Compounds and photoresist compositions including the same

Abstract

To provide a compound and a photoresist composition containing the same.SOLUTION: A compound represented by Formula (1): (wherein X is a group having a valency of r; each R1 is independently an organic group comprising an acid-labile group; m is an integer greater than or equal to 1; k is an integer from 1 to 5; and r is an integer from 2 to 10), wherein the compound is non-polymeric.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to cleavable compounds, photoresist compositions containing such compounds, and patterning methods using such photoresist compositions. The present invention finds particular applicability in lithography applications in the semiconductor manufacturing industry. [Background technology]

[0002] A photoresist composition is a photosensitive material used to transfer a pattern to one or more underlying layers, such as a metal, semiconductor, or dielectric layer, disposed on a substrate. Positive-tone, chemically amplified photoresist compositions are traditionally used for high-resolution processing. Such resist compositions typically contain a polymer with acid-labile groups and a photoacid generator (PAG). A layer of the photoresist composition is patternwise exposed to activating radiation, and the PAG generates acid in the exposed regions. During a post-exposure bake, the acid causes cleavage of the acid-labile groups in the polymer. This results in a difference in solubility characteristics between the exposed and unexposed regions of the photoresist layer in a developer solution. In a positive-tone development (PTD) process, the exposed regions of the photoresist layer become soluble in a developer, typically an aqueous base developer, and are removed from the substrate surface. The unexposed regions, which are insoluble in the developer, remain after development, forming a positive-tone relief image. The resulting relief image allows for selective processing of the substrate.

[0003] To increase the integration density of semiconductor devices and enable the formation of structures with dimensions in the nanometer (nm) range, photoresists and photolithography processing tools with high resolution capabilities have been developed and continue to be developed. One approach to achieving nm-scale feature sizes in semiconductor devices is to use activating radiation with short wavelengths, such as 193 nm or shorter, for exposure of photoresist layers. To further improve lithography performance, immersion lithography tools have been developed to effectively increase the numerical aperture (NA) of the lens in the imaging device. This is achieved by using a fluid with a relatively high refractive index, typically water, between the final surface of the imaging device and the top surface of the semiconductor wafer.

[0004] Deep ultraviolet argon fluoride (ArF) excimer laser immersion tools are currently using multiple (double, triple, or higher) patterning techniques to push the limits of lithography processing up to the 16 nm and 14 nm device nodes. However, the use of multiple patterning can be costly in terms of increased material usage and the number of required process steps compared to single-step direct imaging patterns. Therefore, for advanced device nodes, the need for photoresist compositions for next-generation (e.g., extreme ultraviolet, EUV) lithography using extremely short wavelength activating radiation at 13.5 nm is becoming increasingly important. With the extreme feature sizes associated with these nodes, the performance requirements for photoresist compositions are becoming even more stringent. Desired performance characteristics include, for example, high sensitivity to activating radiation, low unexposed film thickness loss, good contrast, high resolution, and good linewidth roughness (LWR). [Prior art documents] [Patent documents]

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

[0006] Thus, there is a continuing need in the art for new compounds useful in photoresist compositions that can provide improved lithographic performance. [Means for solving the problem]

[0007] Formula (1): [ka] (wherein X is a group having a valence of r, and each L 1 are independently a single bond or a divalent linking group, and each L 2 is a single bond or a linking group, and each Ar 1 are independently substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 3~30 Heteroarylene, substituted C 6~30 The arylene and the substituted C3-30 heteroarylene each independently represent a halogen, C 1~30 Alkyl, C 1~30 Alkoxy, C4-30 cycloalkyl, C 3~30 Heterocycloalkyl, C 2~30 Alkenyl, C 2~30 Alkynyl, C6-30 aryl, C7-30 arylalkyl, C 7~30 Alkylaryl, C 6~30 Aryloxy, C 3~30 Heteroaryl, C 4~30 Alkylheteroaryl, C 4~30 Heteroarylalkyl or C 3~30 and each R is substituted with at least one heteroaryloxy. 1 are independently an organic group containing an acid labile group, and R 2 and R 3 are each independently hydrogen or a substituted or unsubstituted C 1~30 alkyl, and R 2 and R 3are optionally joined together via a single bond or a divalent linking group to form a ring, which ring is substituted or unsubstituted, m is an integer of 1 or greater, k is an integer of 1 to 5, and r is an integer of 2 to 10. The compound is not a polymer and is represented by the formula:

[0008] Also provided is a coated substrate comprising: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of a compound of the invention disposed on the one or more layers to be patterned.

[0009] Another embodiment provides a photoresist composition comprising a compound of the present invention and a solvent.

[0010] Also provided is a method of forming a pattern, comprising applying a layer of a compound of the present invention onto a substrate to provide a photoresist layer, patternwise exposing the photoresist layer to activating radiation to provide an exposed photoresist layer, and developing the exposed photoresist layer to provide a photoresist pattern.

[0011] Another aspect provides a method of forming a pattern, the method including applying a layer of a photoresist composition to a substrate to provide a photoresist composition layer, patternwise exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer, and developing the exposed photoresist composition layer to provide a resist pattern. DETAILED DESCRIPTION OF THE INVENTION

[0012] Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in this description. In this regard, the exemplary embodiments may have different forms and should not be construed as limited to the description set forth herein. Accordingly, exemplary embodiments are described below by reference to the figures only to describe aspects of the present description. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. Phrases such as "at least one," when preceding a list of elements, modify the entire list of elements and not each individual element of the list.

[0013] As used herein, the terms "a," "an," and "the" do not denote a limitation on quantity and should be construed to include both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. The modifier "about," used in connection with a quantity, is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity). All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independent and inclusive of each other. The suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including at least one of that term. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where the event does not occur. The terms "first," "second," etc., as used herein, do not denote order, quantity, or importance, but rather are used to distinguish one element from another. When an element is said to be "on" another element, it may be in direct contact with the other element, or intervening elements may be present between them. In contrast, when an element is said to be "directly on" another element, there are no intervening elements present. It should be understood that the described components, elements, limitations, and / or features of the embodiments can be combined in any suitable manner in the various embodiments.

[0014] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning in the context of the relevant technical field and this disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0015] As used herein, the term "hydrocarbon" refers to an organic compound having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight- or branched-chain saturated hydrocarbon group having the specified number of carbon atoms and having a valence of one; "alkylene" refers to an alkyl group having a valence of two; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid group" refer to groups having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valence of two; "alkenyl" refers to a straight- or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of two; and "cycloalkenyl" refers to a group having at least one carbon atom. "aryl" refers to a monovalent monocyclic or polycyclic aromatic ring system in which all ring members are carbon and may include groups having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "aryl" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group substituted with an alkyl group; "arylalkyl" refers to an alkyl group substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0016] The prefix "hetero" means that the compound or group contains at least one member atom that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) in place of a carbon atom, each heteroatom being independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that contains at least one heteroatom; and "heteroalkyl" refers to an alkyl group having at least one heteroatom in place of a carbon.

[0017] As used herein, the term "(meth)acrylic" includes both acrylic and methacrylic species (i.e., acrylic and methacrylic monomers), and the term "(meth)acrylate" includes both acrylate and methacrylate species (i.e., acrylate and methacrylate monomers).

[0018] Unless expressly specified otherwise, each of the foregoing substituents may be optionally substituted. The term "optionally substituted" refers to substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of a chemical structure or group has been replaced with another terminal substituent, which is typically monovalent, provided that the normal valence of the designated atom is not exceeded. When a substituent is oxo (i.e., =0), two geminal hydrogen atoms on a carbon atom are replaced with terminal oxo groups. It is further noted that an oxo group is attached to a carbon through a double bond to form a carbonyl (C=0), and a carbonyl group is represented herein as -C(O)-. Combinations of substituents or variables are permissible. Exemplary substituents that may be present in a "substituted" position include nitro (-NO), cyano (-CN; sometimes referred to as a "nitrile group"), hydroxyl (-OH), oxo (O), amino (-NH), mono- or di-(C 1~6 ) alkylamino, alkanoyl (acyl, etc. C 2~6 alkanoyl group, etc.), formyl (-C(O)H), carboxylic acid or its alkali metal salt or ammonium salt;C 2~6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl), C 7~13Esters (including acrylates, methacrylates and lactones), such as aryl esters (-C(O)O-aryl or -OC(O)-aryl); amides (-C(O)NR, where R is hydrogen or C 1~6 alkyl), carboxamide (-CHC(O)NR, where 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 (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic). 6~12 Aryl, C having 1-3 separate or fused rings and 6-18 ring carbon atoms 7~19 Arylalkyl, arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(O)2-alkyl), C 6~12 Examples of cyano-substituted C alkyl groups include, but are not limited to, arylsulfonyl (-S(O)-aryl) or tosyl (CHCHSO-). If a group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group excluding the carbon atoms of any substituents. For example, the group -CHCHCN is a cyano-substituted C alkyl group.

[0019] As used herein, the term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that includes one or more fluoro, chloro, bromo, or iodo substituents in place of at least one hydrogen atom. In some embodiments, a combination of halo groups (e.g., bromo and fluoro) can be present. In other embodiments, only fluoro groups can be present. For example, the term "haloalkyl" (e.g., C 1~8 Haloalkyl) refers to an alkyl group substituted with one or more halogens. 1~8 "Haloalkyl" refers to a C alkyl group substituted with one or more halogens. 1~8 It refers to an alkyl group, which is further substituted with one or more other substituents that are not halogens. It should be understood that the substitution of a group with a halogen atom is not considered a heteroatom-containing group because the halogen atom does not replace a carbon atom. Thus, an unsubstituted C 1~8 Haloalkyls are not considered heteroalkyl groups.

