Photoactive compounds, photoresist compositions including the same, and pattern formation methods

Abstract

To provide photoactive compounds, photoresist compositions including the same, and pattern formation methods.SOLUTION: Provided is a photoactive compound comprising an organic cation selected from the group consisting of iodonium cations and sulfonium cations, and an anion represented by any one of Formulae (5a) to (5c).SELECTED DRAWING: None

Description

[Technical Field]

[0001] PHOTOACTIVE COMPOUNDS FOR PHOTORESIST COMPOSITIONS AND PATTERNING METHODS USING SUCH PHOTORESIST COMPOSITIONS FIELD OF THE INVENTION The present invention finds applicability in lithography applications in the semiconductor manufacturing industry. [Background technology]

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

[0003] Chemically amplified photoresists have traditionally been used for high-resolution processing. Such resists typically use a polymer with acid-labile groups, a photoacid generator, and an acid-quenching material. Patternwise exposure to activating radiation through a photomask causes the acid generator to form an acid, which, during post-exposure baking, causes cleavage of the acid-labile groups in the exposed areas of the polymer. To control the diffusion of acid to the unexposed areas and improve contrast, an acid-quenching material is often added to the photoresist composition. A consequence of the lithography process is the creation of differences in solubility characteristics between the exposed and unexposed regions of the resist in a developer. In a positive-tone development (PTD) process, the exposed regions of the photoresist layer become soluble in the developer and are removed from the substrate surface, while the unexposed regions, which are insoluble in the developer, remain after development, forming a positive image. The resulting relief image allows for selective processing of the substrate.

[0004] Non-photoactive acid-quenchable materials commonly used in chemically amplified resists include linear aliphatic amines, cycloaliphatic amines, aromatic amines, linear and cyclic amides, and their derivatives. Another commonly used class of acid-quenchable materials is photoactive quenchers, also known as photodegradable quenchers or photolytic quenchers. Photoactive quenchers have also been used in chemically amplified resist compositions. Photolytic quenchers are typically salts containing a photoactive onium cation and an anion, where the anion is the conjugate base of a weak acid. This salt functions as a base or acid quencher before exposure. Upon exposure, the anion moiety of the photolytic quencher becomes protonated and thus becomes more acidic. Therefore, upon irradiation of a chemically amplified resist containing a photolytic quencher, the concentration of the acid quencher in the exposed area dramatically decreased. Meanwhile, the intact photolytic quencher in the unexposed area can capture acid molecules that diffuse from the exposed area during lithographic processing, thereby improving lithographic performance.

[0005] Photoresist compositions containing photodecomposable quenchers and their uses have been described in the art. There is a need for new photoresists that can provide high-resolution line-space features with excellent contrast and / or contact-hole (CH) features with improved critical dimension uniformity (CDU). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 8,431,325 [Patent Document 2] U.S. Patent No. 4,189,323 Summary of the Invention [Means for solving the problem]

[0007] an organic cation and a compound of formula (1): [ka] (wherein X is an organic group; Y 1 and Y 2 are each independently a substituent that is not hydrogen; 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 Aryl alkyl, 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 comprises 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; X and Y 1 or Y 2 and an anion represented by:

[0008] Also provided is a photoresist composition comprising a photoactive compound and a polymer.

[0009] Also provided is a method of forming a pattern, comprising: applying a layer of the photoresist composition of claim 9 or 10 onto a substrate to obtain a photoresist composition layer; patternwise exposing the photoresist composition layer to activating radiation to obtain an exposed photoresist composition layer; and developing the exposed photoresist composition layer. DETAILED DESCRIPTION OF THE INVENTION

[0010] Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in this description. In this regard, the exemplary embodiments may have different forms and should not be construed as limited to the description set forth herein. Accordingly, exemplary embodiments are described below by reference to the figures only to describe aspects of the present description. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. Phrases such as "at least one," when preceding a list of elements, modify the entire list of elements and not each individual element of the list.

[0011] As used herein, the terms "a," "an," and "the" do not denote quantitative limitations and should be construed to include both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. The modifier "about," used in connection with a quantity, is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measuring the particular quantity). All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independent and inclusive of each other. The suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including at least one of that term. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where the event does not occur. The terms "first," "second," etc., as used herein, do not denote 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 intervening elements may be present between them. In contrast, when an element is said to be "directly on" another element, there are no intervening elements present. It should be understood that the described components, elements, limitations, and / or features of the embodiments can be combined in any suitable manner in the various embodiments.

[0012] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning in the context of the relevant technical field and this disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0013] As used herein, "actinic rays" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, corpuscular rays such as electron beams and ion beams, etc. Furthermore, in the present invention, "light" refers to actinic rays or radiation. Krypton fluoride lasers (KrF lasers) are a specific type of excimer laser and are sometimes called exciplex lasers. "Excimer" stands for "excimer dimer," and "exciplex" stands for "exciplex." Excimer lasers use a mixture of a rare gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine), which, under suitable conditions of electrical stimulation and high pressure, emits coherent stimulated radiation (laser light) in the ultraviolet range. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using far ultraviolet light such as that typified by a mercury lamp or excimer laser, X-rays, extreme ultraviolet light (EUV light), etc., but also writing using particle beams such as electron beams and ion beams.

[0014] As used herein, an "organic group" contains one or more carbon atoms, for example, 1 to 60 carbon atoms. The term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom. The term "alkyl" refers to a straight- or branched-chain saturated hydrocarbon radical having the specified number of carbon atoms and a valence of one; "alkylene" refers to an alkyl radical having a valence of two; "hydroxyalkyl" refers to an alkyl radical substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid" refer to groups having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent radical having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl radical having a valence of two; "alkenyl" refers to a straight- or branched-chain monovalent hydrocarbon radical having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl radical having a valence of two; and "cycloalkenyl" refers to a group having at least one carbon-carbon double bond. "alkynyl" refers to a monovalent hydrocarbon group having at least three carbon atoms, wherein the carbon atom is substituted with an alkyl group; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system that satisfies Huckel's rule and contains carbon in the ring and may optionally contain one or more heteroatoms selected from N, O, and S in place of carbon atoms in the ring; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which all ring members are carbon and may contain a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene" refers to an aryl group having a valence of two; "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-".

