Photoactive compound, photoresist composition containing the same, and pattern formation method

Abstract

To provide a photoactive compound, a photoresist composition containing the same, and a pattern formation method.SOLUTION: A photoactive compound is represented by formula (1a) or (1b). (In formula, R1 is substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, or substituted or unsubstituted C3-30 heteroaryl comprising an aromatic ring heteroatom selected from nitrogen, oxygen, or a combination thereof; R2-R3 are as provided in the specification; R4 is substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, or substituted or unsubstituted C3-30 heteroaryl; and M+ is an organic cation.)

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 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 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. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 8,431,325 [Patent Document 2] U.S. Patent No. 4,189,323 [Patent Document 3] US Patent No. 8,936,000 B2 Summary of the Invention [Problem to be solved by the invention]

[0006] Photoresist compositions containing photodecomposable quenchers and their uses have been described in the art. However, for many other applications, new photoresists are needed that can provide excellent line edge roughness (LWR) and wider depth of focus (DOF) for high-resolution inter-line features. [Means for solving the problem]

[0007] Formula (1a) or (1b): [ka] (In the formula, R 1 is 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 substituted or unsubstituted C containing an aromatic ring heteroatom selected from aryl, nitrogen, oxygen, or a combination thereof; 3~30 Heteroaryl; R 2 is hydrogen, halogen, 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 groups, substituted or unsubstituted C1-C 30 Alkylthio group, substituted or unsubstituted C3-C 10 Cycloalkenyl groups, substituted or unsubstituted C3-C 10 Heterocycloalkenyl group, 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 is an aryloxy group; R 3 is hydrogen or a non-hydrogen substituent; R 4 is 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 or substituted or unsubstituted C 3~30 Heteroaryl; R2 , R 3 and R 4 each of which optionally further comprises one or more divalent linking groups as part of their structure, each of which is independently substituted or unsubstituted; R 2 and R 3 optionally form, together, a ring that optionally further includes one or more divalent linking groups as part of its structure, each of the one or more linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted; and M + is an organic cation) The photoactive compounds are provided.

[0008] Another aspect provides a photoresist composition comprising a photoactive compound and a solvent.

[0009] Yet another aspect provides a method of forming a pattern, the method comprising: (a) forming a photoresist layer from a photoresist composition; (b) patternwise exposing the photoresist layer to activating radiation; and (c) developing the exposed photoresist layer to provide a resist relief image. 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 bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, particle rays such as electron beams and ion beams, etc. Furthermore, in the present invention, "light" refers to actinic rays or radiation.

[0014] An argon fluoride laser (ArF laser) is a specific type of excimer laser, sometimes referred to as an exciplex laser. "Excimer" stands for "excimer dimer," while "exciplex" stands for "exciplex." Excimer lasers use a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine), which, under suitable conditions of electrical stimulation and high voltage, emits coherent, stimulated radiation (laser light) in the ultraviolet range.

[0015] 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.

[0016] As used herein, the term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight or branched chain saturated hydrocarbon group having the specified number of carbon atoms and having a valence of one; "alkylene" refers to an alkyl group having a valence of two; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; and "carbohydrate" refers to an alkyl group having a valence of two. "Boxyl" and "carboxylic acid" 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; "cycloalkylene" refers to a cycloalkyl group having a valence of two; "alkenyl" refers to a straight- or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; and "alkenylene" refers to an alkenyl group having a valence of two; "Cycloalkenyl" refers to a non-aromatic cyclic monovalent hydrocarbon group having at least three carbon atoms and having at least one 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 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 include groups 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-".

[0017] The prefix "hetero" means that the compound or group contains at least one member that is a heteroatom (e.g., 1, 2, 3, or more heteroatoms) in place of a carbon atom, where the heteroatoms are each independently N, O, S, Si, or P; a "heteroatom-containing group" refers to a substituent that contains at least one heteroatom; "heteroalkyl" refers to an alkyl group having at least one heteroatom in place of carbon; "heterocycloalkyl" refers to a cycloalkyl group having at least one heteroatom in place of carbon as a ring member; and "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of two.

[0018] The term "heteroaryl" refers to an aromatic 4- to 8-membered monocyclic, 8- to 12-membered bicyclic, or 11- to 14-membered tricyclic ring system having 1 to 4 heteroatoms (monocyclic), 1 to 6 heteroatoms (bicyclic), or 1 to 9 heteroatoms (tricyclic) each independently selected from N, O, S, Si, or P (e.g., carbon atoms and 1 to 3, 1 to 6, or 1 to 9 N, O, or S heteroatoms in the monocyclic, bicyclic, or tricyclic ring, respectively). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl, or thienyl, quinolinyl, indolyl, thiazolyl, and the like.

[0019] Unless expressly stated otherwise, each of the foregoing substituents may be optionally substituted. The term "optionally substituted" refers to substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of the chemical structure is replaced with another terminal substituent, which is typically monovalent, provided that the normal valence of the designated atom is not exceeded. When a 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 in 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 2~6 Alkyl 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., where 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 6~12Examples of arylsulfonyl include, but are not limited to, arylsulfonyl (-S(=O)-aryl) or tosyl (CHCHSO-). If a group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, excluding carbon atoms of any substituents. For example, the group -CHCHCN is a cyano-substituted C alkyl group.

[0020] 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. It should be understood that substitution of a group with a halogen atom is not considered a heteroatom-containing group because the halogen atom does not replace a carbon atom.

[0021] As used herein, "acid labile group" refers to a group whose bond is cleaved by the catalytic action of an acid, optionally and typically with thermal treatment, resulting in the formation of a polar group, such as a carboxylic acid group or an alcohol group, formed on the polymer; optionally and typically, the moiety attached to the cleaved bond is cleaved from the polymer. In other systems, non-polymeric compounds may contain acid labile groups that can be cleaved by the catalytic action of an acid, resulting in the formation of a polar group, such as a carboxylic acid group or an alcohol group, on the cleaved portion of the non-polymeric compound. Such acids are typically photogenerated acids that cause bond cleavage during post-exposure baking; however, embodiments are not limited thereto; for example, such acids may 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."

[0022] 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 3~30Typically, 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 combinations 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 3~10 heteroarylene, 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.

[0023] The present invention relates to photoactive compounds, such as photodegradable quencher (PDQ) compounds. Specifically, the photoactive compounds of the present invention are salts containing α,β-unsaturated carboxylates that can be used in photoresist compositions to achieve improved roughness and wider DOF of printed features.

[0024] The photoactive compound is of formula (1a) or (1b). [ka]

[0025] In formula (1a), R 1 is 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 substituted or unsubstituted C containing an aromatic ring heteroatom selected from aryl, nitrogen, oxygen, or a combination thereof; 3~30 Heteroaryl. Preferably, R 1 is a substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 substituted or unsubstituted C containing an aromatic ring heteroatom selected from aryl, nitrogen, oxygen, or a combination thereof; 3~20 may be heteroaryl, typically R 1 is a substituted or unsubstituted C 6~20 Substituted or unsubstituted C containing an aromatic ring heteroatom selected from aryl, nitrogen, or oxygen 3~20 may be heteroaryl, substituted C 6~20 Aryl and Substituted C 3~20 Each heteroaryl is independently selected from a halogen, a hydroxyl group, a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C6-C 20 Aryloxy, substituted or unsubstituted C3-C 20 Heteroaryl or of the formula -C(O)OR 8 (In the formula, R 8 is a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10The aryl group may be substituted with at least one of the following groups:

[0026] In formula (1a), R 2 is hydrogen, halogen, 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 groups, substituted or unsubstituted C1-C 30 Alkylthio group, substituted or unsubstituted C3-C 10 Cycloalkenyl groups, substituted or unsubstituted C3-C 10 Heterocycloalkenyl group, 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 An aryloxy group is preferably R 2 is hydrogen, halogen, or substituted or unsubstituted C 1~10 It can be alkyl, typically R 2 can be hydrogen.