[0020] Unless otherwise defined herein, a "divalent linking group" refers to -O-, -S-, -Te-, -Se-, -C(O)-, -C(O)O-, -N(R')-, C(O)N(R')-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 or a divalent group containing one or more of: a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted 1~20 Heteroalkyl, substituted or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30Typically, the divalent linking group is -O-, -S-, -C(O)-, -N(R')-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 R' is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 1~20 Heteroalkyl, substituted or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 More typically, the divalent linking group is -O-, -C(O)-, -C(O)O-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 and R' is at least one of 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 Includes heteroaryl.

[0021] The present invention provides a compound that can be used in photolithography, for example, in a photoresist composition.The photoresist composition containing the compound of the present invention can notably achieve improved lithography performance.The compound is represented by formula (1). [ka]

[0022] In formula (1), X is an r-valent group. For example, when r is 2, X is a divalent group, when r is 3, X is a trivalent group, when r is 4, X is a tetravalent group, when r is 5, X is a pentavalent group, and when r is 6, X is a hexavalent group.

[0023] In formula (1), each R 1 are independently organic groups containing acid-labile groups. As used herein, "acid-labile group" refers to a group having a bond that can be cleaved by the action of acid, optionally (and typically) with thermal treatment, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group. Suitable acid-labile groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-labile groups are also commonly referred to in the art as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-labile protecting groups," "acid-leaving groups," "acid-decomposable groups," and "acid-sensitive groups."

[0024] In formula (1), R 2 and R 3 are each independently hydrogen or a substituted or unsubstituted C 1~30 Preferably, R 2 and R 3 are each independently hydrogen or a substituted or unsubstituted C 1~10 It can be alkyl, typically R 2 and R 3 are each independently hydrogen or a substituted or unsubstituted C 1~6 In some embodiments, R 2 is hydrogen and R 3 is a substituted or unsubstituted C 1~6 Each R is an alkyl. 2 and R 3 may optionally further include a divalent linking group as part of its structure.

[0025] R 2 and R3 are optionally joined together via a single bond or a divalent linking group to form a ring, said ring being substituted or unsubstituted.

[0026] In formula (1), each L 2 is a single bond or a linking group. For example, each L 2 is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 1~30 Heteroarylene, -O-, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R 1b )-, and R 1a and R 1b are each independently hydrogen or C 1~6 It is alkyl. 2 If L contains -O-, one or more other additional groups must be present so as not to form a peroxide (i.e., peroxo-OO-) with the adjacent acetal or ketal oxygen. 2 Preferably, L 2 is a substituted or unsubstituted C 1~10 Alkylene, -O-, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R 1b )-, typically L 2 is a substituted or unsubstituted C 1~6 In some embodiments, L can be one or more of alkylene, -O-, or -C(O)-. 2 is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 1~30 Heteroarylene, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R1b )-; L 2 may optionally further comprise one or more groups of formula -O-, and R 1a and R 1b are each independently hydrogen or C 1~6 It is alkyl.

[0027] In some embodiments, L 2 can be a single bond or a divalent linking group. 2 can be a trivalent linking group, a tetravalent linking group, a pentavalent linking group, or a hexavalent linking group, based on the variable k disclosed below.

[0028] In formula (1), each Ar 1 are independently substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 3~30 Heteroarylene, substituted C 6~30 Arylene and Substituted C 3~30 Each heteroarylene independently represents a halogen, C 1~30 Alkyl, C 1~30 Alkoxy, C 4~30 Cycloalkyl, C 1~30 Heterocycloalkyl, C 2~30 Alkenyl, C 2~30 Alkynyl, C 6~30 Aryl, C 7~30 Aryl alkyl, C 7~30 Alkylaryl, C 6~30 Aryloxy, C 3~30 Heteroaryl, C 4~30 Alkylheteroaryl, C 4~30 Heteroarylalkyl or C 3~30 Preferably, Ar is substituted with at least one of Ar 1 are independently substituted or unsubstituted C 6~14 Arylene or substituted or unsubstituted C 3~10 Heteroarylene, substituted C 6~14 Arylene and Substituted C 3~10 Each heteroarylene independently represents a halogen, C 1~10 Alkyl, C1~10 Alkoxy, C 6~30 Aryl or C 3~30 Heteroaryl is substituted with at least one of Ar 1 is a phenylene group, which is optionally substituted with one or more halogen atoms, such as one or more iodine atoms.

[0029] In formula (1), each L 1 are independently a single bond or a divalent linking group. For example, each L 1 is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 1~30 Heteroarylene, -O-, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R 1b )-, and R 1a and R 1b are each independently hydrogen or C 1~6 Preferably, L 1 is a single bond or a substituted or unsubstituted C 1~10 Alkylene, -O-, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R 1b )-, typically L 1 is a single bond or a substituted or unsubstituted C 1~6 Alkylene, -O-, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R 1b In some embodiments, each L 1 is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 1~30Heteroarylene, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R 1b )-, and each L 1 may optionally further comprise one or more groups of formula -O-, and R 1a and R 1b are each independently hydrogen or C 1~6 It is alkyl. Two or more L 1 If there is, each L 1 can be the same or different.

[0030] In formula (1), each R 1 are independently organic groups comprising acid labile groups. Exemplary acid labile groups include tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. In some embodiments, one or more R 1 The acid labile groups in include ester groups. In some embodiments, one or more R 1 The acid labile groups include acetal groups.

[0031] In some embodiments, R 1 may have a structure represented by one of formulas (2a) or (2b): [ka]

[0032] In formula (2a), R 4 ~R 6 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 C6~20 Aryl or substituted or unsubstituted C 2~20 Heteroaryl, but R 4 ~R 6 No more than one selected from R 4 ~R 6 If one of is hydrogen, R 4 ~R 6 At least one of the other is substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 Provided that it is heteroaryl.

[0033] Each R 4 ~R 6 may optionally further include a divalent linking group as part of its structure. For example, each R 2 ~R4 is -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 2a )- or -C(O)N(R 2b )-, and R 2a and R 2b 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. Typically, R 4 ~R 6 are each independently hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~8 Cycloalkyl or substituted or unsubstituted C 6~14 It is aryl.

[0034] In formula (2b), R 7 and R 8 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 6~20 Aryl or substituted or unsubstituted C2~20 Each R is heteroaryl. 7 and R 8 may optionally further include a divalent linking group as part of its structure. For example, each R 7 and R 8 does not include -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 2a )- or -C(O)N(R 2b )-, and R 2a and R 2b 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. Typically, R 7 and R 8 are each independently hydrogen or a substituted or unsubstituted C 1~10 It is alkyl.

[0035] In formula (2b), R 9 is a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 Heteroaryl. R 9 may optionally further include a divalent linking group as part of its structure. Typically, R 9 is a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~8 Cycloalkyl or substituted or unsubstituted C 6~14 It may be aryl.

[0036] In formula (2a), R 4 ~R 6 Any two of may optionally form a ring together via a single bond or a divalent linking group, and this ring is substituted or unsubstituted. 7 and R8 are optionally joined together via a single bond or a divalent linking group to form a ring, which ring is substituted or unsubstituted. 7 or R 8 Any one or more of R 9 together with each other to form a ring, which may be substituted or unsubstituted.

[0037] In formulas (2a) and (2b), * and *' represent L 1 It represents the binding site for L 1 is a single bond, the corresponding * or *' is Ar 1 It should be understood that the binding site for

[0038] In formula (1), m is an integer of 1 or more, and Ar 1 The binding site -(L 1 -R 1 In some embodiments, m is preferably an integer of 1 to 5, or an integer of 1 to 4, or an integer of 1 to 3, or 1 or 2. Typically, m is an integer of 1 to 3. When m is 2, Ar 1 is a trivalent group, and when m is 3, Ar 1 is a tetravalent group, and when m is 4, Ar 1 is a pentavalent group, and when m is 5, Ar 1 It should be understood that is a hexavalent group.

[0039] In formula (1), k is an integer of 1 to 5, and L 2 Binding site -Ar 1 -(L 1 -R 1 ) m In some embodiments, k is preferably an integer of 1 to 4, or an integer of 1 to 3, or 1 or 2. Preferably, k is an integer of 1 to 3. When k is 2, L 2 is a trivalent group, and when k is 3, L 2is a tetravalent group, and when m is 4, L 2 is a pentavalent group, and when m is 5, L 2 It should be understood that is a hexavalent group.

[0040] In formula (1), r is an integer of 2 to 10, and the moiety -OC(R 2 )(R 3 )-OL 2 -[Ar 1 -(L 1 -R 1 ) m ] k In some aspects, r is preferably an integer from 2 to 4, or 2 or 3. Preferably, r is 2. In some embodiments, each subunit represented by the integer r is the same.

[0041] In some embodiments, m is an integer from 1 to 3, k is 1, and r is 2.

[0042] In some embodiments, in formula (1), the moiety -OL 2 -[Ar 1 -(L 1 -R 1 ) m ] k A group defined by may be represented by formula (3a): [ka]

[0043] In formula (3a), L 1 is a single bond or a substituted or unsubstituted C 1~10 Alkylene, -O-, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R 1b )-, typically L 1 is a single bond or a substituted or unsubstituted C 1~6 Alkylene, -O-, -C(O)-, -C(O)O-, -C(O)NR 1a -or-N(R1b )-, and R 1a and R 1b are each independently hydrogen or C 1~6 It is alkyl.

