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

Abstract

To provide photoactive compounds, photoresist compositions including the same, and pattern formation methods.SOLUTION: The present invention provides a photoactive compound of formula (1a) or (1b): (wherein 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 and R3 are hydrogen or the like; 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).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photoactive compound for a photoresist composition and a patterning method using such a photoresist composition. The present invention finds applicability in lithography applications in the semiconductor manufacturing industry.

Background Art

[0002] A photoresist material is a photosensitive composition typically used to transfer an image onto one or more underlying layers such as a metal, semiconductor, or dielectric layer disposed on a substrate. To increase the integration density of semiconductor devices and enable the formation of structures having dimensions in the nanometer range, photoresists and photolithography processing tools with high resolution capabilities have been developed.

[0003] Conventionally, chemically amplified photoresists have been used for high resolution processing. Such resists typically use a polymer having an acid-labile group, a photoacid generator, and an acid deactivating material. Pattern-like exposure to actinic radiation through a photomask causes the photoacid generator to form an acid, which causes cleavage of the acid-labile groups in the exposed regions of the polymer during post-exposure baking. In many cases, an acid deactivating material is added to the photoresist composition to control the diffusion of the acid into the unexposed regions and improve the contrast. The result of the lithography process is the generation of a difference in solubility characteristics between the exposed and unexposed regions of the resist in the 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 to form a positive image. The resulting relief image enables selective processing of the substrate.

[0004] Non-photoactive acid deactivation materials commonly used in chemically amplified resists include linear aliphatic amines, cycloaliphatic amines, aromatic amines, linear and cyclic amides, and their derivatives. Another class of commonly used acid deactivation materials is photoactive deactivators, known as photodegradable deactivators or photolytic deactivators. Photoactive deactivators are also used in chemically amplified resist compositions. Photodegradable deactivators are typically salts that contain 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 deactivator before exposure. Upon exposure, the anion portion of the photodegradable deactivator becomes protonated and thus more acidic. Therefore, upon irradiation of a chemically amplified resist containing a photodegradable deactivator, the concentration of the acid deactivator in the exposed portion decreases dramatically. On the other hand, intact photodegradable deactivators in the unexposed portion can capture acid molecules diffusing from the exposed portion during the lithography process, thereby enhancing lithography performance.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] Photoresist compositions containing photodegradable deactivators and their use are described in the art. However, for many other applications, there is a need for a novel photoresist that can provide excellent line edge roughness (LWR) and a wider depth of focus (DOF) for high-resolution pitch features.

Means for Solving the Problems

[0007] Formula (1a) or (1b): [Chemical formula] (wherein, 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 aryl or a substituted or unsubstituted C containing an aromatic ring heteroatom selected from 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 group, substituted or unsubstituted C1 - C 30 alkylthio group, substituted or unsubstituted C3 - C 10 cycloalkenyl group, substituted or unsubstituted C3 - C 10 heterocycloalkenyl group, substituted or unsubstituted C 6~30 aryl, substituted or unsubstituted C 7~30 arylalkyl, substituted or unsubstituted C 7~30 alkylaryl or substituted or unsubstituted C6 - C 30 aryloxy group; 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; R 2 , R3 and R 4 Each of them optionally further contains one or more divalent linking groups as part of their structures, and each of the one or more divalent linking groups is independently substituted or unsubstituted; R 2 and R 3 together optionally form a ring that optionally further contains one or more divalent linking groups as part of its structure, each of the one or more linking groups is substituted or unsubstituted, the ring is substituted or unsubstituted; and M + is an organic cation) A photoactive compound is provided.

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

[0009] Yet another aspect is a method of forming a pattern, comprising: (a) forming a photoresist layer from the photoresist composition; (b) patternwise exposing the photoresist layer to actinic radiation; and (c) developing the exposed photoresist layer to provide a resist relief image. DETAILED DESCRIPTION OF THE INVENTION

[0010] Here, exemplary embodiments are referred to in detail, and examples thereof are illustrated in this description. In this regard, these exemplary embodiments may have different forms and should not be construed as limited to the descriptions set forth herein. Thus, the exemplary embodiments are merely described below by reference to the figures for the purpose of describing aspects of this description. As used herein, the term "and / or" encompasses any and all combinations of one or more of the associated listed items. Expressions such as "at least one", when preceding a list of elements, modify the entire list of elements and not individual elements of the list.

[0011] As used herein, the terms "a", "an", and "the" are not meant to limit quantity and should be construed to include both the singular and plural forms unless specifically indicated herein or clearly contradicted by the context. "Or" means "and / or" unless specifically stated otherwise. The modifier "about" used in connection with a quantity includes the recited value and has the meaning determined by the context (e.g., including the degree of error associated with the measurement of a particular quantity). All ranges disclosed herein include the endpoints, and the endpoints are independently combinable with each other. The suffix "(s)" includes both the singular and plural forms of the term it modifies and is thereby intended to include at least one of that term. "Optional" or "optionally" means that the subsequent recited event or circumstance may or may not occur and that the description includes both the case where the event occurs and the case where the event does not occur. The terms "first", "second", etc. do not mean order, quantity, or importance herein, but rather are used to distinguish one element from another. When an element is said to be "on" another element, it can be in direct contact with the other element or intervening elements can be present therebetween. In contrast, when an element is said to be "directly on" another element, no intervening elements are present. It should be understood that the components, elements, limitations, and / or features described for an aspect can be combined in any suitable manner in various aspects.

[0012] Unless otherwise defined, all terms (including technical and scientific terms) used herein 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 construed to have a meaning that is consistent with their meaning in the context of the relevant art and this disclosure, and should not be construed in an idealized or overly formal sense unless expressly so defined herein.

[0013] As used herein, "actinic ray" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and particle beams such as ion beams. Further, in the present invention, "light" means actinic rays or radiation.

[0014] An argon fluoride laser (ArF laser) is a specific type of excimer laser, and it may be referred to as an exciplex laser. "Excimer" is an abbreviation for "excited dimer", while "exciplex" is an abbreviation for "excited complex". An excimer laser uses a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine), and it emits coherent stimulated radiation (laser light) in the ultraviolet range under suitable conditions of electrical stimulation and high pressure.

[0015] Further, "exposure" as used herein includes not only exposure by mercury lamps, far ultraviolet rays typified by excimer lasers, X-rays, extreme ultraviolet rays (EUV light), etc., but also writing by particle beams such as electron beams and ion beams, unless otherwise specified.

[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-chain or branched-chain saturated hydrocarbon group having the specified number of carbon atoms and a valence of one; "alkylene" refers to an alkyl group having a valence of two; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid group" refer to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene group" refers to a cycloalkyl group having a valence of two; "alkenyl" refers to a straight-chain or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of two; "cycloalkenyl" refers to a non-aromatic cyclic monovalent hydrocarbon group having at least one carbon-carbon double bond and having at least three carbon atoms; "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 the Huckel rule, contains carbon in the ring, and optionally contains 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 a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene" refers to an aryl group having a valence of two; "alkylaryl" refers to an aryl group substituted with an alkyl group; "arylalkyl" refers to an alkyl group substituted with an aryl group; "aryloxy" refers to "aryl-O-"; "arylthio" refers to "aryl-S-".