[0027] In formula (1a), R 2 and R 3 each optionally further include one or more divalent linking groups as part of their structure, and each of the one or more divalent linking groups is independently substituted or unsubstituted.

[0028] In formula (1a), R and R 3 optionally form a ring together that 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.

[0029] In formula (1a), R 3 is hydrogen or a non-hydrogen substituent. For example, R 3 is hydrogen or substituted or unsubstituted C 1~20 In some embodiments, R 3 -C(O)-, -C(O)O-, -C(O)N(R 5 )- or a combination thereof 1~20 R may be an organic group. 5 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 In another embodiment, R 3 is a halogen atom, a cyano group, or a substituted or unsubstituted C 1~5 In some embodiments, R 1 is substituted or unsubstituted C 6~30 When R is aryl, 3 is not hydrogen or halogen.

[0030] In formula (1b), R 4 is 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 or substituted or unsubstituted C 3~30 Heteroaryl. Preferably, R 4 is a substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 For example, R 4 is a substituted or unsubstituted C 6~18 Aryl or substituted or unsubstituted C 3~18 may be heteroaryl, substituted C 6~18 Aryl and Substituted C3~18 Heteroaryl is a heteroaryl group that can be substituted with halogen, amino (-NH2), mono- or di-(C 1~6 ) alkylamino, substituted or unsubstituted C 1~6 Alkyl, substituted or unsubstituted C 1~6 Haloalkyl, substituted or unsubstituted C 1~9 Alkoxy, substituted or unsubstituted C 2~6 Alkenyl, substituted or unsubstituted C 6~12 Aryl, substituted or unsubstituted C 3~12 R is substituted with at least one of aryl, ... 4 optionally further includes one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups being independently substituted or unsubstituted.

[0031] In formulas (1a) and (1b), M + is an organic cation. For example, M + can be a sulfonium cation or an iodonium cation. In some embodiments, M + can be a sulfonium cation of formula (2a) or an iodonium cation of formula (2b). [ka]

[0032] In formulas (2a) and (2b), R 10 , R 20 and R 30 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 R can be heteroarylalkyl. 10 , R20 and R 30 may be separate or may be connected to R via a single bond or a divalent linking group. 10 , R 20 or R 30 R can either be bonded to another group to form a ring. 10 , R 20 and R 30 Each of R may optionally include a divalent linking group as part of its structure. 10 , R 20 and R 30 Each of R may independently optionally include an acid labile group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group. 10 , R 20 and / or R 30 Suitable divalent linking groups for linking groups include, for example, -O-, -S-, -Te-, -Se-, -C(O)-, -C(S)-, -C(Te)-, or -C(Se)-, substituted or unsubstituted C 1~5 alkylene or combinations thereof.

[0033] Exemplary sulfonium cations of formula (2a) include: [ka]

[0034] Exemplary iodonium cations of formula (2b) include: [ka]

[0035] In some embodiments, the photoactive compound of formula (1a) can be represented by formula (3a): [ka]

[0036] In formula (3a), ring CY1 is C 3~30 Carbocyclic group or C 3~30 Preferably, ring CY1 is C 3~8 Cycloalkyl, C 6~14 C containing an aromatic ring heteroatom selected from aryl, nitrogen, oxygen, or a combination thereof 3~12 It is heteroaryl.

[0037] In formula (3a), each L 1 may independently be a single bond or a divalent linking group.

[0038] In formula (3a), each R 8 are independently hydroxyl, -F, -I, -CF, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 It may be heteroaryl.

[0039] In formula (3a), a is an integer of 0 to 10. Preferably, a is an integer of 0 to 5, and typically, a is an integer of 0 to 3.

[0040] In formula (3a), L 2 represents a single bond, -C(O)-, -C(O)O- or -C(O)N(R 5a )-(wherein, R 5a is hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 1~10 Heteroalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 Heteroaryl).

[0041] In formula (3a), R 9 is hydrogen, cyano, hydroxyl, -F, -I, -CF3, substituted or unsubstituted C 1~10Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 In some embodiments, R 9 is substituted C 1~10 Alkyl, substituted C 3~20 Cycloalkyl, substituted C 3~20 Heterocycloalkyl, substituted C 6~10 Aryl or substituted C 3~10 When R is heteroaryl, 9 At least one substituent of the group can be hydroxy, -I, or a combination thereof.

[0042] In formula (3a), M + is the same as defined in equation (1a).

[0043] In some embodiments, the photoactive compound of formula (1b) can be represented by formula (3b): [ka]

[0044] In formula (3b), ring CY2 is C 3~30 Carbocyclic group or C 3~30 Preferably, ring CY2 is C 3~8 Cycloalkyl, C 6~14 C containing an aromatic ring heteroatom selected from aryl, nitrogen, oxygen, or a combination thereof 3~12 It is heteroaryl.

[0045] In formula (3b), b is an integer of 0 to 10. Preferably, b is an integer of 0 to 5, and typically, b is an integer of 0 to 3.

[0046] In formula (3b), L 3 represents a single bond, -C(O)-, -C(O)O- or -C(O)N(R 5b )-(wherein, R5b is hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 1~10 Heteroalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 Heteroaryl).

[0047] In formula (3b), R 11 is hydrogen, cyano, hydroxyl, -F, -I, -CF3, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 In some embodiments, R 9 is substituted C 1~10 Alkyl, substituted C 3~20 Cycloalkyl, substituted C 3~20 Heterocycloalkyl, substituted C 6~10 Aryl or substituted C 3~10 When R is heteroaryl, 9 At least one substituent of the group can be hydroxy, -I, or a combination thereof.

[0048] In formula (3b), M + is the same as defined in equation (1b).

[0049] Non-limiting examples of the anionic portion of the photoactive compound of formula (1a) can include one or more of the following compounds: [ka] [ka] [ka]

[0050] Non-limiting examples of the anionic portion of the photoactive compound of formula (1b) can include one or more of the following compounds: [ka]

[0051] The present invention further relates to photoresist compositions comprising a photoactive compound and a solvent, and may contain additional optional components. Typically, the photoresist composition will further comprise a polymer, a photoacid generator (PAG), or a combination thereof.

[0052] According to one embodiment, the photoresist composition further comprises a material that switches its solubility in a base or in an organic solvent under the action of an acid, the material being different from the photoactive compound. For example, this material can be a polymer or a molecular glass.

[0053] The polymer may include one or more repeating 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.

[0054] In some embodiments, the polymer may include repeat units that include acid labile groups. For example, the repeat units that include acid labile groups may be derived from one or more monomers of formula (4), (5), or (6). [ka]

[0055] In equations (4), (5) and (6), R a ~R c are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R a ~R care each independently hydrogen, fluorine, or substituted or unsubstituted C 1~5 It may be alkyl, typically methyl.