[0044] In formula (3a), R 1 R is an organic group containing an acid labile group as defined herein. 1 Exemplary groups for include structures represented by one of formulas (2a) or (2b):

[0045] In formula (3a), each R a is a halogen, C 1~10 Alkyl, C 1~10 Alkoxy, C 6~14 Aryl or C 3~30 In some embodiments, R is heteroaryl. a may be iodine.

[0046] In formula (3a), n1 is an integer of 0 to 4. Preferably, n1 is an integer of 0 to 2, or 0 or 1.

[0047] For example, in formula (1), the moiety -OL 2 -[Ar 1 -(L 1 -R 1 ) m ] k A group defined by may be represented by formula (3b): [ka]

[0048] In formula (3b), R 1a is a substituted or unsubstituted tertiary C 4~20 Alkyl group, substituted or unsubstituted tertiary C 4~20 Cycloalkyl group or substituted or unsubstituted tertiary C 9~20 It is an arylalkyl group. Preferably, R 1a is a substituted or unsubstituted tertiary C 4~10Alkyl group, substituted or unsubstituted tertiary C 4~10 Cycloalkyl group or substituted or unsubstituted tertiary C 9~19 It may be an arylalkyl group.

[0049] In formula (3b), each R a is a halogen, C 1~10 Alkyl, C 1~10 Alkoxy, C 6~14 Aryl or C 3~30 In some embodiments, R is heteroaryl. a may be iodine.

[0050] In formula (3a), n1 is an integer of 0 to 4. Preferably, n1 is an integer of 0 to 2, or 0 or 1.

[0051] In some embodiments, X can comprise an aromatic or heteroaromatic group. For example, X can be represented by one of formulas (4)-(9). [ka]

[0052] In formulas (4) to (9), Ar 2 , Ar 3 and Ar 5 are each independently a substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 3~30 Heteroarylene. Preferably, Ar 2 , Ar 3 and Ar 5 are each independently a substituted or unsubstituted C 6~14 Arylene or substituted or unsubstituted C 3~20 It may be heteroarylene, typically Ar 2 , Ar 3 and Ar 5 are each independently substituted or unsubstituted phenylene. In some embodiments, Ar 2 , Ar 3 and Ar 5may each independently be substituted with 1 to 4 iodine atoms. For example, Ar 2 , Ar 3 and Ar 5 may each independently be substituted with 1 to 3 iodine atoms, or 1 or 2 iodine atoms, or 1 iodine atom.

[0053] In formula (7), Ar 4 is a substituted or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 Heteroaryl. Preferably, Ar 4 is a substituted or unsubstituted C 6~14 Aryl or substituted or unsubstituted C 3~20 It may be heteroaryl, typically Ar 4 is substituted or unsubstituted phenylene. In some embodiments, Ar 4 may be substituted with 1 to 4 iodine atoms. For example, Ar 4 may be substituted with 1 to 3 iodine atoms, or 1 or 2 iodine atoms, or 1 iodine atom.

[0054] In formulas (6) to (8), R 10 and R 11 are each independently hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 6~30 Aryloxy, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 Preferably, R 10 and R 11are each independently a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~8 Cycloalkyl, substituted or unsubstituted C 6~14 Aryl or substituted or unsubstituted C 3~20 It may be heteroaryl.

[0055] In formulas (4) to (9), * and *' indicate the connection points to the respective adjacent oxygen atoms. In formula (8), *'' indicates the connection points to the respective adjacent oxygen atoms.

[0056] In some embodiments, X may be represented by one of formulas (4a)-(9a). [ka]

[0057] In formulas (4a) to (9a), each R b , R c , R d and R e are independently halogen, C 1~30 Alkyl, C 1~30 Alkoxy, C 4~30 Cycloalkyl, C 3~30 Heterocycloalkyl, C 2~30 Alkenyl, C 2~30 Alkynyl, C 6~30 Aryl, C 7~30 Aryl alkyl, C 7~30 Alkylaryl, C 6~30 Aryloxy, C 3~30 Heteroaryl, C 4~30 Alkylheteroaryl, C 4~30 Heteroarylalkyl or C 3~30 Preferably, each R b , R c and R d are independently halogen, C 1~10 Alkyl, C 1~10 Alkoxy, C 4~20 Cycloalkyl, C 3~20 Heterocycloalkyl, C 2~20Alkenyl, C 2~20 Alkynyl, C 6~14 Aryl, C 7~15 Aryl alkyl, C 7~15 Alkylaryl, C 6~14 Aryloxy, C 3~20 Heteroaryl, C 4~20 Alkylheteroaryl, C 4~20 Heteroarylalkyl or C 3~30 It is heteroaryloxy.

[0058] In formulas (6a), (7a) and (8a), R 10a is hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 6~30 Aryloxy, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 Preferably, R 10a is a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 6~14 Aryl or substituted or unsubstituted C 3~20 It may be heteroaryl.

[0059] In formula (6a), R 11a is hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 6~30 Aryloxy, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 Preferably, R 11a is a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 6~14 Aryl or substituted or unsubstituted C 3~20 It may be heteroaryl.

[0060] In formulas (4a) to (9a), n2, n3, and n5 are each independently an integer of 0 to 4. Preferably, n2 and n3 are each independently an integer of 1 to 3, or 1 or 2, or 1.

[0061] In formula (7a), n4 is an integer of 0 to 5. Preferably, n4 is an integer of 1 to 4, or 1 to 3, or 1 or 2.

[0062] In formulae (4a) to (9a), * and *' represent the connection points to the respective adjacent oxygen atoms. In formula (8a), *'' represents the connection point to the respective adjacent oxygen atoms.

[0063] The compound of formula (1) is not a polymer. For example, the compound of formula (1) is not in the polymerized repeat unit of a polymer or oligomer. It should be understood that "not a polymer" also means that the compound of formula (1) is not in a polymer-bound form.

[0064] In some embodiments, the compound contains one or more iodine atoms. For example, the compound can contain 1 iodine atom, 2 iodine atoms, 3 iodine atoms, 4 iodine atoms, 5 iodine atoms, 6 iodine atoms, or 7 or more iodine atoms. In some aspects, the compound can contain 2 to 6 iodine atoms or 2 to 4 iodine atoms.

[0065] Exemplary monomers of formula (1) include: [ka]

[0066] The compound of formula (1) may have a formula weight of 100 to 15,000 grams per mole (g / mol), or 300 to 3,000 g / mol, or 400 to 3,000 g / mol, or 800 to 2,000 g / mol.

[0067] The present invention further relates to photoresist compositions comprising the compounds of the present invention 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.

[0068] The compounds of the present invention may be present in a photoresist composition in an amount of, for example, 0.01 to 100 weight percent (wt%), based on the total solids content of the photoresist composition. The compounds of the present invention can be used in a photoresist composition, for example, as an additive in a small amount relative to the total solids content of the photoresist composition, or as a matrix material in a large amount relative to the total solids content of the photoresist composition. When used as an additive, the compounds are typically present in a photoresist composition in an amount of 0.01 to 50 wt%, more typically 0.01 to 20 wt%, 0.01 to 10 wt%, or 0.1 to 6 wt%, or 0.5 to 5 wt%, based on the total solids content of the photoresist composition. When used as a major solid component, the compounds are typically present in a photoresist composition in an amount greater than 50 wt% to 100 wt%, 70 to 100 wt%, or 70 to 95 wt%, based on the total solids content of the photoresist composition. It will be understood that the term "total solids content" includes the compounds of the present invention and other non-solvent components of the photoresist composition.

[0069] The photoresist composition may further comprise a polymer having one or more repeating units. The repeating units may be one or more units for the purpose of adjusting the properties of the photoresist composition, such as, for example, etch rate and solubility. Exemplary repeating units may include those derived from one or more of (meth)acrylate, vinyl aromatic, vinyl ether, vinyl ketone, and / or vinyl ester monomers.

[0070] In some aspects, upon exposure to incident radiation, the compounds of the present invention, and optional polymers, may undergo chain scission of the polymer backbone along with scission of acid-labile pendant groups, hi some embodiments, the polymer does not contain acid-labile groups.

[0071] In some embodiments, the polymer may be acid-sensitive, for example, the polymer may include repeat units that include acid-labile groups.

[0072] For example, the repeat unit containing an acid labile group can be derived from one or more monomers of formulae (10) to (14). [ka]

[0073] In formulas (10) to (12), each R a are independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, each R a are independently hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl.

[0074] In equation (10), L 3 is a divalent linking group. For example, L 3 can contain 1 to 10 carbon atoms and at least one heteroatom. 1 is -OCH2-, -OCH2CH2O- or -N(R 10a )-, where R 10a is hydrogen or C 1~6 It is alkyl.

[0075] In formulas (10), (11) and (13), R 12 ~R 14 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, but R 12 ~R 14 is hydrogen, and R 12 ~R 14 If one of is hydrogen, R12 ~R 14 At least one of the other is substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 provided that it is heteroaryl. Preferably, R 12 ~R 14 are each independently a substituted or unsubstituted C 1~6 Alkyl or substituted or unsubstituted C 3~10 is cycloalkyl. R 12 ~R 14 Each of may optionally further include a divalent linking group as part of its structure.