[0017] The prefix "hetero" means that a compound or group contains at least one member that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) instead of a carbon atom, and the heteroatom is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent containing at least one heteroatom; "heteroalkyl" refers to an alkyl group having at least one heteroatom instead of carbon; "heterocycloalkyl" refers to a cycloalkyl group having at least one heteroatom as a ring member instead of carbon; "heterocycloalkylene" refers to a heterocycloalkyl group having a divalent valence.

[0018] The term "heteroaryl" means 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 (in the monocyclic case), 1 to 6 heteroatoms (in the bicyclic case), or 1 to 9 heteroatoms (in the tricyclic case), each independently selected from N, O, S, Si, or P (e.g., in the monocyclic, bicyclic, or tricyclic case, carbon atoms and 1 to 3, 1 to 6, or 1 to 9 N, O, or S heteroatoms). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl, etc.

[0019] Unless specifically defined otherwise, each of the foregoing substituents may be optionally substituted. The term "optionally substituted" means being substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of the chemical structure is typically substituted with another terminal substituent that is monovalent, provided that it does not exceed the normal valence of the specified atom. When the substituent is oxo (i.e., =O), two geminal hydrogen atoms on the carbon atom are substituted with the terminal oxo group. Combinations of substituents or variables are allowed. Exemplary substituents that may be present at the "substituted" position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C 1~6) Alkylamino, alkanoyl (such as acyl, etc., alkanoyl group, etc.), formyl (-C(=O)H), carboxylic acid or its alkali metal salt or ammonium salt; C 2~6 Alkanoyl group, etc.), formyl (-C(=O)H), carboxylic acid or its alkali metal salt or ammonium salt; C 2~6 Alkyl ester (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7~13 Aryl ester (-C(=O)O-aryl or -OC(=O)-aryl), etc. esters (including acrylate, methacrylate and lactone); Amide (-C(=O)NR2 (wherein, R is hydrogen or C 1~6 Alkyl), carboxamide (-CH2C(=O)NR2 (wherein, R is hydrogen or C 1~6 Alkyl), halogen, thiol (-SH), C 1~6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1~6 Alkyl, C 2~6 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 having at least one aromatic ring 6~12 Aryl (for example, phenyl, biphenyl, naphthyl, etc. where each ring is either a substituted aromatic or unsubstituted aromatic), C having 1 to 3 separate rings or fused rings and 6 to 18 ring carbon atoms 7~19 Arylalkyl, arylalkoxy having 1 to 3 separate rings 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 6~12Aryl sulfonyl, (-S(=O)2-aryl) or tosyl (CH3C6H4SO2-), among others, are included but not limited thereto. When a group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group excluding the carbon atoms of any substituents. For example, the group -CH2CH2CN is a cyano-substituted C2 alkyl group.

[0020] The term "halogen" means a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo). The prefix "halo" means a group that contains one or more of fluoro, chloro, bromo or iodo substituents in place of a hydrogen atom. Combinations of halo groups (e.g., bromo and fluoro) or only fluoro groups may 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 1~8 alkyl group substituted with at least one halogen and further substituted with one or more other substituents that are not halogen. Since a halogen atom does not replace a carbon atom, it should be understood that substitution of a group with a halogen atom is not considered a heteroatom-containing group.

[0021] As used herein, an "acid-labile group" refers to a group that, optionally and typically with heat treatment, undergoes cleavage of a bond by the catalytic action of an acid to result in the formation of a polar group such as a carboxylic acid group or an alcohol group on the polymer, and optionally and typically, the moiety attached to the cleaved bond is cleaved from the polymer. In other systems, a non-polymeric compound may contain an acid-labile group that undergoes cleavage by the catalytic action of an acid to result 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 an acid is typically a photoacid that causes bond cleavage during post-exposure baking, however, embodiments are not limited thereto, for example, such an acid may be generated thermally. Suitable acid-labile groups include, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group or a ketal group. Acid-labile groups are generally also 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 specifically defined, a "divalent linking group" refers to a divalent group containing one or more 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 heteroarylene or a combination thereof, where 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 3~30It is heteroaryl. Typically, the divalent linking group includes -O-, -S-, -C(O)-, -N(R a )-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 alkylene, substituted or unsubstituted C 3~30 cycloalkylene, substituted or unsubstituted C 3~30 heterocycloalkylene, substituted or unsubstituted C 6~30 arylene, substituted or unsubstituted C 3~30 heteroarylene or one or more combinations thereof, and 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 heteroaryl. 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 at least one combination thereof, and 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 heteroaryl.

[0023] The present invention relates to photoactive compounds, for example, 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 a wider depth of focus (DOF) of printed features.

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

[0025] In formula (1a), R 1 is a substituted or unsubstituted C 1~30 alkyl, a substituted or unsubstituted C 3~30 cycloalkyl, a substituted or unsubstituted C 3~30 heterocycloalkyl, a substituted or unsubstituted C 6~30 aryl or a substituted or unsubstituted C 3~30 heteroaryl containing an aromatic ring heteroatom selected from nitrogen, oxygen or a combination thereof. Preferably, R 1 is a substituted or unsubstituted C 3~20 cycloalkyl, a substituted or unsubstituted C 3~20 heterocycloalkyl, a substituted or unsubstituted C 6~20 aryl or a substituted or unsubstituted C 3~20 heteroaryl containing an aromatic ring heteroatom selected from nitrogen, oxygen or a combination thereof, and typically, R 1 is a substituted or unsubstituted C 6~20 aryl or a substituted or unsubstituted C 3~20 heteroaryl containing an aromatic ring heteroatom selected from nitrogen or oxygen, and the substituted C 6~20 aryl and the substituted C 3~20 heteroaryl are each independently a halogen, a hydroxyl group, a substituted or unsubstituted C 1~10 alkyl, a substituted or unsubstituted C6-C 20 aryl, a substituted or unsubstituted C6-C 20 aryloxy, a substituted or unsubstituted C3-C 20 heteroaryl or the formula -C(O)OR 8 (wherein R 8 is a substituted or unsubstituted C 1~10 alkyl, a substituted or unsubstituted C 3~10 cycloalkyl, a substituted or unsubstituted C 6~10 aryl or a substituted or unsubstituted C 3~10may be substituted with at least one group that may be heteroaryl).

[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 group, substituted or unsubstituted C1-C 30 alkylthio group, substituted or unsubstituted C3-C 10 cycloalkenyl group, substituted or unsubstituted C3-C 10 heterocycloalkenyl group, substituted or unsubstituted C 6~30 aryl, substituted or unsubstituted C 7~30 arylalkyl, substituted or unsubstituted C 7~30 alkylaryl or substituted or unsubstituted C6-C 30 aryloxy group. Preferably, R 2 is hydrogen, halogen or substituted or unsubstituted C 1~10 alkyl, and typically, R 2 may be hydrogen.