[0015] The prefix "hetero" means that the compound or group contains at least one member atom that is a heteroatom (e.g., 1, 2, 3, or more heteroatoms) in place of a carbon atom, where each heteroatom is independently N, O, S, Si, or P; a "heteroatom-containing group" refers to a substituent that contains at least one heteroatom; a "heteroalkyl group" refers to an alkyl group having from 1 to 4 or more heteroatoms in place of carbon; a "heterocycloalkyl group" refers to a cycloalkyl group having from 1 to 4 or more heteroatoms in place of carbon as ring members; a "heterocycloalkylene group" refers to a heterocycloalkyl group having a valence of 2; a "heteroaryl group" refers to an aryl group having from 1 to 4 or more heteroatoms in place of carbon as ring members; and a "heteroarylene group" refers to a heteroaryl group having a valence of 2.

[0016] Unless expressly specified otherwise, each of the foregoing substituents can be optionally substituted. For example, if a group is listed without specifying whether it is substituted or unsubstituted, the group includes both unsubstituted and substituted groups. The term "optionally substituted" refers to substituted or unsubstituted.

[0017] "Substituted" means that at least one hydrogen atom of the chemical structure is replaced with another terminal substituent, typically monovalent, provided that the normal valence of the designated atom is not exceeded. When the substituent is oxo (i.e., =0), two geminal hydrogen atoms on the carbon atom are replaced with the terminal oxo group. Combinations of substituents or variables are permissible. Exemplary substituents that may be present at a "substituted" position include nitro (-NO), cyano (-CN), hydroxyl (-OH), oxo (=0), amino (-NH), mono- or di-(C 1~6 ) alkylamino, alkanoyl (acyl, etc. C 2~6 alkanoyl group, etc.), formyl (-C(=O)H), carboxylic acid or its alkali metal salt or ammonium salt;C 2~6Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7~13 Esters (including acrylates, methacrylates and lactones) such as aryl esters (-C(=O)O-aryl or -OC(=O)-aryl); amides (-C(=O)NR2 where R is hydrogen or C 1~6 alkyl), carboxamide (-CHC(=O)NR (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 Alkenyl, C 2~6 Alkynyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, C with at least one aromatic ring 6~12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., in which each ring is either substituted or unsubstituted aromatic), C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms 7~19 arylalkyl, arylalkoxy 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 Includes, but is not limited to, arylsulfonyl, (-S(=O)2-aryl) or tosyl (CH3C6H4SO2-).

[0018] 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 in place of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or only fluoro groups can be present. 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 a C alkyl group substituted with at least one halogen. 1~8 It refers to an alkyl group, which is further substituted with one or more other substituents that are not halogens.

[0019] As used herein, "acid labile group" refers to a group formed on a polymer that undergoes bond cleavage, optionally and typically accompanied by thermal treatment, resulting in the formation of a polar group, such as a carboxylic acid group or an alcohol group, through the catalytic action of an acid. The moiety linked to the cleaved bond is then separated from the polymer, optionally and typically. In another system, a non-polymeric compound can contain an acid labile group that can be cleaved by the action of an acid, forming a polar group, such as a carboxylic acid group or an alcohol group, at the cleaved portion of the non-polymeric compound. Such acids are typically photogenerated acids, in which bond cleavage occurs during post-exposure bake (PEB). However, embodiments are not limited thereto. For example, such acids can be thermally generated. Suitable acid labile 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 labile groups are also commonly referred to in the art as "acid cleavable groups," "acid cleavable protecting groups," "acid labile protecting groups," "acid leaving groups," "acid decomposable groups," and "acid sensitive groups."

[0020] As used herein, unless otherwise specified, a "divalent linking group" is any of -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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 R refers to a divalent group containing one or more of: a 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 Typically, the divalent linking group includes -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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof; R a 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 More typically, the divalent linking group includes -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 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10heteroarylene, or a combination thereof; R a 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 It is heteroaryl.

[0021] The present invention relates to a photoactive compound, for example, a photodecomposable quencher compound. In particular, the photoactive compound of the present invention is a salt containing a nitrogen atom anion directly bonded to an alkenyl group and optionally directly bonded to a second electron-withdrawing group. The photoactive compound of the present invention is particularly useful in photoresist compositions to achieve improved contrast and improved local critical dimension uniformity (LCDU).

[0022] The photoactive compound includes an organic cation and an anion represented by formula (1): [ka]

[0023] In formula (1), X is an organic group. For example, X may be a substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C7~30 Alkylaryl or substituted or unsubstituted C6-C 30 aryloxy, where X may optionally further include one or more divalent linking groups as part of its structure. In some embodiments, X may include, as part of its structure, -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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 and R may further comprise one or more divalent linking groups selected from heteroarylene, heteroaryl, or combinations thereof. ’ 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 heteroaryl.

[0024] X and Y 1 or Y 2 may optionally be taken together to form a ring, which ring optionally further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0025] In equation (1), Y 1 and Y 2 are each independently a non-hydrogen substituent. 1 and Y 2 each independently contains an electron-withdrawing group, such as a carbonyl group (—C(O)—) or a cyano group (—CN). 1 and Y 2 are each independently halogen, cyano, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl or substituted or unsubstituted C6-C 30 aryloxy, and Y 1 and Y 2 may each independently optionally further include one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -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 Heterocycloalkylene, substituted or unsubstituted C 6~20 Arylene, substituted or unsubstituted C 3~20 heteroarylene, or a combination thereof; 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 Typically, Y 1 and Y 2 are each independently cyano, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 1~10Heteroalkyl, substituted or unsubstituted C 3~10 Cycloalkyl, or substituted or unsubstituted C 3~10 is heterocycloalkyl, and Y 1 and Y 2 may each independently optionally further include one or more divalent linking groups (e.g., —C(O)O—) as part of its structure. In some embodiments, Y 1 and / or Y 2 may contain acid labile groups as part of its structure. For example, Y 1 and Y 2 At least one of the groups contains an acid labile group as part of its structure.

[0026] In equation (1), Y 1 and Y 2 may optionally be joined together to form a ring. For example, Y 1 and Y 2 may optionally be joined together to form a ring, which ring may optionally further include one or more divalent linking groups as part of its structure, each of which may be substituted or unsubstituted, and the ring may be substituted or unsubstituted. 1 and Y 2 may be linked together via a divalent linking group which may include an acid labile group as part of its structure.

[0027] In formula (1), 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 Aryl alkyl, 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 4~30Heteroarylalkyl, or substituted or unsubstituted C 3~30 Preferably, Z is heteroaryloxy. 2 is hydrogen, halogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, substituted or unsubstituted C 7~20 Aryl alkyl, 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 Alkylheteroaryl, substituted or unsubstituted C 4~10 Heteroarylalkyl, or substituted or unsubstituted C 3~10 Typically, Z 2 is a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, substituted or unsubstituted C 7~20 Aryl alkyl, 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 Alkylheteroaryl, substituted or unsubstituted C 4~10 Heteroarylalkyl, or substituted or unsubstituted C 3~10 It may be heteroaryloxy.