[0076] For example, R 12 ~R 14 any one or more of the formula -CHC(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n and each Y can be independently a substituted or unsubstituted C 3~10 heterocycloalkyl, and n is 1 or 2. For example, each Y is independently a group of the formula —O(C a1 )(C a2 )O- group containing substituted or unsubstituted C 3~10 heterocycloalkyl, wherein C a1 and C a2 are each independently hydrogen or substituted or unsubstituted alkyl, and C a1 and C a2 together optionally form a ring.

[0077] R 12 ~R 14 Any two of may be taken together to optionally form a ring which may further include a divalent linking group as part of its structure, and which may be substituted or unsubstituted.

[0078] In equations (12) and (14), R 15 and R 16 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 may be heteroaryl, R 17 is a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 Preferably, R 15 and R 16 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 R can be heterocycloalkyl. 15 and R 16 Each of may optionally further include a divalent linking group as part of its structure.

[0079] Optionally, R 15 and R 16 may optionally together form a ring which may further include a divalent linking group as part of its structure, and which ring may be substituted or unsubstituted.

[0080] Optionally, R 15 or R 16 At least one of the following is R 17 may optionally form a ring which may further include a divalent linking group as part of its structure, and which may be substituted or unsubstituted.

[0081] In equations (13) and (14), X a and X b are each independently a polymerizable group containing an ethylenically unsaturated double bond, and are preferably (meth)acrylate or C2 alkenyl.

[0082] In equations (13) and (14), L 4 and L 5are each independently a single bond or a divalent linking group, and X a When is C2 alkenyl, L 4 is not a single bond, X b When is C2 alkenyl, L 5 is not a single bond. Preferably, L 4 and L 5 are each independently a substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 6~30 In formulas (13) and (14), n6 is 0 or 1, and n7 is 0 or 1. When n6 is 0, L 4 It should be understood that the group is directly attached to the oxygen atom. When n7 is 0, L 5 It should be understood that the group is attached directly to the oxygen atom.

[0083] In some embodiments, each R 12 ~R 17 may optionally further comprise as part of its structure one or more divalent linking groups selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, or -C(O)N(R')-, where R' is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl.

[0084] In some embodiments, in repeat units containing an acid labile group, the acid labile group can be a tertiary alkyl ester. For example, the repeat unit containing a tertiary alkyl ester group can be derived from one or more monomers of formula (10), (11), or (14), where R 12 ~R 14 is not hydrogen and n7 is 1. In one or more embodiments, the polymer further comprises a second repeat unit comprising a tertiary alkyl ester group.

[0085] Exemplary monomers of formula (10) include one or more of the following: [ka]

[0086] Exemplary monomers of formula (11) include one or more of the following: [ka] [ka] In the formula, R d is expressed by the formula R in equation (11). a R′ and R″ 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 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 It is heteroaryl.

[0087] Exemplary monomers of formula (12) include one or more of the following: [ka] In the formula, R d is R a As defined above with respect to

[0088] Exemplary monomers of formula (13) include one or more of the following: [ka]

[0089] Exemplary monomers of formula (14) include one or more of the following: [ka]

[0090] In some embodiments, the polymer has a cyclic acetal or cyclic ketal group, for example, the following structure: [ka] (In the formula, R d is R a The repeating units may be derived from one or more monomers having one or more of the following structures:

[0091] In some embodiments, the polymer may have repeat units with acid labile groups that include tertiary alkoxy groups, such as one or more of the following monomers: [ka]

[0092] When present, repeat units containing acid labile groups are typically present in the polymer in an amount of 5 to 95 mole percent (mol %), more typically 20 to 80 mol %, and even more typically 30 to 50 mol %, based on all repeat units in the polymer.

[0093] In some embodiments, the polymer may further include a repeat unit comprising a polar group, the polar group being pendant to the backbone of the polymer. For example, the polar group may be a lactone group, a hydroxyaryl group, a fluoroalcohol group, or a combination thereof.

[0094] In one or more embodiments, the polymer may further include a third repeat unit derived from one or more lactone-containing monomers of formula (15). [ka] In the formula, R f is hydrogen, fluorine, cyano, or substituted or unsubstituted C1~10 It is alkyl.

[0095] In equation (15), L 6 is a single bond or a divalent linking group. 6 Exemplary divalent linking groups include substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 1~30 Heteroalkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylene, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 15a )- or -C(O)N(R 15b )-, and R 15a and R 15b 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 It may be a heterocycloalkyl.

[0096] In equation (15), R 18 is a substituted or unsubstituted C 4~20 Lactone-containing group or substituted or unsubstituted C 4~20 It is a sultone-containing group. 4~20 Lactone-containing groups and C 4~20 The sultone-containing group can be monocyclic, polycyclic, or fused polycyclic. 6 is a single bond, the moiety -R 18 is directly attached to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)OR 18 ) should be understood.

[0097] Exemplary monomers of formula (15) can include one or more of the following: [ka] In the formula, Rf is as defined for equation (15).

[0098] The polymer may include repeat units that are base soluble and / or have a pKa of less than or equal to 12. For example, repeat units containing polar groups pendant to the backbone of the polymer may be derived from one or more monomers of formulae (16)-(18). [ka] In the formula, each R g is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R g is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It may be alkyl, typically methyl.

[0099] In equation (16), R 19 is a substituted or unsubstituted C 1~60 Or C 1~20 Alkyl, typically C 1~12 Alkyl, substituted or unsubstituted C 3~30 Or C 3~20 Cycloalkyl or substituted or unsubstituted poly(C 1~3 alkylene oxide). Preferably, the substituted C 1~60 or C 1~20 Alkyl, substituted C 3~30 or C 3~20 Cycloalkyl and substituted poly(C 1~3 Alkylene oxide) is halogen, C 1~4 Fluoroalkyl groups, typically fluoroalkyl groups such as fluoromethyl, sulfonamide groups -NH-S(O)2-Y 1 (In the formula, Y 1 is F or C 1~4 The alkyl group is substituted with one or more fluoroalkyl groups (e.g., -NHSO2CF3) or fluoroalcohol groups (e.g., -C(CF3)2OH).

[0100] In equation (17), L 7is a single bond or, for example, optionally -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -NR 17a - or -C(O)N(R 17b )-, optionally substituted aliphatic (C 1~6 Alkylene or C 3~20 R may be a polyvalent linking group selected from alkyl, aryl, aryl groups ... 17a and R 17b is hydrogen and optionally substituted C 1~10 For example, the polymer may be represented by formula (17): 7 is a single bond or a substituted or unsubstituted C 1~20 Alkylene, typically C 1~6 Alkylene, substituted or unsubstituted C 3~20 Cycloalkylene, typically C 3~10 Cycloalkylene and substituted or unsubstituted C 6~24 The polyvalent linking group may further comprise repeat units derived from one or more monomers of the formula:

[0101] In formula (17), n8 is an integer of 1 to 5, typically 1. When n8 is 1, the group L 7 It should be understood that n8 is a divalent linking group. When n8 is 2, the group L 7 It is to be understood that when n8 is 3, the group L 7 is a tetravalent linking group, and when n8 is 4, the group L 7 is a pentavalent linking group, and when n8 is 5, the group L 7 It is understood that is a hexavalent linking group. Thus, in reference to formula (17), the term "polyvalent linking group" refers to any of divalent, trivalent, tetravalent, pentavalent, and / or hexavalent linking groups.

[0102] In equation (18), L 8 represents a single bond or a divalent linking group. 8 is a single bond or a substituted or unsubstituted C 6~30Arylene or substituted or unsubstituted C 6~30 It may be a cycloalkylene.

[0103] In formula (18), n9 is 0 or 1. When n9 is 0, the moiety represented by -OC(O)- is L 8 It is to be understood that is a single bond such that is attached directly to the alkenyl (vinyl) carbon atom.

[0104] In formula (18), Ar 2 is a substituted C optionally containing one or more aromatic ring heteroatoms selected from N, O, S or combinations thereof 5~60 C is an aromatic group, which may be monocyclic, non-fused polycyclic, or fused polycyclic. 5~60 When the aromatic group is polycyclic, the rings or ring groups can be fused (such as naphthyl), non-fused, or combinations thereof. 5~60 When the aromatic group is non-fused, the rings or ring groups can be directly linked (such as biaryl, biphenyl, etc.) or bridged by a heteroatom (such as triphenylamino or diphenylene ether). 5~60 The aromatic group may contain a combination of fused and directly bonded rings (such as binaphthyl).

[0105] In formula (18), y can be an integer from 1 to 12, preferably from 1 to 6, and typically from 1 to 3. Each R x is independently hydrogen or methyl.

[0106] Non-limiting examples of monomers of formulas (16)-(18) may include one or more of the following: [ka] [ka] In the formula, Y 1 is as described above, and R i is R in equations (16) to (18). gis as defined above.

[0107] When present, the polymer typically contains repeat units containing polar groups (pendant to the backbone of the polymer) in an amount of from 1 to 60 mol %, typically from 5 to 50 mol %, more typically from 5 to 40 mol %, based on all repeat units in the polymer.

[0108] Non-limiting exemplary polymers of the present invention include one or more of the following: [ka] In the formula, each R p is herein referred to as R a and is typically methyl, and a, b, and c represent the mole fraction of each repeat unit in the polymer.