[0027] In formula (1a), each of R 2 and R 3 may optionally further contain 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), R2 and R 3 may together optionally form a ring that optionally further contains one or more divalent linking groups as part of its structure, each of the one or more divalent linking groups is substituted or unsubstituted, and the ring is substituted or unsubstituted.

[0029] In formula (1a), R 3 is a hydrogen or non-hydrogen substituent. For example, R 3 can be a hydrogen or substituted or unsubstituted C 1~20 organic group. In some embodiments, R 3 is a C 5 organic group further comprising -C(O)-, -C(O)O-, -C(O)N(R 1~20 )- or combinations thereof, and R 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 heteroaryl. In other embodiments, R 3 can be a halogen atom, a cyano group or substituted or unsubstituted C 1~5 haloalkyl. In some aspects, when R 1 is substituted or unsubstituted C 6~30 aryl, R 3 is not hydrogen or a halogen.

[0030] In formula (1b), R 4 is 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 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 heteroaryl. For example, R 4 can be substituted or unsubstituted C 6~18 aryl or substituted or unsubstituted C 3~18 heteroaryl, and substituted C 6~18 aryl and substituted C3~18 A heteroaryl is each substituted with at least one of 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 heteroaryl or a combination thereof. R 4 optionally further contains one or more divalent linking groups as part of its structure, and each of the one or more divalent linking groups is 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).

Chemical formula

[0032] 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. R 10 , R20 and R 30 Each of which may be separate or may be bonded to another group of R 10 , R 20 or R 30 to form a ring. Each of R 10 , R 20 and R 30 may optionally contain a divalent linking group as part of its structure. Each of R 10 , R 20 and R 30 may independently optionally contain 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 an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group or a ketal group. For the linkage of the R 10 , R 20 and / or R 30 groups, suitable divalent 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 the following.

Chemical formula

[0034] Exemplary iodonium cations of formula (2b) include the following.

Chemical formula

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

Chemical formula

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

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

[0038] In formula (3a), each R 8 can independently be 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 heteroaryl.

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

[0040] In formula (3a), L 2 is 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 May be heteroaryl. 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 heteroaryl, at least one substituent of the substituted R 9 Group may be hydroxy, -I or a combination thereof.

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

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

Chemical formula

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

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

[0046] In formula (3b), L 3 Is 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 heteroaryl. 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 heteroaryl, when the at least one substituent of the substituted R 9 group can be hydroxy, -I or a combination thereof.

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

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

Chemical formula

Chemical formula

Chemical formula

[0050] Non-limiting examples of the anionic moiety of the photoactive compound of formula (1b) may include one or more of the following compounds. [Chemical Formula]

[0051] The present invention further relates to a photoresist composition 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 aspect, the photoresist composition is a material that switches solubility in an organic solvent in the presence of a base or under the action of an acid, and further comprises a material different from the photoactive compound. For example, this material can be a polymer or a molecular glass.

[0053] The polymer may contain one or more repeating units. The repeating units can be, for example, one or more units for the purpose of adjusting the properties of the photoresist composition, such as etch rate and solubility. Exemplary repeating units can 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 contain repeating units containing acid-labile groups. For example, the repeating units containing acid-labile groups can be derived from one or more monomers of formula (4), (5), or (6). [Chemical Formula]

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

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

[0057] In formulas (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 one or less of R 21 ~R 23 can be hydrogen and one or less of R 24 ~R 26 can be hydrogen, and when one of R 21 ~R 23 is hydrogen, at least one of R 21 ~R 23 is substituted or unsubstituted C 6~20 aryl or substituted or unsubstituted C 3~20 heteroaryl, and when one of R 24 ~R 26 is hydrogen, 24 ~R 26 at least one of R 6~20Aryl or substituted or unsubstituted C 3~20 is a heteroaryl, provided. Preferably, R 21 ~R 26 are each independently a substituted or unsubstituted C 1~6 alkyl or a substituted or unsubstituted C 3~10 cycloalkyl. R 21 ~R 26 each may optionally further contain a divalent linking group as part of its structure.

[0058] In formula (4), any two of R 21 ~R 23 may optionally form a ring together via a single bond or a divalent linking group, and this ring may be substituted or unsubstituted. In formula (5), any two of R 24 ~R 26 may optionally form a ring together via a single bond or a divalent linking group, and this ring may be substituted or unsubstituted.

[0059] For example, any one or more of R 21 ~R 26 are independently a group of the formula -CH2C(=O)CH (3-n) Y n (wherein each Y is independently a substituted or unsubstituted C 2~10 heterocycloalkyl, and n is 1 or 2). For example, each Y is independently a group of the formula -O(C a1 )(C a2 )O- (wherein C a1 and C a2 are each independently hydrogen or a substituted or unsubstituted alkyl, and C a1 and C a2 optionally form a ring together) and is a substituted or unsubstituted C 2~10 heterocycloalkyl.

[0060] In formulas (6) and (8), R 27 , R 28 , R 34 and R 35 are each independently hydrogen, a 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 can be heteroaryl; R 16 and R 22 are each independently, substituted or unsubstituted C 1~20 alkyl, substituted or unsubstituted C 3~20 cycloalkyl or substituted or unsubstituted C 3~20 heterocycloalkyl. 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 heterocycloalkyl. Each of R 27 , R 28 , R 34 and R 35 can optionally further contain a divalent linking group as part of their structure.

[0061] In formula (7), R 31 ~R 33 are each independently, 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 can be heteroaryl, provided that no more than one of R 31 ~R 33 can be hydrogen, and provided that when one of R 31 ~R 33 is hydrogen, at least one of the others of R 31 ~R 33 is substituted or unsubstituted C 6~20 aryl or substituted or unsubstituted C 3~20Provided that it is heteroaryl. R 31 ~R 33 Each of them may optionally further contain a divalent linking group as part of its structure.

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

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

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

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

[0066] In some embodiments, R 21 ~R 29 and R 31 ~R 36 each may optionally further contain one or more bicyclic linking groups selected from -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 heterocycloalkyl).

[0067] In some embodiments, in the repeating unit containing an acid-labile group, the acid-labile group may be a tertiary alkyl ester. For example, the repeating unit containing a tertiary alkyl ester group may be derived from one or more monomers of formula (4), (5) or (7), where R 21 ~R 26 or R 34 ~R 36 are not hydrogen, and n1 is 1.

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

Chemical formula

[0069] Exemplary monomers of formula (5) include the following:

Chemical formula

Chemical formula

[0070] Exemplary monomers of formula (6) include the following:

Chemical formula

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

Chemical formula

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

Chemical formula

[0073] In some embodiments, the polymer has a cyclic acetal group or a cyclic ketal group, such as the following structure:

Chemical formula

[0074] In some embodiments, the polymer may have repeating units having acid-labile groups containing a tertiary alkoxy group, for example, one or more of the following monomers. [Chemical formula]

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

[0076] In some embodiments, the polymer may further include repeating units containing a polar group, and this polar group is a pendant group to the main chain 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 repeating unit derived from one or more lactone-containing monomers of formula (9). [Chemical formula]

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

[0079] In formula (9), L 7 is a single bond or a divalent linking group. Preferably, L 7 is a single bond or substituted or unsubstituted C 1~30 alkylene, substituted or unsubstituted C 1~30 heteroalkylene, substituted or unsubstituted C 3~30Cycloalkylene, 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 heterocycloalkyl). L 7 When is a single bond, the moiety -R 37 is directly bonded to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)O-R 37 ).

