rating

[0137] Photoresist compositions were prepared by dissolving solid components in solvents to achieve a total solids content of 1.55 wt% using the materials and proportions described in Table 1. The amounts of components are reported as wt% of the total solids in the photoresist composition. The solvent system contained PGMEA (50 wt%) and diacetone alcohol (50 wt%). The resulting mixture was vibrated on a mechanical vibrator and then filtered through a PTFE disc filter with a pore size of 0.2 μm. The corresponding photoresist compositions were spin-coated onto each 200 mm silicon wafer covered with a BARC stack (60 nm thick AR™ 3 antireflective agent on 80 nm thick AR™ 40A antireflective agent (DuPont Electronics & Industries)) on a TEL Clean Track ACT 8 wafer track (TEL, Tokyo Electron Co.) and soft-baked at 110°C for 60 seconds to provide a photoresist layer with a target thickness of approximately 40 nm. The resist layer thickness was measured using a THERMA-WAVE OP7350. Radiation was applied at 248 nm on a CANON FPA-5000 ES4 scanner at a rate of 3 to 53 millijoules per square centimeter (mJ / cm²). 2 The wafers were exposed to an exposure dose of 100°C for 60 seconds, followed by baking, development with MF™ CD26 TMAH developer (DuPont Electronics & Industries) for 60 seconds, rinsing with DI water, and drying. The photoresist layer thickness was measured in the exposed area of ​​the layer. A contrast profile was generated for each wafer, and E0 was determined from the contrast profile described above. An additional contrast profile for each wafer was generated by plotting the normalized photoresist layer thickness against the logarithm of the exposure dose in the exposed area. The contrast (γ) was determined from the slope between the 80% and 20% photoresist film thickness points on this normalized contrast profile. The results are shown in Table 1.

[0138] Table 1 Indicates a comparison example.

[0139]

[0140] Photolithography Evaluation

[0141] Photoresist compositions were prepared by dissolving solid components in solvents to achieve a total solids content of 4.15 wt% using the materials and amounts described in Table 2. The amounts of components are reported as wt% of the total solids in the photoresist composition. The solvent system contained PGMEA (50 wt%) and diacetone alcohol (50 wt%). Each mixture was vibrated using a mechanical vibrator and then filtered through a PTFE disc filter with a 0.2 μm pore size. Photolithography was performed using a CLEAN TRAC ACT8 (TEL, Tokyo Electron Ltd.) wafer track. A 200 nm wafer for photolithography testing was coated with AR™ 3 BARC (DuPont Electronics & Industries) and soft-baked at 205°C for 60 seconds to obtain a 60 nm film. A coating of AR™ 40A BARC (DuPont Electronics & Industries) was then deposited on the AR™ 3 layer and soft-baked at 215°C for 60 seconds to form a second BARC layer with a thickness of 80 nm. The photoresist composition was then coated onto the double BARC stack and soft-baked at 110°C for 60 seconds to obtain a photoresist film with a thickness of 120 nm.

[0142] The resulting wafer was exposed to 248 nm radiation using a mask with a 1:1 CH pattern (200 nm linewidth) on a CANON FPA-5000 ES4 scanner (NA = 0.8, outer sigma = 0.85, inner sigma = 0.57). The exposed wafer was then baked at 100°C for 60 seconds, developed with 0.26 N TMAH solution for 60 seconds, rinsed with DI water, and spin-dried to form a photoresist pattern. The critical dimension (CD) linewidth of the formed pattern was measured using a HITACHI S-9380 CD-SEM. Local critical dimension uniformity (LCDU) was determined based on the CD measurements. Sizing energy (E) was also measured. 尺寸 The data for ) and LCDU are shown in Table 2.

[0143] Table 2 Indicates a comparison example.

[0144]

[0145] While this disclosure has been described in conjunction with exemplary embodiments now considered to be practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A photoactive compound comprising: Organic cations selected from the iodonium cation shown in formula (7b) and the sulfonium cation shown in formula (7a), (7a) (7b) In equations (7a) and (7b), R 8 To R 12 Each is a substituted or unsubstituted C independently. 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 6-30 Iodoaryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 Heteroarylalkyl; R 8 To R 10 Each is attached to R individually or via a single or divalent linker. 8 To R 10 Another group in it forms a ring; R 11 and R 12 They are either individually or linked together via single or divalent linkages to form a ring; and The anion represented by equation (5a): (5a) in, In equation (5a), R 3 Each is independently a halogen, cyano, or substituted or unsubstituted C group. 1-30 alkyl; a is an integer from 0 to 4; R 4 and R 5 Each is independently hydrogen, or a substituted or unsubstituted C. 1-30 Alkyl groups; and R 4 and R 5 They can be arranged together to form a ring.

2. The photoactive compound of claim 1, wherein, The anion represented by formula (5a) is fluorine-free.

3. The photoactive compound according to claim 1 or 2, wherein, The anion contains one or more acid-indestructible groups.

4. A photoresist composition comprising: The photoactive compound as described in any one of claims 1 to 3; and polymer.

5. The photoresist composition of claim 4, further comprising a photoacid generator different from the photoactive compound, wherein the polymer comprises one or more acid-indestructible groups.

6. A patterning method, the method comprising: A layer of the photoresist composition as described in claim 4 or 5 is applied to a substrate to provide a photoresist composition layer; The photoresist composition layer is patterned and exposed to activated radiation to provide an exposed photoresist composition layer; as well as The exposed photoresist composition layer is then developed.

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