[0109] The polymer typically has a weight average molecular weight (M) of 1,000 to 50,000 Daltons (Da), preferably 2,000 to 30,000 Da, more preferably 4,000 to 25,000 Da, and even more preferably 5,000 to 25,000 Da. w ) M w and number average molecular weight (M n The polydispersity index (PDI) of the first polymer, which is the ratio of the molecular weights (molecules) to the molecular weights (molecules), is typically 1.1 to 3, more typically 1.1 to 2. Molecular weight values ​​are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0110] When used, the polymer is typically present in the photoresist composition in an amount of 10 to 99.9 wt %, typically 25 to 99 wt %, more typically 40 to 95 wt % or 60 to 95 wt %, based on the total solids content of the photoresist composition. In some embodiments, the photoresist composition can include 0.5 to 6 wt % of a compound of the invention and 40 to 95 wt % of the polymer, or the photoresist composition can include 1 to 5 wt % of a compound of the invention and 60 to 85 wt % of the polymer.

[0111] The polymer can be prepared by any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined using a suitable solvent and initiator, or can be fed separately and polymerized in a reactor. For example, the polymer can be obtained by polymerizing each monomer under any suitable conditions, such as heating at an effective temperature, irradiating with activating radiation at an effective wavelength, or a combination thereof.

[0112] Suitable PAGs are capable of generating an acid during post-exposure bake (PEB) that causes cleavage of acid-labile groups present on the polymer of the photoresist composition. The PAG can be in non-polymeric or polymeric form, and can be present, for example, in the polymerized repeat unit of a polymer such as those described above or as part of a different polymer. In some embodiments, the PAG can be included in the composition as a non-polymerizable PAG compound, as a repeat unit of a polymer having a PAG portion derived from a polymerizable PAG monomer, or a combination thereof.

[0113] 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; and a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of an alkyl group and an aryl group; - is a non-polymeric organic anion. 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.

[0114] Useful non-polymeric PAG compounds are known in the art of chemically amplified photoresists and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Nonionic sulfonate and sulfonyl compounds, for example, nitrobenzyl derivatives such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives such as bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, for example Other known photoacid generators include bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Suitable non-polymeric acid generators are further described in Hashimoto et al. (Patent Document 1), columns 37, 11-47, and 41-91.Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, such as those described in U.S. Patent No. 5,629,999 and U.S. Patent No. 5,629,999, nitrobenzyl esters, s-triazine derivatives, benzoin tosylate, t-butylphenyl α-(p-toluenesulfonyloxy)acetate, and t-butyl α-(p-toluenesulfonyloxy)acetate.

[0115] Typically, when the photoresist composition includes a non-polymeric photoacid generator, it is present in the photoresist composition in an amount of from 0.3 to 65 weight percent (wt %), more typically from 1 to 20 wt %, based on the total solids content of the photoresist composition.

[0116] In some embodiments, G + can be a sulfonium cation of formula (19) or an iodonium cation of formula (20). [ka]

[0117] In formulas (19) and (20), each R aa are 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 3~30 Heteroaryl, substituted or unsubstituted C 7~20 Aryl alkyl or substituted or unsubstituted C 4~20 Heteroarylalkyl. Each R aa are either individually or linked to another group R via a single bond or a divalent linking group. aa and each R can be linked to form a ring. aa may optionally include a divalent linking group as part of its structure. aamay optionally include acid labile groups independently selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

[0118] Exemplary sulfonium cations of formula (19) include one or more of the following: [ka]

[0119] Exemplary iodonium cations of formula (20) include one or more of the following: [ka]

[0120] PAGs that are onium salts typically contain an organic anion having a sulfonate group or a non-sulfonate type group (such as a sulfonamidate, sulfonimidate, methide, or borate).

[0121] Exemplary organic anions having a sulfonate group include one or more of the following: [ka]

[0122] Exemplary non-sulfonated anions include one or more of the following: [ka]

[0123] The photoresist composition can optionally include multiple PAGs. The multiple PAGs can be polymeric, non-polymeric, or include both polymeric and non-polymeric PAGs. Preferably, each of the multiple PAGs is non-polymeric.

[0124] In one or more embodiments, the photoresist composition can include a first photoacid generator that includes a sulfonate group on the anion, and the photoresist composition can include a second photoacid generator that is non-polymeric, and the second photoacid generator can include an anion that does not include a sulfonate group.

[0125] In some embodiments, the polymer may optionally further comprise repeat units that include a PAG-containing moiety, such as repeat units derived from one or more monomers of formula (21). [ka] In the formula, R m is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R m is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl.

[0126] In equation (21), Q 1 can be a single bond or a divalent linking group. 1 may contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-. 1 is a 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 or substituted or unsubstituted C 3~30 Preferably, A is one or more of: 1 is an optionally substituted divalent C 1~30 It may be a perfluoroalkylene group. - is a negatively charged anionic moiety (i.e., Z has a negative charge), and its conjugate acid typically has a pKa of -15 to 1. For example, Z -may be a sulfonate anion, a carboxylate anion, an anion of a sulfonamide, an anion of a sulfonimide, or a methide anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonates and fluorinated sulfonimides. + is a positively charged organic cation (i.e., G has a positive charge). 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.

[0127] Exemplary monomers of formula (21) include one or more of the following: [ka] In the formula, G + is an organic cation as defined herein.

[0128] When used, repeat units containing PAG moieties may be included in the polymer in an amount of 1 to 15 mol %, typically 1 to 8 mol %, more typically 2 to 6 mol %, based on the total repeat units in the polymer.

[0129] The photoresist composition further comprises a solvent to dissolve the components of the composition and facilitate coating it onto a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples of suitable solvents include ketones such as 2-heptanone and cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and ethyl acetoacetate; lactones such as γ-butyrolactone (GBL) and ε-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or acyclic carbonates such as dimethyl carbonate, ethylene carbonate, diphenyl carbonate, and propylene 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.

[0130] The total solvent content (i.e., the cumulative solvent content of all solvents) in a photoresist composition is typically 40 to 99 wt %, for example 50 to 99 wt %, or 85 to 99 wt %, based on the total solids content of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the coated photoresist layer and the coating conditions.

[0131] In some embodiments, the photoresist composition may further comprise a material containing one or more base-labile groups ("base-labile material"). As referred to herein, a base-labile group is a functional group that can undergo a cleavage reaction in the presence of an aqueous alkaline developer after the exposure and post-exposure bake steps to provide a polar group such as a hydroxyl, carboxylic acid, sulfonic acid, or the like. The base-labile group will not significantly react (e.g., will not undergo a bond-breaking reaction) before the development step of a photoresist composition containing the base-labile group. Thus, for example, the base-labile group will be substantially inert during the pre-exposure soft bake, exposure, and post-exposure bake steps. "Substantially inert" means that 5% or less, typically 1% or less, of the base-labile groups (or sites) decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-labile group reacts under typical photoresist development conditions, for example, using an aqueous alkaline photoresist developer such as an aqueous solution of 0.26N tetramethylammonium hydroxide (TMAH). For example, a 0.26N aqueous TMAH solution can be used for single puddle development or dynamic development, where the 0.26N TMAH developer is dispensed onto the imaged photoresist layer for a suitable time, such as 10 to 120 seconds (s). An exemplary base-labile group is an ester group, typically a fluorinated ester group. Preferably, the base-labile material is substantially immiscible with and has a lower surface energy than the polymer and other solid components of the photoresist composition. When coated onto a substrate, the base-labile material can thereby separate from the other solid components of the resist composition to the top surface of the formed photoresist layer.

[0132] In some embodiments, the base-labile material can be a polymeric material, also referred to herein as a base-labile polymer, which can include one or more repeating units containing one or more base-labile groups. For example, the base-labile polymer can include repeating units containing two or more base-labile groups, which can be the same or different. Preferred base-labile polymers include at least one repeating unit containing two or more base-labile groups, for example, repeating units containing two or three base-labile groups.

[0133] The base-labile polymer can be a polymer that includes repeat units derived from one or more monomers of formula (22). [ka] In the formula, X e is a polymerizable group selected from C2 alkenyl and (meth)acrylic, and L 9 is a divalent linking group, and R n is a substituted or unsubstituted C 1~20 fluoroalkyl, provided that the carbon atom bonded to the carbonyl (—C(O)—) in formula (22) is substituted with at least one fluorine atom. Exemplary monomers of formula (22) can include one or more of the following: [ka]

[0134] The base-labile polymer can include repeat units containing more than one base-labile group. For example, the base-labile polymer can include repeat units derived from one or more monomers of formula (23). [ka] In the formula, X f and R p are expressed as X in equation (23), respectively. e and R n is as defined for L 10 is a substituted or unsubstituted C 1~20 Alkylene, substituted or unsubstituted C3~20 is a polyvalent linking group comprising one or more of cycloalkylene, —C(O)—, or —C(O)O—, where n10 can be an integer of 2 or greater, such as 2 or 3. Exemplary monomers of formula (23) include one or more of the following: [ka]

[0135] The base-labile polymer may include repeat units containing one or more base-labile groups. For example, the base-labile polymer may include repeat units derived from one or more monomers of formula (24). [ka] In the formula, X g and R q are expressed as X in equation (24), respectively. e and R n is as defined for L 11 is a divalent linking group, and L 12 is a substituted or unsubstituted C 1~20 Fluoroalkylene, the carbon atom bonded to the carbonyl (—C(O)—) in formula (24) is substituted with at least one fluorine atom. Exemplary monomers of formula (24) include one or more of the following: [ka]

[0136] In some embodiments, a base-labile polymer can 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 esters) or acid-labile acetal groups. For example, a base-labile polymer can include a repeat unit that includes 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 repeat unit. In another example, a base-labile polymer can include a first repeat unit that includes a base-labile group and a second repeat unit that includes an acid-labile group.