[0028] In formula (1), Z 2 optionally further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substituted or unsubstituted C1~30 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 combination thereof; 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 It may be heteroaryl.

[0029] In formula (1), X and R 2 may optionally be joined together to form a ring, and this ring may optionally further include one or more divalent linking groups as part of its structure, each of which may be substituted or unsubstituted, and the ring may be substituted or unsubstituted. Typically, X and R 2 together form a ring, and the ring further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0030] Preferably, X is N in formula (1). - For example, the electron-withdrawing group may be attached to the nitrogen anion in formula (1) (i.e., the anionic nitrogen atom in formula (1)).

[0031] In some embodiments, X is selected from the group consisting of formulas (2a)-(2c): [ka] (where * represents N in formula (1) - The moiety may be represented by one of the following:

[0032] In formula (2a), Z1a 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 Aryl alkyl, 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 Preferably, Z is heteroaryloxy. 1a is hydrogen, halogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, substituted or unsubstituted C 7~20 Aryl alkyl, 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 Alkylheteroaryl, substituted or unsubstituted C 4~10 Heteroarylalkyl, or substituted or unsubstituted C 3~10 Typically, Z 1a is a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, substituted or unsubstituted C 7~20 Aryl alkyl, substituted or unsubstituted C 7~20 Alkylaryl, substituted or unsubstituted C 6~20Aryloxy, substituted or unsubstituted C 3~10 Heteroaryl, substituted or unsubstituted C 4~10 Alkylheteroaryl, substituted or unsubstituted C 4~10 Heteroarylalkyl, or substituted or unsubstituted C 3~10 It may be heteroaryloxy.

[0033] In formula (2a), Z 1a optionally further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof; 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 It may be heteroaryl.

[0034] In formula (2a), Y 3 and Y 4 are each independently a substituent that is not hydrogen. 3 and Y 4 are each independently halogen, cyano, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C1-C30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl or substituted or unsubstituted C6-C 30 aryloxy, and Y 3 and Y 4 may each independently optionally further include one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -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 Heterocycloalkylene, substituted or unsubstituted C 6~20 Arylene, substituted or unsubstituted C 3~20 heteroarylene, or a combination thereof; 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 Typically, Y 3 and Y 4 are each independently cyano, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 1~10 Heteroalkyl, substituted or unsubstituted C 3~10 Cycloalkyl, or substituted or unsubstituted C 3~10 is heterocycloalkyl, and Y 3 and Y 4may each independently optionally further include one or more divalent linking groups (e.g., —C(O)O—) as part of its structure. In some embodiments, Y 3 and / or Y 4 may contain acid labile groups as part of its structure. For example, Y 3 and Y 4 At least one of the groups contains an acid labile group as part of its structure.

[0035] In formula (2a), Y 3 and Y 4 may optionally be joined together to form a ring. For example, Y 3 and Y 4 may optionally be joined together to form a ring, which ring may optionally further include one or more divalent linking groups as part of its structure, each of which may be substituted or unsubstituted, and the ring may be substituted or unsubstituted. 3 and Y 4 may be linked together via a divalent linking group which may include an acid labile group as part of its structure.

[0036] In formula (2a), Z 1a and Y 3 or Y 4 optionally together form a ring, which ring optionally further comprises one or more divalent linking groups as part of its structure, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted.

[0037] In formulas (1) and (2a), Z 2 and Y 3 or Y 4 optionally together form a ring, which ring optionally further comprises one or more divalent linking groups as part of its structure, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted.

[0038] In formulas (1) and (2a), Z 1a and Z 2optionally together form a ring. This ring optionally further comprises one or more divalent linking groups as part of its structure, each of which may be substituted or unsubstituted, and the ring may be substituted or unsubstituted. Typically, Z 1a and Z 2 optionally together form a ring, which ring optionally further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0039] In formulas (2b) and (2c), Z 1b and Z 1c are each independently a 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 Aryl alkyl, 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 Preferably, Z is heteroaryloxy. 1b and Z 1c are each independently a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, substituted or unsubstituted C 7~20 Aryl alkyl, 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 4~10Alkylheteroaryl, substituted or unsubstituted C 4~10 Heteroarylalkyl, or substituted or unsubstituted C 3~10 Typically, Z 1b and Z 1c are each independently a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, substituted or unsubstituted C 7~20 Aryl alkyl, 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 Alkylheteroaryl, substituted or unsubstituted C 4~10 Heteroarylalkyl, or substituted or unsubstituted C 3~10 It is heteroaryloxy.

[0040] In formulas (2b) and (2c), Z 1b and Z 1c each independently optionally further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof; 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 C3~30 It may be heteroaryl.

[0041] In formulas (1) and (2b), Z 1b and Z 2 optionally together form a ring. This ring optionally further comprises one or more divalent linking groups as part of its structure, each of which may be substituted or unsubstituted, and the ring may be substituted or unsubstituted. Typically, Z 1b and Z 2 together form a ring, which ring further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0042] In formulas (1) and (2c), Z 1c and Z 2 optionally together form a ring. This ring optionally further comprises one or more divalent linking groups as part of its structure, each of which may be substituted or unsubstituted, and the ring may be substituted or unsubstituted. Typically, Z 1c and Z 2 together form a ring, and this ring further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0043] In some embodiments, the anion represented by formula (1) does not contain or is free of -F, -CF3, or -CF2- groups. "Free of -F, -CF3, or -CF2- groups" should be understood to mean that groups such as -CH2CF3 and -CH2CF2CH3 are excluded from the anion of the photoacid generator. In yet another embodiment, the anion represented by formula (1) does not contain fluorine (i.e., it does not contain a fluorine atom and is not substituted with a fluorine-containing group). In some embodiments, the photoactive compound does not contain fluorine (i.e., both the organic cation and the anion represented by formula (1) do not contain fluorine).

[0044] For example, in formula (1), X and Y1 , Y 2 , and Z 2 At least one of X, Y does not contain fluorine, and preferably 1 , Y 2 , and Z 2 For example, in formulas (1), (2a), (2b), and (2c), Y 1 , Y 2 , Y 3 , Y 4 , Z 1a , Z 1b , Z 1c , and Z 2 At least one of the groups does not contain fluorine, and preferably Y 1 , Y 2 , Y 3 , Y 4 , Z 1a , Z 1b , Z 1c , and Z 2 All of these do not contain fluorine.