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

[0081] Exemplary monomers of formula (9) include the following: [Chemical formula] (wherein R f is as defined for formula (9)) One or more of which may be included.

[0082] The polymer is base-soluble and / or may contain repeating units having a pKa of 12 or less. For example, repeating units containing polar groups pendant on the main chain of the polymer may be derived from one or more monomers of formula (10), (11) or (12). [Chemical]

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

[0084] In formula (10), R 38 is 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, 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) are substituted with one or more of halogen, C 1~4 fluoroalkyl group, typically a fluoroalkyl group such as fluoromethyl, sulfonamide group -NH-S(O)2-Y 1 (wherein Y 1 is F or C 1~4 perfluoroalkyl) (e.g., -NHSO2CF3) or fluoroalcohol group (e.g., -C(CF3)2OH).

[0085] In formula (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 102is selected from hydrogen and optionally substituted C 1~10 alkyl), represents one or more linking moieties selected from, for example, C 1~6 alkylene or C 3~20 cycloalkylene, etc., a polyvalent linking group selected from optionally substituted aliphatic hydrocarbons, aromatic hydrocarbons and combinations thereof. For example, the polymer has the formula (10) (wherein L 8 is a single bond or 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 arylene). The polymer may further include repeating units derived from one or more monomers of).

[0086] In formula (11), n3 is an integer from 1 to 5, typically 1. When n3 is 1, it should be understood that the group L 8 is a divalent linking group. When n3 is 2, it should be understood that the group L 8 is a trivalent linking group. Similarly, 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 should be understood to be 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 more, the carboxylic acid group (-C(O)OH) may be bonded to the same atom of the linking group L 8 In other embodiments, when n is 2 or more, the carboxylic acid group (-C(O)OH) may be bonded to different atoms of the linking group L 8

[0087] In formula (12), L 9 ​represents a single bond or a divalent linking group. Preferably, L 9 is a single bond, a substituted or unsubstituted C 6~30 arylene or a substituted or unsubstituted C 6~30 cycloalkylene.

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

[0089] In formula (12), Ar 1 is a substituted C 5~60 aromatic group that may optionally contain one or more aromatic ring heteroatoms selected from N, O, S, or combinations thereof. The aromatic group can be monocyclic, non-fused polycyclic, or fused polycyclic. C 5~60 When the aromatic group is polycyclic, the rings or ring groups can be fused (such as naphthyl, etc.), non-fused, or combinations thereof. When the polycyclic C 5~60 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). In some embodiments, the polycyclic C 5~60 aromatic group can include a combination with a ring directly bonded to a fused ring (such as binaphthyl).

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

[0091] Non-limiting examples of the monomers of formula (10), (11), or (12) include the following:

Chemical formula

Chemical formula

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

[0093] Non-limiting exemplary polymers of the present invention include the following:

Chemical formula

Chemical formula

Chemical formula

[0094] The polymer can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined using a suitable solvent and initiator, or supplied separately and polymerized in a reactor. For example, the polymer can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with actinic rays 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 that causes cleavage of acid-labile groups present on the polymer of the photoresist composition during post-exposure bake (PEB). The PAG can be in non-polymeric form or polymeric form and can be present, for example, in the polymerized repeating units of a polymer as described above or as part of a different polymer. Suitable non-polymeric PAG compounds have the formula G + A - (wherein 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, and A - is a non-polymerizable organic anion). In some embodiments, the PAG can be included as a non-polymeric PAG compound, a repeating unit of a polymer having a PAG moiety 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-polymer PAG compounds are known in the technical field of chemically amplified photoresists and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate and di-t-butylphenyliodonium camphorsulfonate. Nonionic sulfonates and sulfonyl compounds such as 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 such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate, 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 photoacid generators are further described in Hashimoto et al. (Patent Document 1), column 37, lines 11 to 47 and columns 41 to 91.Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, nitrobenzyl esters, s-triazine derivatives, benzoin tosylate, t-butylphenyl α-(p-toluenesulfonyloxy)acetate, and t-butyl α-(p-toluenesulfonyloxy)acetate as described in (Patent Document 2) and (Patent Document 1).

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

[0099] In some embodiments, G + can be a sulfonium cation or an iodonium cation. For example, G + can be a sulfonium cation as described herein with respect to M + , or G + can be an iodonium cation as described herein with respect to M + . When the photoresist composition further contains a PAG, the cation G + can be the same as M + , or the cation G + can be different from M + .

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

[0101] Exemplary organic anions having a sulfonate group include the following.

Chemical formula

[0102] Exemplary non-sulfonated anions include the following. [Chemical]

[0103] The photoresist composition may optionally contain a plurality of PAGs. The plurality of PAGs can be polymeric, non-polymeric, or can include both polymeric PAGs and non-polymeric PAGs. Preferably, each PAG of the plurality of PAGs is of a non-polymerizable type.

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

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

[0106] In formula (13), R j can be hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 alkyl. 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. Preferably, Q 1 contains 1 to 10 carbon atoms and at least 1 heteroatom, more preferably -C(O)-O-.

[0107] In formula (13), A 1 is 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 6~30It may be one or more of arylene or substituted or unsubstituted C 3~30 heteroarylene. Preferably, A 1 is a divalent C 1~30 perfluoroalkylene group which may be optionally substituted.

[0108] In formula (13), Z - is an anionic moiety, and its conjugate acid typically has a pKa of -15 to 1. Z - may be a sulfonate, carboxylate, anion of sulfonamide, anion of sulfonimide or methide anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonate and fluorinated sulfonimide. G + 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: [Chemical formula] (wherein G + is an organic cation) may be included.

[0110] When included, the polymer may contain repeating units containing a PAG moiety in an amount of 1 to 15 mol%, typically 1 to 8 mol%, more typically 2 to 6 mol% based on all the repeating units in the polymer.

[0111] The photoresist composition may contain a molecular glass compound. The molecular glass compound is a tetrameric calix[4]arene having a free hydroxy group that is stable to bases but modified using acetal chemistry because it contains an acid-cleavable aromatic protecting group as provided in (Patent Document 3). The photoresist composition may contain the molecular glass compound in an amount of 50 to 99% by weight, preferably 55 to 95% by weight, more preferably 60 to 90% by weight, and even more preferably 65 to 90% by weight based on the total weight of the solid content. It will be understood that the "molecular glass compound" used in this context in relation to the components in the photoresist may mean only the molecular glass compound or a combination of the molecular compound with another molecular compound or a polymer useful for the photoresist.

[0112] The photoresist composition further includes 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, iso-propanol, 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; ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone, 2-heptanone and cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (HBM) and ethyl acetoacetate; lactones such as 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 in the photoresist composition (i.e., the cumulative solvent content with respect to all solvents) is typically 40 to 99% by weight, for example 70 to 99% by weight or 85 to 99% by weight, based on the total solids of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the photoresist layer to be coated and the coating conditions.