[0056] In equation (4), L 4 is a divalent linking group. For example, L 4 may contain 1 to 10 carbon atoms and at least one heteroatom. 4 is -OCH2-, -OCH2CH2O- or -N(R 5c )(in the formula -, R 5c is hydrogen or C 1~6 alkyl).

[0057] In equations (4) and (5), R 21 ~R 26 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 heteroaryl, provided that R 21 ~R 23 may be hydrogen and R 24 ~R 26 may be hydrogen, and R 21 ~R 23 If one of is hydrogen, R 21 ~R 23 At least one of the groups other than C is substituted or unsubstituted 6~20 Aryl or substituted or unsubstituted C 3~20 heteroaryl, and R 24 ~R 26 If one of the is hydrogen, 24 ~R 26 At least one of the groups other than C is substituted or unsubstituted 6~20Aryl or substituted or unsubstituted C 3~20 provided that it is heteroaryl. Preferably, R 21 ~R 26 are each independently a substituted or unsubstituted C 1~6 Alkyl or substituted or unsubstituted C 3~10 Cycloalkyl. R 21 ~R 26 Each of may optionally further include a divalent linking group as part of its structure.

[0058] In equation (4), R 21 ~R 23 Any two of may optionally form a ring together via a single bond or a divalent linking group, and this ring may be substituted or unsubstituted. 24 ~R 26 Any two of may together optionally form a ring via a single bond or a divalent linking group, which ring may be substituted or unsubstituted.

[0059] For example, R 21 ~R 26 any one or more of the formula -CHC(=O)CH (3-n) Y n wherein each Y is independently a substituted or unsubstituted C 2~10 heterocycloalkyl, where n is 1 or 2. For example, each Y can independently be a group of the formula —O(C a1 )(C a2 )O-(wherein, C a1 and C a2 are each independently hydrogen or substituted or unsubstituted alkyl, and C a1 and C a2 and optionally form a ring together) 2~10 It may be a heterocycloalkyl.

[0060] In equations (6) and (8), R 27 , R 28 , R 34 and R 35 are each independently hydrogen, substituted or unsubstituted C1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 may be heteroaryl; R 16 and R 22 are each independently a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 Preferably, R 27 , R 28 , R 34 and R 35 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 R can be heterocycloalkyl. 27 , R 28 , R 34 and R 35 Each of may optionally further include a divalent linking group as part of their structure.

[0061] In equation (7), R 31 ~R 33 are each independently a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 may be heteroaryl, provided that R 31 ~R 33 may be hydrogen, and R 31 ~R 33 If one of is hydrogen, R 31 ~R 33 At least one of the groups other than C is substituted or unsubstituted 6~20 Aryl or substituted or unsubstituted C 3~20R is heteroaryl. 31 ~R 33 Each of may optionally further include a divalent linking group as part of its structure.

[0062] In equation (7), R 31 ~R 33 Any two of these together form a ring which may optionally further include a divalent linking group as part of its structure, and the ring group may be substituted or unsubstituted.

[0063] In equations (7) and (8), X a and X b are each independently substituted or unsubstituted C 20 It is a polymerizable group containing an ethylenically unsaturated double bond, such as alkenyl or substituted or unsubstituted norbornyl, preferably (meth)acrylate or C2 alkenyl.

[0064] In equations (7) and (8), L 5 and L 6 are each independently a single bond or a divalent linking group, provided that L 5 is X a is not a single bond when L is C2 alkenyl; 6 is X b is not a single bond when L is C2 alkenyl. 5 and L 6 are each independently a substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 6~30 In formulas (7) and (8), n1 is 0 or 1, and n2 is 0 or 1. When n1 is 0, L 5 It should be understood that the group is directly attached to the oxygen atom. When n2 is 0, L 6 It should be understood that the group is attached directly to the oxygen atom.

[0065] In equation (8), R 34 ~R 36Any two of may together form a ring, which may optionally further include a divalent linking group as part of its structure, which ring may be substituted or unsubstituted.

[0066] In some embodiments, R 21 ~R 29 and R 31 ~R 36 Each of the groups may contain -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ )- or -C(O)N(R')- (wherein R ’ is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 The bicyclic linking group may optionally further include one or more bicyclic linking groups selected from the group consisting of cycloalkyl, ...

[0067] In some embodiments, in repeat units that include an acid labile group, the acid labile group can be a tertiary alkyl ester. For example, the repeat unit that includes a tertiary alkyl ester group can be derived from one or more monomers of formula (4), (5), or (7), where R 21 ~R 26 or R 34 ~R 36 None of the groups are hydrogen, and n1 is 1.

[0068] Exemplary monomers of formula (4) include one or more of the following: [ka]

[0069] Exemplary monomers of formula (5) include the following: [ka] [ka] (In the formula, Rd is R in equation (3). b is as defined in terms of R ’ and R ’’ are each independently a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 Heteroaryl) Contains one or more of the following:

[0070] Exemplary monomers of formula (6) include the following: [ka] (In the formula, R d is R c (as defined above for Contains one or more of the following:

[0071] Exemplary monomers of formula (7) include one or more of the following: [ka]

[0072] Exemplary monomers of formula (8) include one or more of the following: [ka]

[0073] In some embodiments, the polymer has a cyclic acetal or cyclic ketal group, for example, the following structure: [ka] (In the formula, R d is R a (as defined above for The acid labile repeat units may be derived from one or more monomers having one or more of the following structures:

[0074] In some embodiments, the polymer may have repeat units with acid labile groups that include tertiary alkoxy groups, such as one or more of the following monomers: [ka]

[0075] When present, repeat units containing acid labile groups are typically present in the polymer in an amount of from 5 to 95 mol %, more typically from 20 to 80 mol %, and even more typically from 30 to 50 mol %, based on all repeat units in the polymer.

[0076] In some embodiments, the polymer may further include a repeat unit comprising a polar group, the polar group being pendant to the backbone of the polymer. For example, the polar group may be a lactone group, a hydroxyaryl group, a fluoroalcohol group, or a combination thereof.

[0077] In one or more embodiments, the polymer may further include a third repeat unit derived from one or more lactone-containing monomers of formula (9). [ka]

[0078] In equation (9), R f is hydrogen, fluorine, cyano or substituted or unsubstituted C 1~10 It is alkyl.

[0079] In equation (9), L 7 is a single bond or a divalent linking group. 7 is a single bond or a substituted or unsubstituted C 1~30Alkylene, substituted or unsubstituted C 1~30 Heteroalkylene, 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, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ )- or -C(O)N(R ’’ )-(wherein, R ’ and R ’’ are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 L is one or more groups selected from the group consisting of aryl, aryl(s), ... 7 If is a single bond, the moiety -R 37 is directly attached to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)OR 37 ).

[0080] In equation (9), R 37 is a substituted or unsubstituted C 4~20 Lactone-containing group or substituted or unsubstituted C 4~20 It is a sultone-containing group. 4~20 Lactone-containing groups and C 4~20 The sultone-containing group can be monocyclic, polycyclic, or fused polycyclic.

[0081] Exemplary monomers of formula (9) include the following: [ka] (In the formula, R f is as defined for equation (9) may include one or more of the following:

[0082] The polymer may include repeat units that are base soluble and / or have a pKa of less than or equal to 12. For example, repeat units that include a polar group pendant to the backbone of the polymer may be derived from one or more monomers of formula (10), (11), or (12). [ka]

[0083] In formula (10), (11) or (12), R g ~R j are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R g ~R j are each independently hydrogen, fluorine, or substituted or unsubstituted C 1~5 It may be alkyl, typically methyl.