[0045] In some embodiments, as described 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 For example, in formulas (1), (2a), (2b), and (2c), one or more of Y 1 , Y 2 , Y 3 , Y 4 , Z 1a , Z 1b , Z 1c , and Z 2 One or more of the groups contains an acid labile group.

[0046] In some embodiments, the photoactive compound of formula (1) can be represented by one or more of formulas (3a)-(3c): [ka]

[0047] In formulas (3a) and (3b), Y 1 and Y2 is Y in equation (1). 1 and Y 2 In formula (3c), Y 1 and Y 2 is Y in equation (1). 1 and Y 2 is as defined for Y 3 and Y 4 is expressed as Y in equation (2a). 3 and Y 4 is as defined above.

[0048] In formulas (3a) to (3c), R 1 and R 2 are each independently a 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 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 6~30 Aryloxy, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is heteroaryloxy.

[0049] In formulas (3a) to (3c), R 1 and R 2 each independently optionally further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups are -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 3~30Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof; 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 It may be heteroaryl.

[0050] In formulas (3a) to (3c), R 1 and R 2 may optionally be joined together to form a ring, which ring optionally further comprises one or more divalent linking groups as part of its structure, each of which may be substituted or unsubstituted, and the ring may be substituted or unsubstituted. Typically, R 1 and R 2 together form a ring, which ring further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0051] The anions represented by formulas (3a) to (3c) may not contain fluorine. For example, in formulas (3a) and (3b), R 1 , R 2 , Y 1 , and Y 2 At least one of the groups does not contain fluorine, and preferably R 1 , R 2 , Y 1 , and Y 2 For example, in formula (3c), R 1 , R 2 , Y 1 , Y 2 , Y 3 , and Y 4 At least one of the groups does not contain fluorine, and preferably R 1 , R 2 , Y 1 , Y 2 , Y 3, and Y 4 All of these do not contain fluorine.

[0052] 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 At least one of R 1 , R 2 , Y 1 , Y 2 , Y 3 , and Y 4 One or more of the groups contains an acid labile group.

[0053] In some embodiments, the photoactive compound of formula (1) can be represented by one or more of formulas (4a)-(4c): [ka]

[0054] In formulas (4a) and (4b), Y 1 and Y 2 is Y in equation (1). 1 and Y 2 In formula (4c), Y 1 and Y 2 is Y in equation (1). 1 and Y 2 is as defined for Y 3 and Y 4 is expressed as Y in equation (2a). 3 and Y 4 is as defined above.

[0055] In formulas (4a) to (4c), each R 3 are independently halogen, cyano, 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 6~30Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 6~30 Aryloxy, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is heteroaryloxy.

[0056] In formulas (4a) to (4c), each R 3 independently and optionally further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups are -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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof; 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 It may be heteroaryl.

[0057] In the formulas (4a) to (4c), a is an integer of 0 to 4, preferably 0 to 2, and typically 0 or 1.

[0058] In formulas (4a) to (4c), when a is 2 or more, two or more adjacent R 3may optionally be joined together to form a ring, which ring optionally further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0059] The anions represented by formulas (4a) to (4c) may not contain fluorine. For example, in formulas (4a) and (4b), R 3 , Y 1 , and Y 2 At least one of the groups does not contain fluorine, and preferably R 3 , Y 1 , and Y 2 For example, in formula (4c), R 3 , Y 1 , Y 2 , Y 3 , and Y 4 At least one of the groups does not contain fluorine, and preferably R 3 , Y 1 , Y 2 , Y 3 , and Y 4 All of these do not contain fluorine.

[0060] 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 At least one of R 3 , Y 1 , Y 2 , Y 3 , and Y 4 One or more of the groups contains an acid labile group.

[0061] In some embodiments, the photoactive compound of formula (1) can be represented by one or more of formulas (5a)-(5c): [ka]

[0062] In formulas (5a) to (5c), R 3 and a are R in formulas (4a) to (4c), respectively. 3 and a are as defined above.

[0063] In formulas (5a) and (5b), R 4 and R 5 are each independently hydrogen, 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 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 6~30 Aryloxy, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is heteroaryloxy.

[0064] In formulas (5a) and (5b), R 4 and R 5 each independently optionally further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups are -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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof; R ’ is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 1~20Heteroalkyl, substituted or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be heteroaryl.

[0065] In formulas (5a) and (5b), R 4 and R 5 may optionally be joined together to form a ring, which ring optionally further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0066] In formula (5c), R 4 ~R 7 are each independently hydrogen, 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 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 6~30 Aryloxy, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is heteroaryloxy.

[0067] In formula (5c), R 4 ~R 7 each independently optionally further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups are -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 3~30Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof; 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 It may be heteroaryl.

[0068] In formula (5c), R 4 and R 5 may optionally be joined together to form a ring, which ring optionally further comprises one or more divalent linking groups as part of its structure, each of which may be substituted or unsubstituted, and the ring may be substituted or unsubstituted; and / or R 6 and R 7 may optionally be joined together to form a ring, which ring optionally further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0069] The anions represented by formulas (5a) to (5c) may not contain fluorine. For example, in formulas (5a) and (5b), R 3 , R 4 , and R 5 At least one of the groups does not contain fluorine, and preferably R 3 , R 4 , and R 5 For example, in formula (5c), R 3 ~R 7 At least one of the groups does not contain fluorine, and preferably R 3 ~R 7 All of these do not contain fluorine.

[0070] 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 At least one of R 3 ~R 7 One or more of the groups contains an acid labile group.

[0071] In some embodiments, the photoactive compound of Formula (1) has the formula (6a)-(6c): [ka] (In the formula, Y 1 and Y 2 is Y in equation (1). 1 and Y 2 is as defined for Y 3 and Y 4 is expressed as Y in equation (2a). 3 and Y 4 is as defined for R 3 and a is R in formulas (4a) to (4c). 3 and a)

[0072] Exemplary anions represented by formula (1) include the following: [ka] [ka] [ka]

[0073] The photoactive compound also includes an organic cation. For example, the organic cation can be a sulfonium cation or an iodonium cation. In some embodiments, the organic cation can be a sulfonium cation of formula (7a) or an iodonium cation of formula (7b): [ka]

[0074] In formulas (7a) and (7b), R 8 ~R 12 are each independently a substituted or unsubstituted 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 6~30 Iodoaryl, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 7~20 Aryl alkyl, or substituted or unsubstituted C 4~20 heteroaryl, alkyl, or a combination thereof. 8 ~R 10 may be independent or may be connected to another group R via a single bond or a divalent linking group. 8 ~R 10 may be linked to form a ring. 11 and R 12 may be independent or may be linked to each other via a single bond or a divalent linking group to form a ring. 8 ~R 12 may optionally include a divalent linking group as part of its structure. 8 ~R 12 may optionally include acid labile groups independently selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

[0075] Exemplary sulfonium cations of formula (7a) include one or more of the following: [ka]

[0076] Exemplary iodonium cations of formula (7b) include one or more of the following: [ka]

[0077] The photoactive compounds may be prepared using any suitable method in the art, including those described in the Examples herein.