[0137] The base-labile polymer can be prepared by any suitable method in the art. For example, the base-labile polymer can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof. Additionally or alternatively, one or more base-labile groups can be grafted onto the main chain of the polymer using a suitable method.

[0138] In some embodiments, the base-labile substance is a single molecule containing one or more base-labile ester groups, preferably one or more fluorinated ester groups. Single-molecule base-labile substances typically have an M in the range of 50 to 1,500 Da. W Exemplary base-labile substances include one or more of the following: [ka]

[0139] If present, the base-labile material is typically present in a photoresist composition in an amount of from 0.01 to 10 weight percent, typically from 1 to 5 weight percent, based on the total solids content of the photoresist composition.

[0140] In addition to or instead of the base-labile polymer, the photoresist composition can further include one or more polymers different from the photoresist polymers described above. For example, the photoresist composition can include additional polymers as described above but with different compositions, or polymers similar to those described above but without each of the essential repeating units. Additionally or alternatively, the one or more additional polymers can include those well known in the photoresist art, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornenes, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene-based polymers, polyvinyl alcohols, or combinations thereof.

[0141] The photoresist composition may further comprise one or more additional optional additives. For example, optional additives may include actinic dyes and contrast agents, anti-striation agents, plasticizers, rate enhancers, sensitizers, photolytic quenchers (PDQs) (also known as photolytic bases), base quenchers, thermal acid generators, surfactants, and the like, or combinations thereof. When present, optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 wt %, based on the total solids content of the photoresist composition.

[0142] PDQ generates a weak acid upon irradiation. The acid generated from the photolytic deactivator is not strong enough to react rapidly with the acid labile groups present in the resist matrix. Exemplary photolytic deactivators include, for example, photolytic cations, preferably C 1~20 Carboxylic acid or C 1~20 Also included are those useful for preparing strong acid generator compounds paired with anions of weak acids (pKa > 1), such as anions of sulfonic acids. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, and the like. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, and the like. In a preferred embodiment, the photolytic quencher is a photolytic organic zwitterionic compound, such as diphenyliodonium-2-carboxylate.

[0143] The photodegradable deactivator may be in a non-polymeric form or a polymer-bound form. When in a polymeric form, the photodegradable deactivator is present in polymerized units on the first polymer or the second polymer. The polymerized units containing the photodegradable deactivator are typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, and more preferably 1 to 2 mol %, based on the total repeat units of the polymer.

[0144] Exemplary basic quenching agents include, for example, straight-chain aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(2-hydroxypropyl)ethylenediamine; n-tert-butyldiethanolamine; tris(2-acetoxyethyl)amine; 2,2′,2″,2′′-(ethane-1,2-diylbis(azanetriyl))tetraethanol; 2-(dibutylamino)ethanol; and 2,2′,2″-nitrilotriethanol; Cycloaliphatic amines such as N-(2-acetoxyethyl)morpholine, N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N,N-bis(2-hydroxyethyl)pival ... 1 ,N 1 ,N 3 ,N 3 linear and cyclic amides and derivatives thereof, such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines, such as primary and secondary aldimines and ketimines; optionally substituted diazines, such as pyrazines, piperazines, and phenazines; optionally substituted diazoles, such as pyrazoles, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones, such as 2-pyrrolidone; and cyclohexylpyrrolidine.

[0145] The basic quenching agent may be in a non-polymeric form or a polymer-bound form. If in a polymeric form, the quenching agent may be present within the repeating units of the polymer. The repeating units containing the quenching agent 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 the total repeating units of the polymer.

[0146] The photoresist composition may further comprise one or more surfactants, including fluorinated and / or non-fluorinated surfactants. The surfactant may be ionic or non-ionic, with non-ionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluoro C4 surfactants, such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols, such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In one embodiment, the photoresist composition further comprises a surfactant polymer comprising a fluorine-containing repeating unit.

[0147] A pattern formation method using the photoresist composition of the present invention will now be described. Suitable substrates onto which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates can be used in the present invention, such as semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multichip modules; flat panel display substrates; substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs); and the like, with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 mm to 300 mm, although wafers with smaller and larger diameters can be suitably used in accordance with the present invention. The substrate may include one or more layers or structures that may optionally include active or operable portions of the device to be formed.

[0148] Typically, one or more lithographic layers, such as a hardmask layer, e.g., a spin-on carbon (SOC), amorphous carbon, or metal hardmask layer, a CVD layer, such as a silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer, an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of the substrate before coating the photoresist composition of the invention. Such layers, together with an overcoated photoresist layer, form a lithographic material stack.

[0149] Optionally, a layer of adhesion promoter can be applied to the substrate surface before coating with the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films can be used, such as a silane, typically an organosilane such as trimethoxyvinylsilane, triethoxyvinylsilane, or hexamethyldisilazane, or an aminosilane coupler such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names AP3000™, AP8000™, and AP9000S™ (available from DuPont Electronics & Industrial, Marlborough, Massachusetts).

[0150] The photoresist composition can be coated onto a substrate by any suitable method, such as spin coating, spray coating, dip coating, doctor blading, etc. For example, application of a layer of photoresist can be achieved by spin-coating the photoresist in a solvent using a coating track, in which the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically spun at a speed of up to 4,000 revolutions per minute (rpm), e.g., 200 to 3,000 rpm, e.g., 1,000 to 2,500 rpm, for a period of 15 to 120 seconds, resulting in a layer of photoresist composition on the substrate. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by varying the spin speed and / or the total solids content of the composition. Photoresist composition layers formed from the compositions of the present invention typically have a dry layer thickness of 3 to 30 micrometers (μm), preferably greater than 5 to 30 μm, and more preferably 6 to 25 μm.

[0151] The photoresist composition is typically then soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. Soft-baking can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft-baking temperature and time will depend, for example, on the photoresist composition and thickness. Soft-baking temperatures are typically 80 to 170°C, more typically 90 to 150°C. Soft-baking times are typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and even more typically 1 minute to 2 minutes. The heating time can be readily determined by one skilled in the art based on the components of the composition.

[0152] The photoresist layer is then patternwise exposed to activating radiation to create a solubility differential between exposed and unexposed regions. References herein to exposing a photoresist composition to radiation that activates the composition indicate that the radiation can form a latent image in the photoresist composition. Exposure is typically carried out through a patterned photomask having optically transparent and optically opaque regions corresponding to the exposed and unexposed regions of the resist layer, respectively. Such exposure can alternatively be carried out without a photomask in a direct-write process typically used for electron beam lithography. Activating radiation typically has a wavelength of less than 400 nm, less than 300 nm, or less than 200 nm, with wavelengths of 248 nm (KrF), 193 nm (ArF), or 13.5 nm (EUV) being preferred, or electron beam lithography also being preferred. Preferably, the activating radiation has a wavelength of 248 nm. This method is utilized in immersion or dry (non-immersion) lithography techniques. Exposure energy is typically between 1 and 200 millijoules per square centimeter (mJ / cm), depending on the components of the photoresist composition. 2 ), preferably 10 to 100 mJ / cm 2 , more preferably 20 to 50 mJ / cm 2 is.

[0153] After the photoresist layer is exposed to activating radiation, the exposed photoresist layer is subjected to a post-exposure bake (PEB) or heating step. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for PEB will depend, for example, on the photoresist composition and layer thickness. PEB is typically performed at a temperature of 70-150°C, preferably 75-120°C, for a time of 30-120 seconds. A latent image is formed in the photoresist, defined by polarity-switching regions (exposed regions) and non-switching regions (unexposed regions).

[0154] The exposed photoresist layer is then developed with a suitable developer to selectively remove areas of the layer that are soluble in the developer, while the remaining insoluble areas form the resulting photoresist pattern. In a positive-tone development (PTD) process, the exposed areas of the photoresist layer are removed during development, leaving the unexposed areas of the photoresist layer after development. Conversely, in a negative-tone development (NTD) process, the unexposed areas of the photoresist layer are removed during development, leaving the exposed areas of the photoresist layer after development. Application of the developer can be accomplished by any suitable method, such as those described above with respect to application of the photoresist composition; spin coating is typical. The development time is a period effective to remove the soluble areas of the photoresist, typically between 5 and 60 seconds. Development is typically performed at room temperature.

[0155] Suitable PTD developers for the PTD process include aqueous basic developers such as tetramethylammonium hydroxide (TMAH), preferably 0.26N TMAH, quaternary ammonium hydroxide solutions such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable NTD developers for the NTD process include organic solvents such that the cumulative content of the organic solvent in the NTD developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0156] Coated substrates can be formed from the photoresist compositions of the invention, including (a) a substrate having one or more layers to be patterned on its surface, and (b) a layer of a photoresist composition over the one or more layers to be patterned.