[0084] In equation (10), R 38 is a substituted or unsubstituted C 1~100 Or C 1~20 Alkyl, typically C 1~12 Alkyl; substituted or unsubstituted C 3~30 Or C 3~20 cycloalkyl; or substituted or unsubstituted poly(C 1~3 alkylene oxide). Preferably, the substituted C 1~100 Or C 1~20 Alkyl, substituted C 3~30 Or C 3~20 Cycloalkyl and substituted poly(C 1~3 Alkylene oxide) is halogen, C 1~4 Fluoroalkyl groups, typically fluoroalkyl groups such as fluoromethyl, sulfonamide groups -NH-S(O)2-Y 1 (In the formula, Y 1 is F or C 1~4 The alkyl group is substituted with one or more fluoroalkyl groups (e.g., -NHSO2CF3) or fluoroalcohol groups (e.g., -C(CF3)2OH).

[0085] In equation (11), L 8 is a single bond or optionally -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -NR 102 - or -C(O)N(R 102 )-(wherein, R 102 is hydrogen and optionally substituted C 1~10 alkyl), e.g., C 1~6 Alkylene or C 3~20 represents a polyvalent linking group selected from optionally substituted aliphatic and aromatic hydrocarbons, such as cycloalkylene, and combinations thereof. For example, the polymer may be a polymer represented by formula (10): 8 is a single bond or a substituted or unsubstituted C 1~20 Alkylene, substituted or unsubstituted C 3~20 Cycloalkylene and substituted or unsubstituted C 6~24 Arylene, typically substituted or unsubstituted C 1~6 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene or substituted or unsubstituted C 6~24 The polyvalent linking group may further comprise repeat units derived from one or more monomers of the formula:

[0086] In formula (11), n3 is an integer of 1 to 5, and is typically 1. When n3 is 1, the group L 8 It should be understood that n3 is a divalent linking group. When n3 is 2, the group L 8 It should be understood that when n3 is 3, the group L 8 is a tetravalent linking group; when n3 is 4, the group L 8 is a pentavalent linking group; and when n3 is 5, the group L 8 It should be understood that is a hexavalent linking group. Thus, in relation to formula (10), the term "polyvalent linking group" refers to any of divalent, trivalent, tetravalent, pentavalent, and / or hexavalent linking groups. In some embodiments, when n is 2 or greater, the carboxylic acid group (-C(O)OH) is linked to the linking group L 8In other embodiments, when n is 2 or greater, the carboxylic acid group (—C(O)OH) can be attached to the same atom of the linking group L 8 can be bonded to different atoms of the

[0087] In equation (12), L 9 represents a single bond or a divalent linking group. 9 is a single bond, substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 6~30 It may be a cycloalkylene.

[0088] In formula (12), n4 is 0 or 1. When n4 is 0, the moiety represented by -OC(O)- is L 9 It should be understood that is a single bond so as to be attached directly to the alkenyl (vinyl) carbon atom.

[0089] In formula (12), Ar 1 is a substituted C which may optionally contain one or more aromatic ring heteroatoms selected from N, O, S or combinations thereof 5~60 C is an aromatic group, which may be monocyclic, non-fused polycyclic, or fused polycyclic. 5~60 When the aromatic group is polycyclic, the rings or ring groups can be fused (such as naphthyl), non-fused, or combinations thereof. 5~60 When the aromatic group is non-fused, the rings or ring groups can be directly linked (such as biaryl, biphenyl, etc.) or bridged by a heteroatom (such as triphenylamino or diphenylene ether). 5~60 The aromatic groups may contain a combination of fused and directly bonded rings (such as binaphthyl).

[0090] In formula (12), y can be an integer from 1 to 12, preferably from 1 to 6, and typically from 1 to 3. Each R x may independently be hydrogen or methyl.

[0091] Non-limiting examples of monomers of formula (10), (11) or (12) include: [ka] [ka] (In the formula, Y 1 is as described above, and R i is as defined in equations (10) to (12). One or more of the following may be mentioned.

[0092] When present, the polymer typically contains repeat units containing polar groups (pendant to the backbone of the polymer) in an amount of from 1 to 60 mol %, typically from 5 to 50 mol %, more typically from 5 to 40 mol %, based on all repeat units in the polymer.

[0093] Non-limiting exemplary polymers of the present invention include: [ka] [ka] [ka] where x, y, and z are each the mole fraction of the associated repeat unit, and the mole fractions for each polymer sum to 1. Contains one or more of the following:

[0094] 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.

[0095] The photoresist composition further comprises a photoacid generator (PAG). Suitable PAGs are capable of generating an acid during post-exposure bake (PEB) that causes cleavage of acid-labile groups present on the polymer of the photoresist composition. The PAG can be in non-polymeric or polymeric form, for example, present in the polymerized repeat unit of a polymer as described above or as part of a different polymer. Suitable non-polymeric PAG compounds have the formula G + A - (In the formula, G + is an organic cation selected from an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of an alkyl group and an aryl group; a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of an alkyl group and an aryl group; - is a non-polymerizable organic anion). In some embodiments, the PAG can be included as a non-polymerized PAG compound, a repeat unit of a polymer having a PAG portion derived from a polymerizable PAG monomer, or a combination thereof.

[0096] Particularly suitable non-polymeric organic anions include those whose conjugate acids have a pKa of −15 to 1. Particularly preferred anions are fluorinated alkyl sulfonates and fluorinated sulfonimides.

[0097] Useful non-polymeric PAG compounds are known in the chemically amplified photoresist art and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Nonionic sulfonate and sulfonyl compounds, for example, nitrobenzyl derivatives 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)diazomethane; glyoxime derivatives, for example For example, 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, are also known to function as photoacid generators. Suitable non-polymeric acid generators are further described in Hashimoto et al. (Patent Document 1), columns 37, 11-47, and 41-91.Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, such as those described in U.S. Patent No. 5,629,999 and U.S. Patent No. 5,629,999, nitrobenzyl esters, s-triazine derivatives, benzoin tosylate, t-butylphenyl α-(p-toluenesulfonyloxy)acetate, and t-butyl α-(p-toluenesulfonyloxy)acetate.

[0098] Typically, when the photoresist composition includes a non-polymeric photoacid generator, it is present in the photoresist composition in an amount of from 1 to 65 weight percent, more typically from 2 to 20 weight percent, based on the total solids content of the photoresist.

[0099] In some embodiments, G + can be a sulfonium cation or an iodonium cation. For example, G + is M + or may be a sulfonium cation as described herein for G + is M + The photoresist composition may further comprise a PAG, and the cation G may be an iodonium cation as described herein for + is M + or the cation G + is M + may differ from

[0100] PAGs that are onium salts typically contain an organic anion having a sulfonate group or a non-sulfonate type group such as a sulfonamidate, sulfonimidate, methide, or borate.

[0101] Exemplary organic anions having a sulfonate group include: [ka]

[0102] Exemplary non-sulfonated anions include: [ka]

[0103] The photoresist composition can optionally include multiple PAGs. The multiple PAGs can be polymeric, non-polymeric, or can include both polymeric and non-polymeric PAGs. Preferably, each PAG in the multiple PAGs is non-polymeric.