[0078] 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.

[0079] The polymer may contain one or more types of repeating units. The repeating units may be one or more units for the purpose of adjusting the properties of the photoresist composition, such as, for example, etch rate and solubility. Exemplary repeating units may include those derived from one or more of (meth)acrylate, vinyl aromatic, vinyl ether, vinyl ketone, 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 groups, acid-labile groups, base-solubilizing groups, lactone-containing groups, sultone-containing groups, polar groups, crosslinkable groups, crosslinking groups, etc., or combinations thereof.

[0080] In one or more embodiments, the polymer may include repeat units formed from monomers that include acid labile groups. Suitable acid labile groups include, for example, tertiary ester groups, acetal groups, ketal groups, and tertiary ether groups. [ka] [ka] (In these formulas, R dis hydrogen, halogen, substituted or unsubstituted C 1~6 Alkyl, or substituted or unsubstituted C 3~6 (cycloalkyl).

[0081] When a repeat unit having an acid labile group is present in the polymer, it is typically present in an amount of from 25 to 75 mol %, more typically from 25 to 50 mol %, and even more typically from 30 to 50 mol %, based on all repeat units in the polymer.

[0082] In some embodiments, the polymer may include repeat units derived from one or more lactone-containing monomers. Suitable lactone-containing monomers include, for example, one or more of the following: [ka] (In these formulas, R d is hydrogen, halogen, substituted or unsubstituted C 1~6 Alkyl, or substituted or unsubstituted C 3~6 (cycloalkyl).

[0083] In some embodiments, the polymer may include repeat units having base-solubilizing groups and / or having a pKa of less than or equal to 12. Exemplary base-solubilizing groups may include fluoroalcohol groups, carboxylic acid groups, carboximide groups, sulfonamide groups, or sulfonimide groups.

[0084] Non-limiting examples of monomers containing base solubilizing groups include one or more of the following: [ka] [ka] [ka] (In these formulas, each R iare independently hydrogen, halogen, substituted or unsubstituted C 1~6 Alkyl, or substituted or unsubstituted C 3~6 (cycloalkyl).

[0085] The polymer may optionally contain one or more additional repeating units. The additional repeating structural units may be, for example, one or more additional units for the purpose of adjusting the properties of the photoresist composition, such as etch rate and solubility. Exemplary additional units may include those derived from one or more of (meth)acrylate, vinyl aromatic, vinyl ether, vinyl ketone, and / or vinyl ester monomers. When present in the first and / or second polymer, the one or more additional repeating units may be used in an amount of up to 50 mol %, typically 3 to 50 mol %, based on the total repeating units of the polymer.

[0086] Non-limiting exemplary polymers of the present invention include one or more of the following: [ka] [ka] [ka] (In these formulas, each x, y, and z is the mole fraction of the associated repeat unit, the sum of the mole fractions for each polymer is 1, and each R d are independently hydrogen, halogen, substituted or unsubstituted C 1~6 Alkyl, or substituted or unsubstituted C 3~6 (cycloalkyl).

[0087] Further non-limiting exemplary polymers of the present invention include one or more of the following: [ka] (In these formulas, each x, y, and z is the mole fraction of the associated repeat unit, the sum of the mole fractions for each polymer is 1, and each R d are 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 (M) 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 ) M w and number average molecular weight (M n The polydispersity index (PDI) of the first polymer, which is the ratio of the molecular weights (molecules) to the molecular weights (molecules), is typically 1.1 to 3, more typically 1.1 to 2. Molecular weight values ​​are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0089] In the photoresist compositions of the invention, the polymer is typically present in the photoresist composition in an amount of from 10 to 99.9 weight percent, typically from 25 to 99 weight percent, and more typically from 50 to 95 weight percent, based on the total solids content of the photoresist composition, it being understood that total solids includes the polymer, PAG, and other non-solvent components.

[0090] The polymer can be prepared by any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined using a suitable solvent and initiator, or can be separately fed and polymerized in a reactor. For example, the polymer can be obtained by polymerizing each monomer under any suitable conditions, such as heating at an effective temperature, irradiating with actinic radiation of an effective wavelength, or a combination thereof.

[0091] The photoresist composition may further contain a photoacid generator (PAG). The PAG may be ionic or non-ionic. The PAG may be in polymeric or non-polymeric form. In the polymeric form, the PAG may be present as a moiety in the repeat unit of a polymer derived from polymerizable PAG monomers.

[0092] Suitable PAG compounds have the formula G + A - G + is a photoactive cation, and A - is an anion capable of generating a photoacid. The photoactive cation is preferably selected from onium cations, preferably iodonium or sulfonium cations such as those described above with respect to the photoactive compounds of the present invention (e.g., those of formula (7a) and / or (7b)). Particularly suitable anions include those whose conjugate acids have pKas of -15 to 10. The anion is typically an organic anion having a sulfonate group or a non-sulfonate-type group (such as a sulfonamidate, sulfonimidate, methide, or borate).

[0093] In some embodiments, the anion of the PAG does not contain or is free of -F, -CF3, or -CF2- groups. "Free of -F, -CF3, or -CF2- groups" should be understood to mean that groups such as -CH2CF3 and -CH2CF2CH3 are excluded from the anion of the PAG. In yet other embodiments, the anion of the PAG does not contain fluorine (i.e., it does not contain fluorine atoms and is not substituted with fluorine-containing groups). In some embodiments, the photoacid generator does not contain fluorine (i.e., both the photoactive cation and the anion do not contain fluorine).

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

[0095] Exemplary non-sulfonated anions include one or more of the following: [ka]

[0096] Commonly used onium salts include, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Other useful PAG compounds are known in the chemically amplified photoresist art, such as nonionic sulfonyl compounds, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl) Examples of suitable photoacid generators include diazomethane, glyoxime derivatives such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, sulfonate derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate, 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. Suitable photoacid generators are described in detail in Patent Document 1 and Patent Document 2.