[0114] The polymer can typically be present in the photoresist composition in an amount of 10 to 99.9% by weight, typically 25 to 99% by weight, more typically 50 to 95% by weight, based on the total solids of the photoresist composition. It will be understood that the "total solids" includes the photoactive compound, the polymer, the 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 (a "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, etc. in the presence of an aqueous alkaline developer after the exposure step and the post-exposure baking step. The base-labile group will not significantly react (e.g., undergo a bond cleavage reaction) prior to the development step of the photoresist composition containing the base-labile group. Thus, for example, the base-labile group will be substantially inert during 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 group (or moiety) decomposes, cleaves or reacts during the pre-exposure soft bake, exposure and post-exposure bake steps. The base-labile group is highly reactive under typical photoresist development conditions using an aqueous alkaline photoresist developer such as, for example, an aqueous solution of 0.26 normal (N) tetramethylammonium hydroxide (TMAH). For example, a 0.26 N aqueous solution of TMAH can be used for single paddle development or dynamic development, for example, where a 0.26 N TMAH developer is dispensed onto the imaged photoresist layer for a suitable time such as 10 to 120 seconds (s). Exemplary base-labile groups are ester groups, typically fluorinated ester groups. Preferably, the base-labile material is substantially immiscible with the polymer and other solid components of the photoresist composition and has a lower surface energy than them. When coated on a substrate, the base-labile material can thereby separate from the other solid components of the resist composition to the upper surface of the formed photoresist layer.

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

[0117] The base-labile polymer has the formula (14a):

Chemical formula

[0118] Exemplary monomers of formula (14a) can include the following.

Chemical formula

[0119] The base-labile polymer can include repeating units containing two or more base-labile groups. For example, the base-labile polymer has the formula (14b):

Chemical formula

[0120] Exemplary monomers of formula (14b) include the following.

Chemical formula

[0121] The base-labile polymer can contain repeating units containing one or more base-labile groups. For example, the base-labile polymer has the formula (14c):

Chemical formula

[0122] Exemplary monomers of formula (14c) can include the following.

Chemical formula

[0123] In a further preferred embodiment of the present invention, the base-labile polymer may include 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 ester) or acid-labile acetal groups. For example, the base-labile polymer may include repeating units 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 may include 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 show a reduction in defects associated with the resist relief image 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, irradiation with actinic radiation at an effective wavelength, or a combination thereof. Additionally or alternatively, one or more base-labile groups can be grafted onto the polymer backbone 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. The base-labile material that is a single molecule typically has an M W in the range of 50 to 1,500 Da. Exemplary base-labile materials include the following.

Chemical formula

[0126] When present, the base-labile material is typically present in the photoresist composition in an amount of 0.01 to 10 wt% or 1 to 5 wt% based on the total solids of the photoresist composition.

[0127] In addition to or instead of the base - labile polymer, the photoresist composition may further comprise one or more polymers in addition to and different from the photoresist polymers described above. For example, the photoresist composition may be as described above, but may contain additional polymers with different compositions or polymers similar to those described above but lacking each of the essential repeating units. In addition to or instead of, one or more additional polymers may include those selected from those well - known in photoresist technology, such as polyacrylate, polyvinyl ether, polyester, polynorbornene, polyacetal, polyethylene glycol, polyamide, polyacrylamide, polyphenol, novolak, styrene - based polymers, polyvinyl alcohol, or combinations thereof.

[0128] The photoresist composition may further comprise one or more additional optional additives. For example, optional additives may include chemoselective dyes and contrast agents, striation inhibitors, plasticizers, speed accelerators, sensitizers, photodegradable deactivators (PDQs, also known as photodegradable bases), basic deactivators, thermal acid generators, surfactants, etc., or combinations thereof. When present, the optional additives are typically present in the photoresist composition in an amount of 0.01 - 10 wt% based on the total solids of the photoresist composition.

[0129] The PDQ generates a weak acid upon irradiation. The acid generated from the photodegradable deactivator is not strong enough to react rapidly with the acid - labile groups present in the resist matrix. Exemplary photodegradable deactivators include, for example, photodegradable cations, preferably, for example, C 1~20 carboxylic acid or C 1~20Also included are those useful for preparing a strong acid generator compound paired with an anion of a weak acid (pKa>1) such as an anion of sulfonic acid. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In a preferred embodiment, the photodegradable deactivator is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0130] The photodegradable deactivator can be in a non-polymeric form or a polymer-bound form. In the case of the polymer form, the photodegradable deactivator is present within the 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%, more preferably 1 to 2 mol% based on all the repeating units of the polymer.

[0131] Exemplary basic deactivators 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; cyclic aliphatic amines such as 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butyl piperazine-1,4-dicarboxylate and N-(2-acetoxy-ethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3- Linear and cyclic amides such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate, and their derivatives; ammonium salts such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates and phosphonates; imines such as primary and secondary aldimines and ketimines; diazines such as optionally substituted pyrazine, piperazine and phenazine; diazoles such as optionally substituted pyrazole, thiadiazole and imidazole; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidine are included.

[0132] The basic deactivator can be in non-polymeric form or polymer-bonded form. When in polymeric form, the deactivator can be present within the repeating unit of the polymer. The repeating unit containing the deactivator 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 all the repeating units of the polymer.

[0133] Exemplary surfactants include fluorinated and non-fluorinated surfactants, which can be ionic or non-ionic, with non-ionic surfactants being preferred. Exemplary fluorinated non-ionic surfactants include perfluoro C4 surfactants such as the FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols such as the POLYFOX PF-636, PF-6320, PF-656 and PF-6520 fluorosurfactants manufactured by Omnova. In certain embodiments, the photoresist composition further includes a surfactant polymer containing fluorine-containing repeating units.

[0134] A pattern forming method using the photoresist composition of the present invention will now be described. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A variety of electronic device substrates, for example, semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multi-chip modules; flat panel display substrates; substrates for light emitting diodes (LEDs) such as organic light emitting diodes (OLEDs), etc. can be used in the present invention, and semiconductor wafers are 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. A typical wafer substrate diameter is 200 to 300 millimeters (mm), but wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate can include one or more layers or structures that can optionally include the active or operable portion of the device to be formed.

[0135] Typically, one or more lithography layers such as a hard mask layer, for example, a spin-on carbon (SOC), amorphous carbon or metal hard mask layer, a CVD layer such as a silicon nitride (SiN), silicon oxide (SiO) or silicon oxynitride (SiON) layer, an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of the substrate before the photoresist composition of the present invention is coated. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0136] Optionally, the layer of adhesion promoter can be applied to the substrate surface before coating the photoresist composition. When an adhesion promoter is desired, any suitable adhesion promoter for the polymer film can be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents 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 the substrate by any suitable method, such as spin coating, spray coating, dip coating, doctor blading, etc. For example, the application of the layer of photoresist can be achieved by spin coating the photoresist in a solvent using a coating track, in which case the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically rotated at a speed of up to 4,000 revolutions per minute (rpm), for example 200 to 3,000 rpm, for a period of 15 to 120 seconds to obtain a layer of the photoresist composition on the substrate. It will be well understood by those skilled in the art that the thickness of the layer to be coated can be adjusted by varying the spin speed and / or the total solids content of the composition. The photoresist layer formed from the composition of the present invention typically has a dry layer thickness of 10 to 500 nanometers (nm), preferably 15 to 200 nm, more preferably 20 to 120 nm.