[0104] In one or more embodiments, the photoresist composition can include a first photoacid generator that includes a sulfonate group on the anion, and the photoresist composition can include a second photoacid generator that is non-polymeric, and the second photoacid generator can include an anion that does not include a sulfonate group.

[0105] In some embodiments, the polymer may optionally further comprise a repeat unit comprising a PAG-containing moiety, for example, a repeat unit derived from one or more monomers of formula (13). [ka]

[0106] In equation (13), R j is hydrogen, fluorine, cyano or substituted or unsubstituted C 1~10 Preferably, R j is hydrogen, fluorine or substituted or unsubstituted C 1~5 Alkyl, typically methyl. Q 1 can be a single bond or a divalent linking group. 1 may contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0107] In equation (13), A 1 is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 2~30 Heterocycloalkylene, substituted or unsubstituted C 6~30Arylene or substituted or unsubstituted C 3~30 Preferably, A is one or more of: 1 is an optionally substituted divalent C 1~30 It may be a perfluoroalkylene group.

[0108] In equation (13), Z - is the anionic moiety, the conjugate acid of which typically has a pKa of -15 to 1. Z - can be a sulfonate, carboxylate, anion of a sulfonamide, anion of a sulfonimide, or a methide anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonates and fluorinated sulfonimides. + is an organic cation as defined above. In some embodiments, G + is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of an alkyl group and an aryl group; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of an alkyl group and an aryl group.

[0109] Exemplary monomers of formula (13) include the following: [ka] (In the formula, G + is an organic cation) may be included.

[0110] If included, the polymer may contain repeat units comprising PAG moieties in an amount of 1 to 15 mol %, typically 1 to 8 mol %, more typically 2 to 6 mol %, based on all repeat units in the polymer.

[0111] The photoresist composition may include a molecular glass compound. The molecular glass compound is a tetrameric calix[4]arene having free hydroxy groups that is modified using acetal chemistry to include base-stable but acid-cleavable aromatic protecting groups, as provided in U.S. Patent No. 6,277,693. The photoresist composition may include the molecular glass compound in an amount of 50 to 99 wt. %, preferably 55 to 95 wt. %, more preferably 60 to 90 wt. %, and even more preferably 65 to 90 wt. %, based on the total weight of solids. It will be understood that "molecular glass compound," as used in this context of a component in a photoresist, may refer to the molecular glass compound alone or a combination of the molecular compound with another molecular compound or a polymer useful in photoresists.

[0112] 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); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2 Examples of suitable solvents include ketones such as cyclohexanone and cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and 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, and diphenyl carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Among these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof.

[0113] 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 70 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.

[0114] The polymer will typically be present in the photoresist composition in an amount of 10 to 99.9 weight percent, typically 25 to 99 weight percent, and more typically 50 to 95 weight percent, based on the total solids of the photoresist composition, where "total solids" will be understood to include the photoactive compound, polymer, PAG, and other non-solvent components.

[0115] 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 to provide a polar group such as a hydroxyl, carboxylic acid, sulfonic acid, or the like in the presence of an aqueous alkaline developer after the exposure and post-exposure bake steps. The base-labile group will not react significantly (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 moieties) decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-labile group is highly reactive under typical photoresist development conditions, for example, using an aqueous alkaline photoresist developer such as an aqueous solution of 0.26N (N) tetramethylammonium hydroxide (TMAH). For example, a 0.26N aqueous solution of TMAH can be used for single puddle development or dynamic development, in which 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 and has a lower surface energy than the polymer 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 resist composition to the top surface of the formed photoresist layer.

[0116] In some embodiments, the base-labile material, also referred to herein as a base-labile polymer, can be a polymeric material, which can include one or more repeat units containing one or more base-labile groups. For example, the base-labile polymer can include repeat units containing two or more base-labile groups, which can be the same or different. Preferred base-labile polymers include at least one repeat unit containing two or more base-labile groups, for example, repeat units containing two or three base-labile groups.

[0117] The base labile polymer has the formula (14a): [ka] (In the formula, X e is a substituted or unsubstituted C2 20 is a polymerizable group selected from alkenyl or substituted or unsubstituted (meth)acryloyl, and L 10 is, for example, a substituted or unsubstituted C 1~20 Alkylene, substituted or unsubstituted C 3~20 is a divalent linking group that may contain one or more of cycloalkylene, —C(O)—, or —C(O)O—; R n is a substituted or unsubstituted C 1~20 fluoroalkyl, provided that the carbon atom bonded to the carbonyl (C=O) in formula (14a) is substituted with at least one fluorine atom. The polymer may be a polymer containing repeating units derived from one or more of the monomers.

[0118] Exemplary monomers of formula (14a) can include: [ka]

[0119] The base labile polymer can include repeat units containing two or more base labile groups. For example, the base labile polymer can be represented by formula (14b): [ka] (In the formula, X f and R p are X in equation (14a), respectively. e and R n as defined in terms of L 11 is a substituted or unsubstituted C 1~20 Alkylene, substituted or unsubstituted C 3~20 is a polyvalent linking group containing one or more of cycloalkylene, —C(O)—, or —C(O)O—; and n4 is an integer of 2 or greater, for example, 2 or 3. The repeating units may be derived from one or more monomers.

[0120] Exemplary monomers of formula (14b) include: [ka]

[0121] The base labile polymer can include repeat units containing one or more base labile groups. For example, the base labile polymer can be represented by formula (14c): [ka] (In the formula, X g and R q are X in equation (14a), respectively. e and R n as defined in terms of L 12 is a divalent linking group; L 13 is a substituted or unsubstituted C 1~20 fluoroalkylene, and the carbon atom bonded to the carbonyl (C═O) in formula (14c) is substituted with at least one fluorine atom. The repeating units may be derived from one or more monomers.

[0122] Exemplary monomers of formula (14c) can include: [ka]

[0123] In a further preferred embodiment of the present invention, the base-labile polymer can contain one or more base-labile groups and one or more acid-labile groups, such as one or more acid-labile ester moieties (e.g., t-butyl esters) or acid-labile acetal groups. For example, the base-labile polymer can contain a repeating unit containing a base-labile group and an acid-labile group, i.e., both the base-labile group and the acid-labile group are present on the same repeating unit. In another example, the base-labile polymer can contain a first repeating unit containing a base-labile group and a second repeating unit containing an acid-labile group. Preferred photoresists of the present invention can exhibit reduced defects associated with resist relief images formed from the photoresist composition.

[0124] The base-labile polymer can be prepared using any suitable method in the art, including those described herein for the first and second polymers. For example, the base-labile polymer can be obtained by polymerization of the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof. Additionally or alternatively, one or more base-labile groups can be grafted onto the backbone of the polymer using a suitable method.

[0125] In some embodiments, the base-labile material is a single molecule containing one or more base-labile ester groups, preferably one or more fluorinated ester groups. Single-molecule base-labile materials typically have an M in the range of 50 to 1,500 Da. W Exemplary base-labile materials include: [ka]

[0126] If present, the base-labile material is typically present in a photoresist composition in an amount of from 0.01 to 10% or from 1 to 5% by weight based on the total solids content of the photoresist composition.