[0097] Typically, when the photoresist composition includes an additional non-polymeric PAG, the PAG is present in the photoresist composition in an amount of from 0.1 to 55 weight percent, more typically from 1 to 25 weight percent, based on the total solids content of the photoresist composition. When used in polymeric form, the additional PAG is typically included in the polymer in an amount of from 1 to 25 mole percent, typically from 1 to 8 mole percent, or 2 to 6 mole percent, based on the total repeat units in the polymer.

[0098] The photoresist composition further comprises a solvent for dissolving the components of the composition and facilitating its coating on a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) (DAA); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, Examples of suitable solvents include ketones such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and ethyl acetoacetate; lactones such as gamma-butyrolactone (GBL) and epsilon-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, and DAA, or combinations thereof.

[0099] The total solvent content (i.e., the cumulative solvent content of all solvents) in a photoresist composition is typically 40 to 99 wt %, for example 60 to 99 wt %, or 85 to 99 wt %, based on the total solids content of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the coated photoresist layer and the coating conditions.

[0100] In some embodiments, the photoresist composition may further comprise a material containing one or more base-labile groups ("base-labile material"). As referred to herein, a base-labile group is a functional group that can undergo a cleavage reaction in the presence of an aqueous alkaline developer after the exposure and post-exposure bake steps to provide a polar group such as a hydroxyl, carboxylic acid, sulfonic acid, or the like. The base-labile group will not significantly react (e.g., will not undergo a bond-breaking reaction) before the development step of a photoresist composition containing the base-labile group. Thus, for example, the base-labile group will be substantially inert during the pre-exposure soft bake, exposure, and post-exposure bake steps. "Substantially inert" means that 5% or less, typically 1% or less, of the base-labile groups (or sites) decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-labile group reacts under typical photoresist development conditions, for example, using an aqueous alkaline photoresist developer such as an aqueous solution of 0.26N tetramethylammonium hydroxide (TMAH). For example, a 0.26N aqueous TMAH solution can be used for single puddle development or dynamic development, where the 0.26N TMAH developer is dispensed onto the imaged photoresist layer for a suitable time, such as 10 to 120 seconds (s). An exemplary base-labile group is an ester group, typically a fluorinated ester group. Preferably, the base-labile material is substantially immiscible with the first and / or second polymers and other solid components of the photoresist composition and has a lower surface energy than the first and / or second polymers and other solid components of the photoresist composition. When coated onto a substrate, the base-labile material can thereby separate from the other solid components of the photoresist composition to the top surface of the formed photoresist layer.

[0101] In some embodiments, the base-labile material can be a polymeric material, also referred to herein as a base-labile polymer, which can include one or more repeating units containing one or more base-labile groups. For example, the base-labile polymer can include repeating units containing two or more base-labile groups, which can be the same or different. Preferred base-labile polymers include at least one repeating unit containing two or more base-labile groups, for example, repeating units containing two or three base-labile groups.

[0102] The base-labile polymer can be prepared by any suitable method in the art.For example, the base-labile polymer can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof.In addition to this, or instead, one or more base-labile groups can be grafted onto the main chain of the polymer using a suitable method.

[0103] In some embodiments, the base-labile substance is a single molecule containing one or more base-labile ester groups, preferably one or more fluorinated ester groups. Single-molecule base-labile substances typically have an M in the range of 50 to 1,500 Da. W It has.

[0104] If present, the base-labile material is typically present in a photoresist composition in an amount of from 0.01 to 10 weight percent, typically from 1 to 5 weight percent, based on the total solids content of the photoresist composition.

[0105] In addition to or instead of the base-labile polymer, the photoresist composition can further include one or more polymers different from the photoresist polymers described above. For example, the photoresist composition can include an additional polymer as described above, but with a different composition. Additionally or alternatively, the one or more additional polymers can include those well known in the photoresist art, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornenes, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrenic polymers, polyvinyl alcohols, or combinations thereof.

[0106] The photoresist composition may further comprise one or more additional optional additives. For example, optional additives may include actinic dyes and contrast agents, anti-striation agents, plasticizers, rate enhancers, sensitizers, photolytic quenchers (PDQs) (also known as photolytic bases), base quenchers, thermal acid generators, surfactants, and the like, or combinations thereof. When present, optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 weight percent, based on the total solids content of the photoresist composition.

[0107] PDQ generates a weak acid upon irradiation. The acid generated from the photolytic deactivator is not strong enough to react rapidly with the acid labile groups present in the resist matrix. Exemplary photolytic deactivators include, for example, photolytic cations, preferably, for example, C 1~20 Carboxylic acid or C 1~20 Also included are those useful for preparing strong acid generator compounds paired with anions of weak acids (pKa > 1), such as anions of sulfonic acids. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, and the like. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, and the like. In a preferred embodiment, the photolytic quencher is a photolytic organic zwitterionic compound, such as diphenyliodonium-2-carboxylate.

[0108] PDQ may be in a non-polymeric form or a polymer-bound form. Polymerized units containing a photodegradable quencher are typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, and more preferably 1 to 2 mol %, based on the total repeat units of the polymer.

[0109] Exemplary basic quenching agents include, for example, straight-chain aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(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″-nitrilotriethanol; Cycloaliphatic amines such as N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N-(2-hydroxyethyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N-(2-acetoxyethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3linear and cyclic amides and derivatives thereof, 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; optionally substituted diazines, such as pyrazine, piperazine, and phenazine; optionally substituted diazoles, such as pyrazole, thiadiazole, and imidazole; and optionally substituted pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0110] The basic quenching agent may be in a non-polymeric form or in a polymer-bound form. When in a polymeric form, the quenching agent may be present in the repeating unit of the polymer. The repeating unit containing the quenching agent is typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, more preferably 1 to 2 mol %, based on the total repeating units of the polymer.

[0111] Exemplary surfactants include fluorinated and non-fluorinated surfactants, and may be ionic or non-ionic, with non-ionic surfactants being preferred. Exemplary fluorinated non-ionic 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 comprising a fluorine-containing repeating unit.

[0112] A patterning method using the photoresist composition of the present invention will now be described. Suitable substrates onto 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, including semiconductor wafers, polycrystalline silicon substrates, packaging substrates such as multichip modules, flat panel display substrates, and substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), 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), although wafers with smaller and larger diameters can be suitably used in accordance with the present invention. The substrate may include one or more layers or structures that may optionally include working or operable portions of the device being formed.

[0113] Typically, one or more lithography layers, such as a hard mask layer, e.g., a spin-on carbon (SOC), amorphous carbon, or metal hard mask layer, a CVD layer such as a 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 the photoresist composition of the invention. Such layers, together with an overcoated photoresist layer, form a lithography material stack.