[0157] A photoresist pattern can be used, for example, as an etch mask, thereby allowing the pattern to be transferred to one or more subsequent underlying layers by known etching techniques, typically dry etching such as reactive ion etching. The photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, which in turn is used as an etch mask for pattern transfer to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such pattern formation processes, the photoresist composition can be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0158] The present invention is further illustrated by the following non-limiting examples. [Example]

[0159] Synthesis of MD1 The synthesis scheme of the monomer represented by MD1 is shown in Scheme 1. Scheme 1 [ka]

[0160] In a reaction vessel, 1-ethylcyclopentyl-2-hydroxybenzoic acid (30.0 grams (g), 128.2 millimoles (mmol)) was suspended in N,N-dimethylformamide (DMF) to form a 6% by weight solution. Cesium carbonate (83.5 g, 256.4 mmol) and sodium iodide (1.92 g, 12.82 mmol) were added neat to the solution to form a reaction mixture. Next, (2-chloroethoxy)ethene (16.4 g, 153.8 mmol) was slowly added dropwise to the reaction mixture with stirring. The resulting reaction mixture was heated to an internal temperature of 70°C for 18 hours. The reaction mixture was then allowed to cool to room temperature and diluted with deionized (DI) water (1.5 liters (L)), and the aqueous mixture was extracted with methyl tert-butyl ether (3 x 300 mL). The organic layers were combined, washed with DI water (5 x 200 mL), and the solvent was removed under reduced pressure to give intermediate SM1 as a colorless oil (37.0 g, 95% yield).

[0161] Proton nuclear magnetic resonance spectroscopy ( 1H-NMR (500 MHz, chloroform-d) chemical shifts (δ, parts per million (ppm)): 7.72 (dd, 1H, ArH), 7.42 (ddd, 1H, ArH), 7.00 (td, 1H, ArH), 6.97 (d, 1H, ArH), 6.55 (dd, 1H, alkenyl-H), 4.31-4.21 (m, 3H, CH₂ / alkenyl-H), 4.12-4.03 (m, 3H, CH₂ / alkenyl-H), 2.33-2.24 (m, 2H, CH₂), 2.14 (q, 2H, CH₂), 1.86-1.71 (m, 4H, CH₂), 1.69-1.56 (m, 2H, CH₂), 0.96 (t, 3H, CH₂).

[0162] A reaction vessel was charged with 4,4'-sulfonyldiphenol (2.00 g, 8.0 mmol) and propylene glycol monomethyl ether acetate (PGMEA) to obtain a 20 wt% solution. Trace amounts of water were removed by azeotropic distillation. Trifluoroacetic acid (0.02 g, 0.2 mmol) and vinyl ether monomer intermediate SM1 (4.99 g, 16.4 mmol) were added to the anhydrous solution to obtain a reaction mixture. The reaction mixture was stirred at room temperature (approximately 23 °C) for 24 hours. The reaction solution was then passed through an alumina column, and the solvent was removed under reduced pressure to obtain MD1 (5.58 g, 80.0% yield).

[0163] 1 H-NMR(acetone-d6),δ(ppm):7.88(d,4H,ArH),7.24(d,4H,ArH),7.64(d,2H,ArH),7.43(m,2H,ArH),7.07(d,2H,ArH),7.00(m,2H,ArH),5.82(q, 2H,CH),4.07(m,4H,CH2),3.93(m,4H,CH2),2.25(m,4H,CH2),2.10(m,4H,CH2)1.84-1.59(m,12H,3CH2),1.51(d,6H,CH3) and 0.92(t,6H,CH3).

[0164] Synthesis of MD2 The synthesis scheme of the monomer represented by MD2 is shown in Scheme 2. Scheme 2 [ka]

[0165] In a reaction vessel, 1-ethylcyclopentyl-2-hydroxy-5-iodobenzoate (36.0 g, 100 mmol) was suspended in DMF to give a 9 wt% solution. Cesium carbonate (65.1 g, 200 mmol) and sodium iodide (1.50 g, 10 mmol) were added neat to the solution to form a reaction mixture. Next, (2-chloroethoxy)ethene (12.8 g, 120 mmol) was slowly added dropwise to the reaction mixture with stirring. The reaction mixture was heated to an internal temperature of 70°C for 4 hours. Then, (2-chloroethoxy)ethene (10.7 g, 100 mmol) was added to the reaction mixture, and the reaction mixture was heated at 70°C for an additional 14 hours. The reaction mixture was allowed to cool to room temperature and then diluted with DI water (1.5 L), and the aqueous mixture was extracted with methyl tert-butyl ether (3 x 250 mL). The organic layers were combined, washed with water (5×200 mL), and the solvent was removed under reduced pressure to give the vinyl ether monomer intermediate SM2 as a colorless oil (37.5 g, 87% yield).

[0166] 1 H-NMR (500 MHz, chloroform-d) δ (ppm): 7.94 (d, 1H, ArH), 7.66 (dd, 1H, ArH), 6.73 (d, 1H, ArH), 6.51 (dd, 1H, alkenyl-H), 4.27-4.18 (m, 3H, CH₂ / alkenyl-H), 4.08-4.00 (m, 3H, CH₂ / alkenyl-H), 2.29-2.18 (m, 2H, CH₂), 2.09 (q, 2H, CH₂), 1.82-1.68 (m, 4H, CH₂), 1.67-1.57 (m, 2H, CH₂), 0.93 (t, 3H, CH₂).

[0167] A reaction vessel was charged with 4,4'-sulfonyldiphenol (2.00 g, 8.0 mmol) and PGMEA to obtain a 35 wt% solution. Trace amounts of water were removed by azeotropic distillation. Trifluoroacetic acid (0.02 g, 0.2 mmol) and vinyl ether monomer intermediate SM2 (7.83 g, 16.4 mmol) were added to the anhydrous solution to obtain a reaction mixture. The reaction mixture was stirred at room temperature (approximately 23 °C) for 24 hours. The reaction mixture was then passed through an alumina column, and the solvent was removed under reduced pressure to obtain MD2 (7.43 g, 75.7% yield).

[0168] 1 H-NMR(acetone-d6),δ(ppm):7.89(d,4H,ArH),7.87(s,2H,ArH),7.75(d,2H,ArH),7.24(d,4H,ArH),6.95(d,2H,ArH),5.77(q,2H,CH), 4.06(m,4H,CH2),3.89(m,4H,CH2),2.23(m,4H,CH2),2.09(m,4H,CH2)1.84-1.59(m,12H,3CH2),1.51(d,6H,CH3) and 0.92(t,6H,CH3).

[0169] Synthesis of MD3 The synthesis scheme of the monomer represented by MD3 is shown in Scheme 3. Scheme 3 [ka]

[0170] In a reaction vessel, 1-ethylcyclopentyl-hydroxy-3,5-diiodobenzoate (36.5 g, 75 mmol) was suspended in DMF to form a 12 wt% solution. Cesium carbonate (48.9 g, 150 mmol) and sodium iodide (1.12 g, 7.5 mmol) were added neat to form a reaction mixture. Next, (2-chloroethoxy)ethene (12.8 g, 120 mmol) was slowly added dropwise to the reaction mixture with stirring. The reaction mixture was heated to an internal temperature of 70°C for 16 hours. Additional (2-chloroethoxy)ethene (9.6 g, 100 mmol) was then added to the reaction mixture, and the reaction temperature was increased to 85°C for 1 hour. The reaction mixture was allowed to cool to room temperature and then diluted with DI water (1.5 L), and the aqueous mixture was extracted with ethyl acetate (4 x 200 mL). The organic layers were combined, washed with DI water (5 x 200 mL), and the solvent was removed under reduced pressure to give intermediate SM3 as a colorless oil (37.5 g, 90% yield).

[0171] 1 H-NMR (500 MHz, chloroform-d) δ (ppm): 8.20 (d, 1H, ArH), 7.92 (d, 1H, ArH), 6.52 (dd, 1H, alkenyl-H), 4.30-4.20 (m, 3H, CH2 / alkenyl-H), 4.10 (t, 2H, CH2), 4.05 (dd, 1H, alkenyl-H), 2.28-2.15 (m, 2H, CH2), 2.10 (q, 2H, CH2), 1.84-1.71 (m, 4H, CH2), 1.70-1.60 (m, 2H, CH2), 0.93 (t, 3H, CH3).

[0172] A reaction vessel was charged with 4,4'-(perfluoropropane-2,2-diyl)diphenol (2.00 g, 5.9 mmol) and PGMEA to obtain a 35 wt% solution. Trace amounts of water were removed by azeotropic distillation. Trifluoroacetic acid (0.02 g, 0.2 mmol) and vinyl ether monomer intermediate SM3 (7.14 g, 12.2 mmol) were added to the anhydrous solution to obtain a reaction mixture. The reaction mixture was stirred at room temperature (approximately 23 °C) for 24 hours. The reaction mixture was then passed through an alumina column, and the solvent was removed under reduced pressure to obtain MD3 (7.2 g, 79.0% yield).

[0173] 1 H NMR(acetone-d6),δ(ppm):8.36(s,2H,ArH),8.22(s,2H,ArH),7.33(d,4H,ArH),7.13(d,4H,ArH),5.69(q,2H,CH),4.14(m,4 H,CH2),4.01(m,4H,CH2),2.20(m,4H,CH2),2.09(m,4H,CH2)1.84-1.59(m,12H,CH2),1.54(d,6H,CH3) and 0.93(t,6H,CH3).

[0174] Synthesis of MD4 The synthesis scheme of the monomer represented by MD4 is shown in Scheme 4. Scheme 4 [ka]

[0175] A reaction vessel was charged with 4,4'-sulfonyldiphenol (2.00 g, 8.0 mmol) and PGMEA to obtain a 35 wt% solution. Trace amounts of water were removed by azeotropic distillation. Trifluoroacetic acid (0.02 g, 0.2 mmol) and vinyl ether monomer intermediate SM3 (9.59 g, 16.4 mmol) were added to the anhydrous solution to obtain a reaction mixture. The reaction mixture was stirred at room temperature (approximately 23 °C) for 24 hours. The reaction mixture was then passed through an alumina column, and the solvent was removed under reduced pressure to obtain MD4 (8.3 g, 71.7% yield).