[0138] The photoresist composition is then typically soft baked to minimize the solvent content in the layer, thereby forming a non-sticky coating and improving the adhesion of the layer to the substrate. Soft baking is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The temperature and time of soft baking will depend, for example, on the photoresist composition and thickness. The soft bake temperature is typically 80 - 170 °C, more typically 90 - 150 °C. The soft bake time is typically 10 seconds - 20 minutes, more typically 1 minute - 10 minutes, and even more typically 1 minute - 2 minutes. The heating time can be readily determined by one of ordinary skill in the art based on the components of the composition.

[0139] The photoresist layer is then patternwise exposed to actinic radiation to provide a difference in solubility between the exposed and unexposed regions. References herein to the exposure of the photoresist composition to actinic radiation that activates the composition indicate that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions corresponding to the exposed and unexposed regions of the resist layer, respectively. Such exposure can alternatively be performed without a photomask in a direct writing process, which is typically used for electron beam lithography. Actinic 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 actinic radiation is 193 nm radiation or EUV radiation. This method is utilized in immersion or dry (non-immersion) lithography techniques. The exposure energy typically ranges from 1 to 200 millijoules per square centimeter (mJ / cm 2 ), preferably 10 - 100 mJ / cm 2 , more preferably 20 - 50 mJ / cm 2 and depends on the exposure tool and the components of the photoresist composition.

[0140] After the exposure of the photoresist layer, post-exposure baking (PEB) of the exposed photoresist layer is performed. The PEB can be carried out, for example, on a hot plate or in an oven, and a hot plate is typical. The conditions for the PEB will depend, for example, on the photoresist composition and the layer thickness. The PEB is typically carried out at a temperature of 70 to 150 °C, preferably 75 to 120 °C, and over a period of 30 to 120 seconds. A latent image defined by a polarity switching region (exposed region) and a non-switching region (non-exposed region) is formed in the photoresist.

[0141] The exposed photoresist layer is then developed with a developer suitable for selectively removing the regions of the layer that are soluble in the developer, while the remaining insoluble regions form the resulting photoresist pattern relief image. In the case of a positive tone development (PTD) process, the exposed regions of the photoresist layer are removed during development and the non-exposed regions remain. Conversely, in a negative tone development (NTD) process, the exposed regions of the photoresist layer remain and the non-exposed regions are removed during development. The application of the developer can be achieved by any suitable method as described above with respect to the application of the photoresist composition, and spin coating is typical. The development time is a period effective for removing the soluble regions of the photoresist, and a time of 5 to 60 seconds is typical. The development is typically carried out at room temperature.

[0142] Suitable developers for the PTD process include aqueous base developers such as tetramethylammonium hydroxide (TMAH), preferably 0.26 normal (N) TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and other quaternary ammonium hydroxide solutions, 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 the 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 the NTD developer include, for example, those selected from ketones, esters, ethers, hydrocarbons and mixtures thereof. The NTD developer is typically 2-heptanone or n-butyl acetate.

[0143] The coated substrate can be formed from the photoresist composition of the present invention. Such a coated substrate includes (a) a substrate having one or more layers to be patterned on its surface; and (b) a layer of the photoresist composition on one side of the one or more layers to be patterned.

[0144] The photoresist pattern can be used, for example, as an etch mask, thereby enabling the pattern to be transferred to one or more underlying continuous 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 a lower hard mask layer, which in turn is used as an etch mask for pattern transfer to one or more layers under the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such patterning processes, 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 Example. The synthesis reaction was carried out under normal atmospheric conditions. All chemicals were used as received from commercial suppliers without further purification.

[0147] Synthesis of Triphenylsulfonium α-Cyanocinnamate (PAC1)

Chemical formula

[0148] Synthesis of bis(4-(tert-butyl)phenyl)iodonium α-cyanocinnamate (PAC2) 10.0 g of α-cyanocinnamic acid (57.74 mmol) was combined with 150 mL of THF to prepare a solution, and 2 g of LiOH in 25 mL of DI water was added to the solution. The resulting mixture was stirred at room temperature (about 25 °C) for 1 hour. Then, THF was removed under reduced pressure to afford the lithium α-cyanocinnamate salt. To 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, and the mixture was stirred at room temperature (about 25 °C) for 4 hours. Then, the organic phase was 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 afford the crude photoactive compound PAC2. The crude product was dissolved in 40 mL of acetone, and this solution was poured into 300 mL of heptane to afford 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 (in d6-acetone), δ (ppm): 7.89 (m, 4H, ArH), 7.78 (m, 3H, ArH), 7.38 (m, 7H), 1.21 (s, 18H, 6(CH3)). The 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) 5.0 g of 4-trifluoromethylcinnamic acid (23.13 mmol) was combined with 150 mL of THF to prepare a solution. 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 (about 25 °C) for 1 hour. Then, THF was removed under reduced pressure to afford lithium 4-trifluoromethylcinnamate salt. To 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, and the mixture was stirred at room temperature (about 25 °C) for 4 hours. Then, the organic phase was 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 afford the crude photoactive compound PAC3. The crude product was dissolved in 20 mL of acetone, and this solution was poured into 150 mL of heptane to afford 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 1H NMR (d6-acetone), 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(CH3)). The 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-fluoro cinnamic acid (6.0 mmol) and 10 mL of THF, and 0.2 g of LiOH in 5 mL of DI water was added to the solution. The resulting mixture was stirred at room temperature (about 25 °C) for 1 hour. Then, THF was removed under reduced pressure to afford the lithium α-fluoro cinnamate salt. To the lithium α-fluoro cinnamate 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 (about 25 °C) for 4 hours. Then, the organic phase was 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 afford the 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 give a white solid. The yield of PAC4 was 2.2 g (65.5%). 1 1H 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)). The UPLC purity was 99.92% as detected by UV absorbance at 210 nm.

[0151] Synthesis of bis(4-(tert-butyl)phenyl)iodonium (E)-3-cyclohexyl acrylate (PAC5) 1.0 g of (E)-3-cyclohexylacrylic acid (6.48 mmol) was combined with 10 mL of THF to prepare a solution. 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 (about 25 °C) for 1 hour. Then, THF was removed under reduced pressure to afford the lithium 3-cyclohexylacrylate salt. To 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, and the mixture was stirred at room temperature (about 25 °C) for 4 hours. Then, the organic phase was 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 afford the 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 1H NMR (d6-acetone), 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). The 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) 1.0 g of (E)-3-(4-iodophenyl)acrylic acid (3.65 mmol) was combined with 10 mL of THF to prepare a solution. 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 (about 25 °C) for 1 hour. Then, THF was removed under reduced pressure to afford 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 (about 25 °C) for 4 hours. Then, the organic phase was 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 afford the 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 1H NMR (d6-acetone), 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(CH3)). The UPLC purity was 99.88% as detected by UV absorbance at 210 nm.