[0114] Optionally, a layer of adhesion promoter can be applied to the substrate surface before coating with the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films can be used, such as a silane, typically an organosilane such as trimethoxyvinylsilane, triethoxyvinylsilane, or hexamethyldisilazane, or an aminosilane coupler such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names AP™ 3000, AP™ 8000, and AP™ 9000S, available from DuPont Electronics & Industrial (Marlborough, Massachusetts).

[0115] The photoresist composition can be coated onto a substrate by any suitable method, such as spin coating, spray coating, dip coating, doctor blading, etc. For example, application of a photoresist layer can be achieved by spin-coating the photoresist in a solvent using a coating truck, in which the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically spun at a speed of up to 4,000 revolutions per minute (rpm), e.g., 200 to 3,000 rpm, e.g., 1,000 to 2,500 rpm, for a time period of 15 to 120 seconds, resulting in a layer of photoresist composition on the substrate. Those skilled in the art will appreciate that the thickness of the coated layer can be adjusted by varying the spin speed and / or the total solids content 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] The photoresist composition is typically then soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. Soft-baking can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft-baking temperature and time will depend, for example, on the photoresist composition and thickness. The soft-baking temperature is typically 80 to 170°C, more typically 90 to 150°C. The soft-baking time is typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and even more typically 1 minute to 2 minutes. The heating time can be easily determined by one skilled in the art based on the components of the composition.

[0117] The photoresist layer is then patternwise exposed to activating radiation to create a solubility differential between exposed and unexposed regions. References herein to exposing a photoresist composition to radiation that activates the composition indicate that the radiation can form a latent image in the photoresist composition. Exposure is typically carried out through a patterned photomask having optically transparent and optically opaque regions corresponding to the exposed and unexposed regions of the resist layer, respectively. Such exposure can alternatively be carried out without a photomask in a direct-write process, typically used for electron beam lithography. Activating radiation typically has a wavelength of 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 electron beam lithography being preferred. Preferably, the activating radiation is 248 nm radiation. This method is utilized in immersion or dry (non-immersion) lithography techniques. Exposure energies are typically between 1 and 200 millijoules per square centimeter (mJ / cm), depending on the exposure tool and the components of the photoresist composition. 2 ), preferably 10 to 100 mJ / cm 2 , more preferably 20 to 50 mJ / cm 2 is.

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

[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 the remaining insoluble areas form the resulting photoresist pattern relief image. In a positive-tone development (PTD) process, the exposed areas of the photoresist layer are removed during development, leaving the unexposed areas. Conversely, in a negative-tone development (NTD) process, the exposed areas of the photoresist layer remain, while the unexposed areas are removed during development. Application of the developer can be accomplished by any suitable method, such as those described above with respect to application of the photoresist composition; spin coating is typical. The development time is a period effective to remove the soluble areas of the photoresist, typically between 5 and 60 seconds. Development is typically performed at room temperature.

[0120] Suitable developers for the PTD process include aqueous base developers, such as quaternary ammonium hydroxide solutions such as TMAH, preferably 0.26N TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent-based, meaning that the cumulative content of organic solvent 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.

[0121] Coated substrates can be formed from the photoresist compositions of the invention. Such coated substrates include (a) a substrate having one or more layers to be patterned on its surface; and (b) a layer of a photoresist composition over the one or more layers to be patterned.

[0122] The photoresist pattern can be used, for example, as an etch mask, allowing the pattern to be transferred to one or more subsequent underlying layers by known etching techniques, typically dry etching such as reactive ion etching. The photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, which in turn is 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, for example, oxygen plasma ashing. When used in one or more such pattern formation processes, the photoresist composition 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 present invention is further illustrated by the following non-limiting examples. [Example]

[0124] Synthesis Examples. Synthesis reactions were carried out under a nitrogen atmosphere. All chemicals were used as received from commercial suppliers and without further purification. Proton nuclear magnetic resonance (NMR) of all compounds was performed. 1 H-NMR spectra were obtained on a 500 megahertz (MHz) NMR spectrometer. Chemical shifts are reported in δ (parts per million, ppm) relative to the internal standard tetramethylsilane. Multiplicities are indicated as singlet (s), doublet (d), triplet (t), multiplet (m), doublet of doublets (dd), triplet of doublets (dt), triplet of triplets (tt), or broad singlet (br).

[0125] Synthesis of Q1 [ka] To a solution of compound A (0.66 grams (g), 1.99 millimoles (mmol)) in 10 milliliters (mL) of dichloromethane (DCM) was added compound B (0.68 g, 2 mmol) and 10 mL of deionized (DI) water. The resulting biphasic reaction mixture was stirred at room temperature for 1 hour. The organic layer was then separated and washed with 5 mL of DI water. After washing, the organic layer was again separated, and the solvent was removed under reduced pressure to yield 1.1 g (96%) of product Q1 as a beige solid. 1 H-NMR (d, dimethyl sulfoxide-d 6( DMSO-d6)) 7.92-7.75 ppm (17H,m), 7.64-7.56 ppm (2H,m), and 1.64 ppm (6H,m).

[0126] Synthesis of Q2 [ka] To a solution of compound A (0.66 g, 1.99 mmol) in 10 mL of DCM was added compound C (0.9 g, 2 mmol) and 10 mL of DI water. Following the same procedure as in the synthesis of Q1, 1.3 g (93%) of product Q2 was obtained as a white-orange solid. 1 H-NMR(d,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).

[0127] Synthesis of Q3 [ka] To a solution of compound D (0.5 g, 1.55 mmol) in 10 mL of DCM, compound B (0.6 g, 3 mmol) and 10 mL of DI water were added. Following the same procedure as in the synthesis of Q1, 0.75 g (80%) of product Q3 was obtained as a pale yellow oil. 1 H-NMR(d,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).

[0128] Synthesis of Q4 [ka] To a solution of compound E (2.0 g, 6.26 mmol) in 20 mL of DCM was added compound B (2.0 g, 5.82 mmol) and 20 mL of DI water. The resulting biphasic reaction mixture was then stirred at room temperature for 4 hours. The organic layer was separated and washed five times with 15 mL of DI water each. The organic layer was again separated and the solvent was removed under reduced pressure to give Q4 as a white solid. 1 H-NMR(d,DMSO-d6)7.69-7.59 ppm(17H,m), 7.64-7.42 ppm(2H,m), and 2.6 ppm(6H,s).