[0127] In addition to or instead of the base-labile polymer, the photoresist composition can further include one or more polymers in addition to and different from the photoresist polymers described above. For example, the photoresist composition can include additional polymers as described above but with different compositions, or polymers similar to those described above but without each of the essential repeating units. 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.

[0128] 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 wt %, based on the total solids content of the photoresist composition.

[0129] 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 1~20Also 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.

[0130] The photodegradable deactivator may be in a non-polymeric form or a polymer-bound form. When in a polymeric form, the photodegradable deactivator is present in polymerized units on the first polymer or the second polymer. The polymerized units containing the photodegradable deactivator are typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, and more preferably 1 to 2 mol %, based on the total repeat units of the polymer.

[0131] Exemplary basic quenching agents include, for example, linear 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-(2-acetoxyethyl)morpholine, 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 and cyclohexylpyrrolidine, such as 2-pyrrolidone.

[0132] The basic quenching agent may be in a non-polymeric form or a polymer-bound form. If 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.

[0133] 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.

[0134] A pattern formation 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 active or operable portions of the device to be formed.

[0135] Typically, one or more lithographic layers, such as a hardmask layer, e.g., a spin-on carbon (SOC), amorphous carbon, or metal hardmask 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 lithographic material stack.

[0136] 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 & Imaging (Marlborough, Massachusetts).

[0137] 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, for a period of 15 to 120 seconds to obtain a layer of the 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 layers formed from the compositions of the present invention typically have a dry layer thickness of 10 to 500 nanometers (nm), preferably 15 to 200 nm, and more preferably 20 to 120 nm.

[0138] 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. Soft-baking temperatures are typically 80 to 170°C, more typically 90 to 150°C. Soft-baking times are 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 readily determined by one skilled in the art based on the components of the composition.

[0139] 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. Alternatively, such exposure can 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 193 nm radiation or EUV 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.

[0140] 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.

[0141] 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.

[0142] Suitable developers for the PTD process include aqueous base developers, such as tetramethylammonium hydroxide (TMAH), preferably 0.26N TMAH, quaternary ammonium hydroxide solutions such as 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. NTD developers are typically 2-heptanone or n-butyl acetate.

[0143] 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.

[0144] A photoresist pattern can be used, for example, as an etch mask, thereby 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, such as 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.

[0145] The present invention is further illustrated by the following examples. [Example]

[0146] Synthesis Examples: Synthetic reactions were carried out under normal atmospheric conditions. All chemicals were used as received from commercial suppliers and without further purification.

[0147] Synthesis of triphenylsulfonium α-cyanocinnamate (PAC1) [ka] A solution was prepared by combining 5 grams (g) of α-cyanocinnamic acid (28.87 millimoles (mmol)) with tetrahydrofuran (75 mL, THF). 1 g of LiOH in 15 milliliters (mL) of deionized (DI) water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25°C) for 1 hour. The THF was then removed under reduced pressure to yield the lithium α-cyanocinnamate salt. 50 mL of DI water, 75 mL of dichloromethane (DCM), and 9.9 g of triphenylsulfonium bromide (28.87 mmol) were added to the lithium α-cyanocinnamate salt, and the mixture was stirred at room temperature (approximately 25°C) for 4 hours. The organic phase was then washed with DI water (5 x 50 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield crude photoactive compound PAC1. The crude product was dissolved in 20 mL of acetone, and the solution was poured into 150 mL of heptane to give PAC1 as a colorless precipitate, which was isolated by filtration and dried to give a colorless solid. The yield of PAC1 was 3.4 g (35%). Proton nuclear magnetic resonance spectroscopy ( 1 H-NMR (in acetone-d6), chemical shifts (δ, parts per million (ppm)): 8.10 (m, 7H), 7.80 (m, 11H, ArH), 7.40 (m, 3H). Ultra-performance liquid chromatography (UPLC) purity was 99.21% as detected by ultraviolet (UV) absorbance at 210 nm.

[0148] Synthesis of bis(4-(tert-butyl)phenyl)iodonium α-cyanocinnamate (PAC2) A solution was prepared by combining 10.0 g of α-cyanocinnamic acid (57.74 mmol) with 150 mL of THF. 2 g of LiOH in 25 mL of DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. The THF was then removed under reduced pressure to yield the lithium α-cyanocinnamate salt. 100 mL of DI water, 150 mL of DCM, and 24.8 g of bis(4-(tert-butyl)phenyl)iodonium acetate (54.82 mmol) were added to the lithium α-cyanocinnamate salt, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 100 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield crude photoactive compound PAC2. The crude product was dissolved in 40 mL of acetone, and the solution was poured into 300 mL of heptane to give PAC2 as a colorless precipitate, which was isolated by filtration and dried to give a colorless solid. The yield of PAC2 was 21.7 g (66.5%). 1 H NMR (acetone-d6), δ (ppm): 7.89 (m, 4H, ArH), 7.78 (m, 3H, ArH), 7.38 (m, 7H), 1.21 (s, 18H, 6(CH3)). UPLC purity was 99.30% as detected by UV absorbance at 210 nm.

[0149] Synthesis of bis(4-(tert-butyl)phenyl)iodonium 4-trifluoromethylcinnamate (PAC3) A solution was prepared by combining 5.0 g of 4-trifluoromethylcinnamic acid (23.13 mmol) with 150 mL of THF. 0.8 g of LiOH in 25 mL of DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. The THF was then removed under reduced pressure to yield the lithium 4-trifluoromethylcinnamate salt. 100 mL of DI water, 150 mL of DCM, and 10.4 g of bis(4-(tert-butyl)phenyl)iodonium acetate (23.0 mmol) were added to the lithium 4-trifluoromethylcinnamate salt, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 50 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield crude photoactive compound PAC3. The crude product was dissolved in 20 mL of acetone, and the solution was poured into 150 mL of heptane to give PAC3 as a colorless precipitate, which was isolated by filtration and dried to give a colorless solid. The yield of PAC3 was 8.9 g (63.5%). 1 H NMR (in acetone-d6), δ (ppm): 7.90 (d, 4H, ArH), 7.53 (d, 2H, ArH), 7.49 (d, 2H, ArH), 7.38 (d, 4H, ArH), 7.22 (d, 1H, CH=CH), 6.42 (d, 1H, CH=CH), 1.19 (s, 18H, 6(CH)). UPLC purity was 99.30% as detected by UV absorbance at 210 nm.

[0150] Synthesis of bis(4-(tert-butyl)phenyl)iodonium (Z)-3-fluoro-3-phenylacrylate (PAC4) A solution was prepared by combining 1.0 g of α-fluorocinnamic acid (6.0 mmol) with 10 mL of THF. 0.2 g of LiOH in 5 mL of DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25°C) for 1 hour. The THF was then removed under reduced pressure to yield the lithium α-fluorocinnamate salt. To the lithium α-fluorocinnamate salt, 10 mL of DI water, 10 mL of DCM, and 2.0 g of bis(4-(tert-butyl)phenyl)iodonium acetate (4.42 mmol) were added, and the mixture was stirred at room temperature (approximately 25°C) for 4 hours. The organic phase was then washed with DI water (5 x 15 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield crude photoactive compound PAC4 as a white solid. The crude product was suspended in 25 mL of heptane, and the product was isolated by filtration and dried to yield a white solid. The yield of PAC4 was 2.2 g (65.5%). 1 H NMR (in acetone-d6), δ (ppm): 8.12 (d, 4H, ArH), 7.50 (m, 6H, ArH), 7.33-7.26 (m, 3H, ArH), 6.50 (d, 1H, CH=CF), 1.20 (s, 18H, 6(CH3)). UPLC purity was 99.92% as detected by UV absorbance at 210 nm.