[0153] Synthesis of triphenylsulfonium cinnamate (PAC7)

Chemical formula

[0154] 5.0 g of silver cinnamate (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. The 1 1H NMR showed the expected product with a 1:1 cation-to-anion ratio. The mixture was filtered to remove the 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 afford PAC7 as a colorless oil. The yield of PAC7 was 1.7 g (70.8%). 1 1H-NMR (d6 in acetone), 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). The UPLC purity was 99.75% as detected by UV absorbance at 210 nm.

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

[0156] 2.5 g of silver benzoate (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. The 11H-NMR showed the expected product with a 1:1 cation-to-anion ratio. The mixture was filtered to remove the 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 afford CPAC8 as a colorless oil. The UPLC purity was 99.63% as detected by UV absorbance at 210 nm.

[0157] Synthesis of Triphenylsulfonium (E)-3-(thiophen-3-yl)acrylate (CPAC9) 2.55 g of (E)-3-(thiophen-3-yl)acrylic acid (16.2 mmol), 50 mL of acetone, and 50 mL of DI water were combined to prepare a solution, and then 1.80 g (7.76 mmol) of silver oxide was added to the solution in small portions. The resulting mixture was stirred at room temperature (ca. 25 °C) for 48 h. The precipitate was isolated by filtration, washed with acetone, and dried under reduced pressure. The yield of silver (E)-3-(thiophen-3-yl)acrylate was 3.30 g.

[0158] 3.30 g of silver (E)-3-(thiophen-3-yl)acrylate (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 (ca. 25 °C) for 12 h. The 1 1H-NMR showed the expected product with a 1:1 cation-to-anion ratio. The mixture was filtered to remove the 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 afford CPAC9 as a colorless oil. The UPLC purity was 99.64% as detected by UV absorbance at 210 nm. [Chemical formula]

[0159] Photoresist formulation 1. The photoresist composition was prepared by dissolving the solid components in a solvent using the materials and amounts shown in Table 1 up to 2.6 wt% total solids. Each mixture was shaken using a mechanical shaker and filtered through a PTFE disk filter having a pore size of 0.2 μm. The amounts of the polymer, PAG, and photoactive compound are reported as weight % based on the total solids 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. A 200 nm wafer for the photolithography test was coated with AR (trademark) 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 (trademark) 40 BARC (DuPont Electronics & Industrial) was placed on top of the AR (trademark) 3 layer and soft baked at 205 °C for 60 seconds to form a second BARC layer with a thickness of 80 nm. Next, a photoresist composition was 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. The wafer was exposed to 248 nm radiation using a Canon FPA-5000 ES4 scanner (NA = 0.8, outer sigma = 0.85, inner sigma = 0.57) with a mask having a 1:1 line-space (L / S) pattern (120 nm line width). The exposed wafer was baked after exposure at 100 °C for 60 seconds, developed in a 0.26 N TMAH solution for 60 seconds, then rinsed with DI water and spin dried to form a photoresist pattern. Measurement of the critical dimension (CD) line width of the formed pattern was performed using a HITACHI S-9380 CD-SEM. The line width roughness (LWR) was determined from the deviation of the line width measured over a predetermined length and evaluated using the 3 sigma (3σ) deviation of the width from the distribution of a total of 100 arbitrary line width measurement points. The LWR data is shown in Table 1.

[0161]

Table 1

[0162] Photoresist formulation 2. The photoresist composition was prepared by dissolving the solid components in a solvent using the materials and amounts shown in Table 2 up to 2.42 wt% total solids. Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disk-shaped filter having a pore size of 0.2 μm. The amounts of polymer, PAG, and photoactive compound are reported as weight % based on the total solids 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. A 200 nm wafer for the photolithography test was 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 having a thickness of 80 nm. Then, the photoresist composition was coated onto the dual BARC stack and soft baked at 110 °C for 60 seconds to obtain a photoresist thin film layer having a thickness of 120 nm.

[0164] A wafer was exposed to 248 nm radiation using a CANON FPA-5000 ES4 scanner (NA = 0.8, outer sigma = 0.85, inner sigma = 0.57) with a mask having a 1:1 L / S pattern (120 nm line width). The exposed wafer was subjected to post-exposure bake at 100 °C for 60 seconds, developed in a 0.26 N TMAH solution for 60 seconds, then rinsed with DI water and spin-dried to form a photoresist pattern. CD line width measurement of the formed pattern was performed using a HITACHI S-9380 CD-SEM. LWR was determined from the deviation of the line width measured over a predetermined length and evaluated using the 3σ deviation of the width from the distribution of a total of 100 arbitrary line width measurement points. The LWR data is shown in Table 2.

[0165]

Table 2

[0166] Photoresist formulation 3. The photoresist composition was prepared by dissolving the solid components in a solvent using the materials and amounts shown in Table 3 up to 1.55 wt% total solids. Each mixture was shaken using a mechanical shaker and filtered through a PTFE disk-shaped filter having a pore size of 0.2 μm. The amounts of the polymer, PAG, and photoactive compound are reported as wt% based on the total solids 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 a photolithography test 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 disposed on the organic BARK thin film layer to form a second layer having a thickness of 20 nm. Next, a photoresist composition was spin-coated onto the BARC / SiARC two-layer stack and soft-baked at 110 °C for 60 seconds to obtain a photoresist thin film layer having a thickness of 40 nm.

[0168] Using a mask having a groove pattern with a CD of 20.25 nm and a pitch of 36, the wafer was exposed to 13.5 nm radiation using an ASML NXE3400B scanner. The exposed wafer was baked after exposure at 100 °C for 60 seconds, developed with a 0.26 N TMAH solution for 60 seconds, rinsed with DI water, and spin-dried to form a resist groove pattern. The CD linewidth measurement of the formed groove pattern was performed using a HITACHI CG5000 CD-SEM.

[0169] Table 3 shows the EUV sizing energy (E 2 ) measured for the examples, which was the irradiation energy reported in millijoules per square centimeter (mJ / cm size ) at which the groove pattern was resolved up to 18 nm. Table 3 also shows the depth of focus (DOF) for the examples, which is the total distance range of focus that maintains the printing characteristics without any printing 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 a photoresist composition having unexpected lithography performance, achieving a reduction in LWR of up to 20%. The improvement in LWR was observed with no effect on photospeed and with an improvement in DCOF.