[0129] Synthesis of Q5 [ka] To a solution of compound E (1.0 g, 3.13 mmol) in 20 mL of DCM was added compound C (1.4 g, 3.9 mmol) and 20 mL of DI water. Following the same procedure as in the synthesis of Q4, Q5 was obtained as a white solid. 1 H-NMR(d,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).

[0130] Contrast evaluation Photoresist compositions were prepared by dissolving the solid components in a solvent to a total solids content of 1.55 wt% using the materials and proportions shown in Table 1. Component amounts are reported as weight percent based on the total solids content of the photoresist composition. The solvent system included PGMEA (50 wt%) and diacetone alcohol (50 wt%). The resulting mixture was shaken on a mechanical shaker and then filtered through a PTFE disk filter with a 0.2 micron pore size. A 200 mm silicon wafer overcoated with a BARC stack (60 nm thick AR™ 3 antireflective material (DuPont Electronics & Industrial) on an 80 nm thick AR™ 40A antireflective material) was spin-coated with each photoresist composition on a TEL Clean Track ACT 8 wafer track (TEL, Tokyo Electron Co.) and soft-baked at 110°C for 60 seconds to obtain a photoresist layer with a target thickness of approximately 40 nm. The resist layer thickness was measured using a THERMAL-WAVE OP7350. The wafer was irradiated with 3 to 53 millijoules per square centimeter (mJ / cm 2The wafers were exposed to 248 nm radiation using a CANON FPA-5000 ES4 scanner at an exposure dose of 100 Å. The wafers were post-exposure baked at 100°C for 60 seconds, developed in MF™ CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with DI water, and dried. Photoresist layer thickness measurements were taken in the exposed areas of the layer. A contrast curve was generated for each wafer, and E was determined from the contrast curve as described above. An additional contrast curve was generated for each wafer by plotting the normalized photoresist layer thickness in the exposed area against the logarithm of the dose. The contrast (γ) was determined from the normalized contrast curve as the slope between the 80% and 20% photoresist film thickness points. The results are shown in Table 1.

[0131] [Table 1]

[0132] [ka]

[0133] Lithography Evaluation Photoresist compositions were prepared by dissolving solid components in solvent using the materials and amounts shown in Table 2 to a total solids content of 4.15 wt%. Component amounts are reported as weight percent based on the total solids content of the photoresist composition. The solvent system included PGMEA (50 wt%) and diacetone alcohol (50 wt%). Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disk filter with a 0.2 micron pore size. Lithography was performed using a CLEAN TRACK ACT8 (TEL, Tokyo Electron Co.) wafer track. 200 nm wafers for photolithography testing were coated with AR™ 3 BARC (DuPont Electronics & Industrial) and soft-baked at 205°C for 60 seconds to obtain a 60 nm film. A coating of AR™ 40A BARC (DuPont Electronics & Industrial) was then placed 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. A photoresist composition was then coated onto the dual BARC stack and soft-baked at 110° C. for 60 seconds to obtain a photoresist film layer with a thickness of 120 nm.

[0134] The resulting wafer was exposed to 248 nm radiation using a CANON FPA-5000 ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57) with a mask having a 1:1 CH pattern (200 nm linewidth). The exposed wafer was post-exposure baked at 100°C for 60 seconds, developed in a 0.26 N TMAH solution for 60 seconds, then rinsed with DI water and spin-dried to form a photoresist pattern. Critical dimension (CD) linewidth measurements of the formed patterns were performed using a HITACHI S-9380 CD-SEM. Local critical dimension uniformity (LCDU) was determined based on the CD measurements. Sizing energy (E size ) and LCDU data are shown in Table 2.

[0135] [Table 2]

[0136] [ka]

[0137] While the present disclosure has been described in conjunction with what are presently considered to be practical exemplary embodiments, it is to 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. an organic cation selected from the group consisting of iodonium cations and sulfonium cations; Formulas (5a) to (5c): 【Chemical 1】 (In formulas (5a) to (5c), Each R ３ are independently halogen, cyano, 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 ６～３０ Aryl, substituted or unsubstituted C ７～３０ Aryl alkyl, substituted or unsubstituted C ７～３０ Alkylaryl, substituted or unsubstituted C ６～３０ Aryloxy, substituted or unsubstituted C ３～３０ Heteroaryl, substituted or unsubstituted C ４～３０ Alkylheteroaryl, substituted or unsubstituted C ４～３０ Heteroarylalkyl, or substituted or unsubstituted C ３～３０ heteroaryloxy; Each R ３ may independently and optionally further include one or more divalent linking groups as part of its structure; a is an integer of 0 to 4, and when a is 2 or more, two or more adjacent R ３ may optionally be joined together to form a ring; In formulas (5a) and (5b), R ４ and R ５ are each independently hydrogen, 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 ６～３０ Aryl, substituted or unsubstituted C ７～３０ Aryl alkyl, substituted or unsubstituted C ７～３０ Alkylaryl, substituted or unsubstituted C ６～３０ Aryloxy, substituted or unsubstituted C ３～３０ Heteroaryl, substituted or unsubstituted C ４～３０ Alkylheteroaryl, substituted or unsubstituted C ４～３０ Heteroarylalkyl, or substituted or unsubstituted C ３～３０ heteroaryloxy; R ４ and R ５ may each independently optionally further include one or more divalent linking groups as part of its structure; R ４ and R ５ may optionally be joined together to form a ring; In formula (5c), R ４ ~R ７ are each independently hydrogen, 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 ６～３０ Aryl, substituted or unsubstituted C ７～３０ Aryl alkyl, substituted or unsubstituted C ７～３０ Alkylaryl, substituted or unsubstituted C ６～３０ Aryloxy, substituted or unsubstituted C ３～３０ Heteroaryl, substituted or unsubstituted C ４～３０ Alkylheteroaryl, substituted or unsubstituted C ４～３０ Heteroarylalkyl, or substituted or unsubstituted C ３～３０ heteroaryloxy; R ４ ~R ７ may each independently optionally further include one or more divalent linking groups as part of its structure; R ４ and R ５ may optionally be joined together to form a ring, and / or R ６ and R ７ may optionally be joined together to form a ring and an anion represented by any one of the following: A photoactive compound comprising:

2. 2. The photoactive compound of claim 1, wherein the anion represented by formulas (5a) to (5c) does not contain fluorine.

3. The photoactive compound of claim 1 , wherein the anion comprises one or more acid labile groups.

4. The photoactive compound of claim 1; a polymer; A photoresist composition comprising:

5. 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 labile groups.

6. Applying a layer of the photoresist composition of claim 4 or 5 to a substrate to obtain a photoresist composition layer; patternwise exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer; A pattern forming method comprising:

Images