[0151] Synthesis of bis(4-(tert-butyl)phenyl)iodonium (E)-3-cyclohexylacrylate (PAC5) A solution was prepared by combining 1.0 g of (E)-3-cyclohexylacrylic acid (6.48 mmol) with 10 mL of THF. 0.15 g of LiOH in 5 mL of DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. The THF was then removed under reduced pressure to yield the lithium 3-cyclohexylacrylate salt. 10 mL of DI water, 10 mL of DCM, and 2.0 g of bis(4-(tert-butyl)phenyl)iodonium acetate (4.42 mmol) were added to the lithium 3-cyclohexylacrylate salt, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 15 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield crude photoactive compound PAC5 as a white solid. The crude product was suspended in 25 mL of heptane, and the product was isolated by filtration and dried to give a white solid. The yield of PAC5 was 1.7 g (47.9%). 1 H NMR (in acetone -d6), δ (ppm): 7.83 (d, 4H, ArH), 7.39 (d, 4H, ArH), 6.51 (2H, CH=CH), 5.75 (d, 1H, CH=CH), 2-1.75 (6H, aliphatic -H), 1.19 (s, 18H, 6(CH3)), 1.18-1.08 (m, 5H aliphatic -H). UPLC purity was 99.66% as detected by UV absorbance at 210 nm.

[0152] Synthesis of bis(4-(tert-butyl)phenyl)iodonium (E)-3-(4-iodophenyl)acrylate (PAC6) A solution was prepared by combining 1.0 g of (E)-3-(4-iodophenyl)acrylic acid (3.65 mmol) with 10 mL of THF. 0.15 g of LiOH in 5 mL of DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. The THF was then removed under reduced pressure to yield the lithium 3-cyclohexylacrylate salt. To the lithium 3-cyclohexylacrylate salt, 10 mL of DI water, 10 mL of DCM, and 1.5 g of bis(4-(tert-butyl)phenyl)iodonium acetate (3.32 mmol) were added, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 15 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield crude photoactive compound PAC6 as a white solid. The crude product was suspended in 25 mL of heptane, and the product was isolated by filtration and dried to give a white solid. The yield of PAC6 was 1.7 g (70.8%). 1 H NMR (in acetone-d6), δ (ppm): 8.06 (d, 4H, ArH), 7.67 (d, 2H, ArH), 7.46 (d, 4H, ArH), 7.26 (d, 2H, ArH), 6.93 (2H, CH=CH), 6.33 (d, 1H, CH=CH), 1.21 (s, 18H, 6(CH)). UPLC purity was 99.88% as detected by UV absorbance at 210 nm.

[0153] Synthesis of triphenylsulfonium cinnamate (PAC7) [ka] A solution was prepared by combining 10.0 g of cinnamic acid (67.49 mmol), 200 mL of acetone, and 200 mL of DI water, and then 7.0 g (30.2 mmol) of silver oxide was added portionwise to the solution. The resulting mixture was stirred at room temperature (approximately 25°C) for 48 hours. The precipitate was isolated by filtration, washed with acetone, and dried under reduced pressure. The yield of silver cinnamate salt was 13.5 g.

[0154] 5.0 g of cinnamate silver salt (5.0 g, 19.6 mmol) was dissolved in 150 mL of methanol and 30 mL of DI water to form a solution, and then 6.0 g of triphenylsulfonium bromide (17.47 mmol) was added to the solution. The reaction mixture was stirred at room temperature (about 25° C.) for 12 hours. 1 H NMR showed the expected product with a 1:1 cation to anion ratio. The mixture was filtered to remove insoluble salts, and the solvent was removed under reduced pressure. The resulting residue was dissolved in acetone and filtered through a plug of diatomaceous earth. The solvent was removed from the filtrate under reduced pressure to yield PAC7 as a colorless oil. The yield of PAC7 was 1.7 g (70.8%). 1 H-NMR (in acetone-d6), δ (ppm): 8.08 (m, 6H, ArH), 7.88-7.78 (m, 9H, ArH), 7.41 (m, 2H), 7.27 (m, 2H, ArH), 7.20 (m, 2H, ArH), 6.50 (d, 1H, CH=CH). UPLC purity was 99.75% as detected by UV absorbance at 210 nm.

[0155] Synthesis of triphenylsulfonium benzoate (CPAC8) A solution was prepared by combining 5.0 g of benzoic acid (18.42 mmol), 100 mL of acetone, and 100 mL of DI water, and then 4.27 g (18.42 mmol) of silver oxide was added portionwise to the solution. The resulting mixture was stirred at room temperature (approximately 25°C) for 48 hours. The precipitate was isolated by filtration, washed with acetone, and dried under reduced pressure. The yield of benzoate silver salt was 7.3 g.

[0156] 2.5 g of benzoate silver salt (10.9 mmol) was dissolved in 100 mL of methanol and 20 mL of DI water to form a solution, and then 2.5 g of triphenylsulfonium bromide (7.28 mmol) was added to the solution. The reaction mixture was stirred at room temperature (about 25° C.) for 12 hours. 1H-NMR indicated the expected product with a 1:1 cation to anion ratio. The mixture was filtered to remove insoluble salts, and the filtrate solvent was removed under reduced pressure. The resulting residue was dissolved in acetone and filtered through a plug of diatomaceous earth. The solvent was removed from the filtrate under reduced pressure to yield CPAC8 as a colorless oil. UPLC purity was 99.63% as detected by UV absorbance at 210 nm.

[0157] Synthesis of triphenylsulfonium (E)-3-(thiophen-3-yl)acrylate (CPAC9) A solution was prepared by combining 2.55 g of (E)-3-(thiophen-3-yl)acrylic acid (16.2 mmol), 50 mL of acetone, and 50 mL of DI water, and then 1.80 g (7.76 mmol) of silver oxide was added portionwise to the solution. The resulting mixture was stirred at room temperature (approximately 25°C) for 48 hours. The precipitate was isolated by filtration, washed with acetone, and dried under reduced pressure. The yield of (E)-3-(thiophen-3-yl)acrylate silver salt was 3.30 g.

[0158] 3.30 g of (E)-3-(thiophen-3-yl)acrylate silver salt (10.9 mmol) was dissolved in 100 mL of methanol and 20 mL of DI water to form a solution, and then 3.48 g of triphenylsulfonium bromide (10.0 mmol) was added to the solution. The reaction mixture was stirred at room temperature (about 25° C.) for 12 hours. 1 H-NMR showed the expected product with a 1:1 cation to anion ratio. The mixture was filtered to remove insoluble salts, and then the solvent was removed under reduced pressure. The resulting residue was dissolved in acetone and filtered through a plug of diatomaceous earth. The solvent was removed from the filtrate under reduced pressure to yield CPAC9 as a colorless oil. UPLC purity was 99.64% as detected by UV absorbance at 210 nm. [ka]

[0159] Photoresist Formulation 1. Photoresist compositions were prepared by dissolving the solid components in solvent using the materials and amounts shown in Table 1 to a total solids content of 2.6 wt%. Each mixture was shaken using a mechanical shaker and filtered through a PTFE disk filter with a 0.2 μm pore size. The amounts of polymer, PAG, and photoactive compound are reported as weight percent based on the total solids content of the photoresist composition. The solvent system contained propylene glycol monomethyl ether acetate (PGMEA) (50 wt%) and methyl 2-hydroxyisobutyrate (50 wt%).