[0172] Although the present disclosure has been described in conjunction with what are presently considered to be practical and exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, the invention is intended to cover various modifications and equivalent configurations included within the spirit and scope of the appended claims. Furthermore, the present invention includes the following Aspects 1 to 20: [Aspect 1] Formula (1a) or (1b): [Chemical Formula] (wherein, R 1 is a substituted or unsubstituted C 1~30 alkyl, a substituted or unsubstituted C 3~30 cycloalkyl, a substituted or unsubstituted C 3~30 heterocycloalkyl, a substituted or unsubstituted C 6~30 aryl or a substituted or unsubstituted C containing an aromatic ring heteroatom selected from nitrogen, oxygen, or a combination thereof 3~30 heteroaryl; R 2 is hydrogen, halogen, a substituted or unsubstituted C 1~30 alkyl, a substituted or unsubstituted C 1~30 heteroalkyl, a substituted or unsubstituted C 3~30 cycloalkyl, a substituted or unsubstituted C 3~30 heterocycloalkyl, a substituted or unsubstituted C 2~30 alkenyl, a substituted or unsubstituted C 2~30 alkynyl, a substituted or unsubstituted C1 - C 30 alkoxy group, a substituted or unsubstituted C1 - C 30 alkylthio group, a substituted or unsubstituted C3 - C 10A cycloalkenyl group, a substituted or unsubstituted C3-C 10 heterocycloalkenyl group, a substituted or unsubstituted C 6~30 aryl, a substituted or unsubstituted C 7~30 arylalkyl, a substituted or unsubstituted C 7~30 alkylaryl or a substituted or unsubstituted C6-C 30 aryloxy group; R 3 is hydrogen or a non-hydrogen substituent; R 4 is a substituted or unsubstituted C 1~30 alkyl, a substituted or unsubstituted C 3~30 cycloalkyl, a substituted or unsubstituted C 3~30 heterocycloalkyl, a substituted or unsubstituted C 6~30 aryl or a substituted or unsubstituted C 3~30 heteroaryl; R 2 、R 3 and R 4 each optionally further contains one or more divalent linking groups as part of their structures, and each of said one or more divalent linking groups is independently substituted or unsubstituted; R 2 and R 3 together form a ring, a ring optionally further containing one or more divalent linking groups as part of its structure, each of said one or more divalent linking groups is substituted or unsubstituted, and said ring is substituted or unsubstituted; and M + is an organic cation) of the photoactive compound. [Aspect 2] R 3 is a substituted or unsubstituted C 1~20 organic group, the photoactive compound according to Aspect 1. [Aspect 3] R 3 further contains -C(O)-, -C(O)O-, -C(O)N(R 5 )- or a combination thereof, and R 5 is hydrogen, a substituted or unsubstituted C 1~10Alkyl, substituted or unsubstituted C 1~10 Heteroalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 The photoactive compound according to embodiment 2, which is heteroaryl. [Embodiment 4] R 3 is a halogen atom, a cyano group or C 1~5 The photoactive compound according to embodiment 1, which is haloalkyl. [Embodiment 5] R 1 is 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 The photoactive compound according to embodiment 1, which is heteroaryl containing an aromatic ring heteroatom selected from nitrogen or oxygen. [Embodiment 6] R 4 is 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 The photoactive compound according to embodiment 1, which is heteroaryl. [Embodiment 7] M + The photoactive compound according to embodiment 1, which is a sulfonium cation or an iodonium cation. [Embodiment 8] The photoactive compound according to embodiment 1; and a solvent A photoresist composition comprising. [Embodiment 9] The photoresist composition according to embodiment 8, further comprising a material that switches solubility in an organic solvent in the presence of a base or under the action of an acid, and the material is different from the photoactive compound. [Embodiment 10] The photoresist composition according to embodiment 9, further comprising a photoacid generator different from the photoactive compound. [Embodiment 11] A method of forming a pattern, comprising: (a) forming a photoresist layer from the photoresist composition according to Aspect 8 on a substrate; (b) patternwise exposing the photoresist layer to actinic radiation; and (c) developing the exposed photoresist layer to provide a resist relief image. A method as described above. [Aspect 12] R 3 is a substituted or unsubstituted C 1~20 organic group, and the photoresist composition according to Aspect 8. [Aspect 13] R 3 further comprises -C(O)-, -C(O)O-, -C(O)N(R 5 )- or a combination thereof, and R 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 heteroaryl, and the photoresist composition according to Aspect 8. [Aspect 14] R 3 is a halogen atom, a cyano group or C 1~5 haloalkyl, and the photoresist composition according to Aspect 8. [Aspect 15] R 1 is 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 heteroaryl containing an aromatic ring heteroatom selected from nitrogen or oxygen, and the photoresist composition according to Aspect 8. [Aspect 16] R 4 is substituted or unsubstituted C 3~20 cycloalkyl, substituted or unsubstituted C 3~20Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 The photoresist composition according to aspect 8, which is heteroaryl. [Aspect 17] R 4 is 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 The photoresist composition according to aspect 8, which is heteroaryl. [Aspect 18] M + The photoresist composition according to aspect 8, which is a sulfonium cation or an iodonium cation. [Aspect 19] R 3 is substituted or unsubstituted C 1~20 The method according to aspect 11, which is an organic group. [Aspect 20] R 3 further includes -C(O)-, -C(O)O-, -C(O)N(R 5 )- or a combination thereof, and R 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 The method according to aspect 11, which is heteroaryl.

Claims

1. Formula (3a): 【Chemical 1】 (wherein Ring CY1 is C ３～８ cycloalkyl, C ６～１４ aryl or C containing an aromatic ring heteroatom selected from nitrogen, oxygen or a combination thereof ３～１２ heteroaryl; Each L １ is independently a single bond; Each R ８ is, independently, hydroxyl, -F, -I, -CF ３ , or substituted or unsubstituted C １～１０ alkyl; a is an integer from 0 to 5; L ２ is a single bond; R ９ is hydrogen, cyano, hydroxyl, -F, -I, -CF ３ , or substituted or unsubstituted C １～１０ alkyl; M ＋ is a sulfonium cation of formula (2a) or an iodonium cation of formula (2b): 【Chemical 2】 (In formulas (2a) and (2b), R １０ 、 R ２０ and R ３０ are each independently a substituted or unsubstituted C １～２０ alkyl, a substituted or unsubstituted C ３～２０ cycloalkyl, a substituted or unsubstituted C ２～２０ alkenyl, a substituted or unsubstituted C ６～３０ aryl, a substituted or unsubstituted C ６～３０ iodoaryl, a substituted or unsubstituted C ３～３０ heteroaryl, a substituted or unsubstituted C ７～２０ arylalkyl or a substituted or unsubstituted C ４～２０ heteroarylalkyl; R １０ , R ２０ and R ３０ each of which may be either separate or linked to another group of R １０ , R ２０ or R ３０ through a single bond or a divalent linking group to form a ring; R １０ 、 R ２０ and R ３０ each of which may optionally contain a divalent linking group as part of its structure; R １０ , R ２０ and R ３０ each of which may optionally contain an acid-labile group selected independently 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; R １０ 、 R ２０ and / or R ３０ For the divalent linking group for linking of the group, -O-, -S-, -Te-, -Se-, -C(O)-, -C(S)-, -C(Te)- or -C(Se)-, substituted or unsubstituted C １～５ alkylene or combinations thereof are included) and; The anion of formula (3a) is not α-cyano-4-hydroxysinnamate) The photoactive compound of.

2. Ring CY1 is C ６～１４ The photoactive compound according to claim 1, wherein it is aryl.

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

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

5. The photoactive compound according to claim 1; A solvent A photoresist composition containing.

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

7. The photoresist composition according to claim 6, further comprising a photoacid generator different from said photoactive compound.

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

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