[0160] Lithography Evaluation 1. 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 thin film. Next, a coating of AR™ 40 BARC (DuPont Electronics & Industrial) was placed on the AR™ 3 layer and soft-baked at 205°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 thin film layer with a thickness of 70 nm. Wafers were exposed to 248 nm radiation using a Canon FPA-5000 ES4 scanner (NA = 0.8, outer sigma = 0.85, inner sigma = 0.57) using a mask with a 1:1 line-space (L / S) pattern (120 nm linewidth). The exposed wafers were 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 spun dry to form photoresist patterns. Critical dimension (CD) linewidth measurements of the formed patterns were performed using a Hitachi S-9380 CD-SEM. Linewidth roughness (LWR) was determined from the deviation in linewidth measured over a given length and evaluated using the three-sigma (3σ) deviation of the width from the distribution of a total of 100 random linewidth measurement points. LWR data are shown in Table 1.

[0161] [Table 1]

[0162] Photoresist Formulation 2. Photoresist compositions were prepared by dissolving the solid components in solvent using the materials and amounts shown in Table 2 to a total solids content of 4.2 wt.%. Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disk filter with a 0.2 μm pore size. The amounts of polymer, PAG, and photoactive compound are reported as weight percent based on the total solids content of the photoresist composition. The solvent system contained PGMEA (50 wt.%) and methyl 2-hydroxyisobutyrate (50 wt.%).

[0163] Lithography Evaluation 2. 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 thin film. Next, a coating of AR™ 40A BARC (DuPont Electronics & Industrial) was placed on the AR™ 3 layer and soft-baked at 205°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 thin film layer with a thickness of 120 nm.

[0164] Wafers were 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 containing a 1:1 L / S pattern (120 nm linewidth). The exposed wafers were post-exposure baked at 100 °C for 60 seconds, developed in a 0.26 N TMAH solution for 60 seconds, rinsed with DI water, and spin-dried to form photoresist patterns. CD linewidth measurements of the formed patterns were performed using a HITACHI S-9380 CD-SEM. LWR was determined from the deviation in linewidth measured over a given length and evaluated using the 3σ deviation of the width from the distribution of a total of 100 random linewidth measurement points. LWR data are shown in Table 2.

[0165] [Table 2]

[0166] Photoresist Formulation 3. Photoresist compositions were prepared by dissolving the solid components in solvent using the materials and amounts shown in Table 3 to a total solids content of 1.55 wt. %. Each mixture was shaken using a mechanical shaker and filtered through a PTFE disk filter with a 0.2 μm pore size. The amounts of polymer, PAG, and photoactive compound are reported as weight percent based on the total solids content of the photoresist composition. The solvent system contained PGMEA (50 wt. %) and methyl 2-hydroxyisobutyrate (50 wt. %).

[0167] Lithography Evaluation 3. Lithography was performed using a CLEAN TRACK ACT8 (TEL, Tokyo Electron Co.) wafer track. A 300 nm wafer for photolithography testing was coated with an organic BARC thin film layer to obtain a 60 nm thin film, and then a silicon-containing antireflective coating (SiARC) thin film layer was placed on the organic BARC thin film layer to form a second layer with a thickness of 20 nm. A photoresist composition was then spin-coated onto the BARC / SiARC bilayer stack and soft-baked at 110°C for 60 seconds to obtain a photoresist thin film layer with a thickness of 40 nm.

[0168] Wafers were exposed to 13.5 nm radiation using an ASML NXE3400B scanner with a mask containing a 20.25 nm CD and a 36-pitch groove pattern. The exposed wafers were post-exposure baked at 100°C for 60 seconds, developed in a 0.26 N TMAH solution for 60 seconds, rinsed in DI water, and spun dry to form the resist groove pattern. CD linewidth measurements of the formed groove pattern were performed using a HITACHI CG5000 CD-SEM.

[0169] Table 3 shows that the groove pattern was resolved down to 18 nm and the millijoules per square centimeter (mJ / cm 2 The EUV sizing energy (E) measured for the examples was the exposure energy reported in units of size ) Table 3 also shows the depth of focus (DOF) for the examples, which is the total distance range of focus that preserves the printed features without any print defects.

[0170] [Table 3]

[0171] As demonstrated by comparing the results in Tables 1, 2, and 3, the photoactive compounds of the present invention result in photoresist compositions with unexpected lithographic performance, achieving LWR reductions of up to 20%. The LWR improvement was observed without affecting photospeed and with improved DCOF.

[0172] 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. Formula (3a): 【Chemical 1】 (In the formula, Ring CY1 is C 3-8 cycloalkyl, C 6-14 aryl, or C 3-12 heteroaryl containing an aromatic ring heteroatom selected from nitrogen, oxygen, or a combination thereof; Each L １ are independently a single bond; Each R ８ are independently hydroxyl, -F, -I, -CF ３ , or substituted or unsubstituted C １～１０ is alkyl; a is an integer from 0 to 5; L ２ is a single bond; R ９ represents hydrogen, cyano, hydroxyl, -F, -I, -CF ３ , or substituted or unsubstituted C １～１０ is alkyl; M ＋ is a sulfonium cation of formula (2a) or an iodonium cation of formula (2b): 【Chemistry 2】 (In formulas (2a) and (2b), R 10 , R 20 and R 30 are each independently 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 arylalkyl or substituted or unsubstituted C 4-20 heteroarylalkyl; Each of R 10 , R 20 and R 30 can be either separate or linked to another group at R 10 , R 20 or R 30 via a single bond or a divalent linking group to form a ring; Each of R 10 , R 20 and R 30 may optionally include a divalent linking group as part of its structure; Each of R 10 , R 20 and R 30 independently may optionally comprise an acid labile group selected from a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group; Divalent linking groups for linking the R 10 , R 20 and / or R 30 groups include —O—, —S—, —Te—, —Se—, —C(O)—, —C(S)—, —C(Te)—, or —C(Se)—, substituted or unsubstituted C 1-5 alkylene, or combinations thereof. and The anion of formula (3a) is not α-cyano-4-hydroxycinnamate. photoactive compounds.

2. Ring CY1 is C ６～１４ The photoactive compound of claim 1 which is aryl.

3. 2. The photoactive compound of claim 1, wherein a is an integer from 0 to 3.

4. R ９ But substitution C １～１０ alkyl and the substituted R ９ 10. The photoactive compound of claim 1, wherein at least one substituent of the group is hydroxy, -I, or a combination thereof.

5. The photoactive compound of claim 1; Solvent and A photoresist composition comprising:

6. 6. The photoresist composition of claim 5, further comprising a material that switches its solubility in a base or in an organic solvent under the action of an acid, said material being different from the photoactive compound.

7. 7. The photoresist composition of claim 6, further comprising a photoacid generator different from the photoactive compound.

8. 1. A method of forming a pattern, comprising: (a) forming a photoresist layer on a substrate from the photoresist composition of claim 5; (b) patternwise exposing the photoresist layer to activating radiation; (c) developing the exposed photoresist layer to provide a resist relief image.

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