[0176] 1 H-NMR (acetone-d6), δ(ppm):8.29(d,2H,ArH),7.96(d,2H,ArH),7.89(d,4H,ArH),7.24(d,4H,ArH),5.77(q,2H,CH),4.09(m, 4H,CH2),3.96(m,4H,CH2),2.20(m,4H,CH2),2.09(m,4H,CH2)1.84-1.59(m,12H,CH2),1.51(d,6H,CH3) and 0.92(t,6H,CH3).

[0177] MD5 Synthesis The synthesis scheme of the monomer represented by MD5 is shown in Scheme 5. Scheme 5 [ka]

[0178] In a reaction vessel, 2-phenylpropan-2-yl 2-hydroxy-5-iodobenzoate (11.5 g, 30 mmol) was suspended in DMP to give an 11.5 wt% solution. Cesium carbonate (19.5 g, 60 mmol) and sodium iodide (0.5 g, 3 mmol) were added neat to the solution to form a reaction mixture. Next, (2-chloroethoxy)ethene (3.8 g, 36 mmol) was slowly added dropwise to the reaction mixture with stirring. The reaction mixture was heated to an internal temperature of 70°C for 4 hours. Additional (2-chloroethoxy)ethene (3.2 g, 30 mmol) was then added to the reaction mixture, and the reaction mixture was heated at 70°C for an additional 16 hours. The reaction mixture was allowed to cool to room temperature and then diluted with DI water (1.0 L), and the aqueous mixture was extracted with ethyl acetate (3 x 100 mL). The organic layers were combined, washed with DI water (5×100 mL), and the solvent was removed under reduced pressure to give intermediate SM4 as a colorless oil (11.1 g, 82% yield).

[0179] 1 H-NMR (500 MHz, acetone-d₆) δ (ppm): 7.90 (s, 1H, ArH), 7.79 (d, 1H, ArH), 7.53 (d, 2H, ArH), 7.34 (t, 2H, ArH), 7.23 (t, 1H, ArH), 7.00 (d, 1H, ArH), 6.57 (dd, 1H, alkenyl-H), 4.34 (t, 2H, CH₂), 4.27 (d, 1H, alkenyl-H), 4.13 (t, 2H, CH₂), 4.01 (d, 1H, alkenyl-H), 1.86 (s, 6H, CH₃).

[0180] A reaction vessel was charged with 4,4'-sulfonyldiphenol (2.00 g, 8.0 mmol) and PGMEA to obtain a 35 wt% solution. Trace amounts of water were removed by azeotropic distillation. Trifluoroacetic acid (0.02 g, 0.2 mmol) and vinyl ether monomer intermediate SM4 (6.17 g, 12.3 mmol) were added to the anhydrous solution to obtain a reaction mixture. The reaction mixture was stirred at room temperature (approximately 23 °C) for 24 hours. The reaction mixture was then passed through an alumina column, and the solvent was removed under reduced pressure to obtain MD5 (6.9 g, 72.0% yield).

[0181] 1 H-NMR (acetone-d6), δ(ppm):7.96(t,2H,ArH),7.84(d,4H,ArH),7.78(dt,2H,ArH),7.53(d,4H,ArH),7.33(t,4H,ArH),7.23(t,2H,A rH),7.15(d,4H,ArH),6.96(d,2H,ArH),5.75(q,2H,CH),4.08(m,4H,CH2),3.92(m,4H,CH2),1.86(d,12H,CH3) and 1.45(d,6H,CH3).

[0182] Synthesis of C1 The synthesis scheme of the monomer represented by C1 is shown in Scheme 6. Scheme 6 [ka]

[0183] A reaction vessel was charged with 4,4'-sulfonyldiphenol (10.0 g, 40.0 mmol) and PGMEA to obtain a 20 wt% solution. Trace amounts of water were removed by azeotropic distillation. Trifluoroacetic acid (0.11 g, 0.98 mmol) and vinyl ether SC1 (10.34 g, 81.9 mmol) were added to the solution to obtain a reaction mixture. The reaction mixture was stirred at room temperature for 24 hours. The reaction mixture was then passed through an alumina column, and the solvent was removed under reduced pressure to obtain C1 (15.4 g, 76.0% yield).

[0184] 1H-NMR(acetone-d6)δ:7.91(d,4H,ArH),7.18(d,4H,ArH),5.72(q,2H,CH),3.26(m,2H, CH), 1.82(m,2H,CH2), 1.68(m,2H,CH2), 1.47(d,6H,CH3) and 1.90-1.20(m,12H,CH2).

[0185] Synthesis of polymer P1 Polymer P1 was prepared from monomers MA1, MB1, and MC1 in a molar ratio of 45 / 45 / 10. A monomer feed solution was prepared by dissolving MA1 (35.3 g, 218 mmol), MB1 (44.5 g, 218 mmol), and MC1 (24.2 g, 48 mmol) in 104 g of PGMEA. Separately, an initiator solution was prepared by dissolving 6.6 g (26.6 mmol) of dimethyl 2,2'-azobis(2-methylpropionate) (obtained from Wako Pure Chemical Industries, Ltd. as V-65) in 19.8 g of PGMEA / tetrahydrofuran (THF) (1:1 by weight). [ka]

[0186] The polymerization was carried out in a three-neck round-bottom flask equipped with a water condenser and a thermometer to monitor the reaction in the flask. The flask was charged with 53.3 g of PGMEA and heated to 75 °C. The monomer feed solution and initiator solution were each fed into the flask over a 4-hour period using a syringe pump. After the additions were complete, the contents of the reaction mixture were stirred for an additional 2 hours. The contents were then cooled to room temperature, diluted with 40 g of THF, and precipitated into 3 L of a 7:3 (v / v) mixture of heptane and isopropanol. The resulting reaction product was isolated by filtration and dried overnight at 35 °C under reduced pressure. The solid product was then dissolved in methanol and combined with a solution of sodium methoxide in methanol. The reaction mixture was heated to 67 °C for 4 hours. The reaction was then allowed to cool to room temperature, and an acidic resin was added to neutralize the pH. Polymer P1 was isolated as a white solid by precipitating the polymer solution into deionized (DI) water and drying the product under vacuum at 35° C. (62 g, Mw=8.5 kg / mol, PDI=1.55).

[0187] Photoresist Compositions and Evaluation Example 1 A photoresist composition was prepared by combining the components shown in Table 1, where the amounts are expressed in weight percent (wt%), with the sum of the non-solvent components being 100 wt%. The total solids content of the photoresist composition was 1.55 wt%. The photoresist composition was prepared in a solvent mixture of PGMEA and methyl-2-hydroxyisobutyrate in a 1:1 weight ratio.

[0188] The photoresist compositions were evaluated for line / space (l / s) patterning under KrF exposure using a bright-field mask pattern. The photoresist compositions were shaken on a mechanical shaker and then filtered through a PTFE disk filter with a pore size of 0.2 microns. On a TEL Clean Track ACT 8 wafer track, 200 mm silicon wafers overcoated with a BARC stack (60 nm thick AR3™ antireflective material laminated over 80 nm thick AR40A™ antireflective material (DuPont Electronics & Industrial)) were spin-coated with each photoresist composition and soft-baked at 110°C for 60 seconds to achieve a target photoresist layer thickness of approximately 40 nm. The wafers were each exposed to 248 nm radiation on a Canon FPA-5000 ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57) using a mask with a 120 nm l / s pattern. The wafers were post-exposure baked at 100°C for 60 seconds and then developed using MF-CD26™ TMAH developer (DuPont The resulting pattern was developed for 60 seconds in a HITACHI Electronics & Industrial Laboratory, rinsed with DI water, and then dried. The critical dimension (CD) of the resulting l / s pattern was measured using a HITACHI S-9380 CD SEM. The sizing energy (E size The line width roughness (LWR) and line width roughness (CD) were determined based on CD measurements. The sizing energy was the irradiation energy at which the target 120 nm l / s pattern was resolved. The results are shown in Table 1.

[0189] [Table 1]

[0190] The structures of PAG (PAG-1) and quencher (Q1) were as follows: [ka]

[0191] As shown in Table 1 above, the inventive photoresist compositions PR-1 to PR-5 achieved improved LWR (reduced LWR values) compared to the comparative photoresist compositions PR-6* and PR-7*.

[0192] Example 2 A photoresist composition was prepared by combining the components shown in Table 2. The amounts are expressed in weight percent, with the total of non-solvent components being 100 weight percent. The total solids content of the photoresist composition was 1.55 weight percent. The photoresist composition was prepared in a solvent mixture of PGMEA and methyl-2-hydroxyisobutyrate in a 1:1 weight ratio.

[0193] The photoresist compositions in Table 2 were evaluated for trench (TR) patterning using a dark field mask pattern under KrF exposure as described above. size The LWR of the area and space was determined based on the CD measurement. The sizing energy was determined from the irradiation energy at which the target 120 nm TR pattern was resolved. The results are shown in Table 2.

[0194] [Table 2]

[0195] As shown in Table 2 above, the inventive photoresist compositions PR-8 to PR-12 achieved improved LWR (i.e., reduced LWR) compared to the comparative photoresist compositions PR-13* to PR-14*.

[0196] While the present disclosure has been described in conjunction with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. Formula (1): 【Chemical 1】 (In the formula, X is a group represented by formula (6), (7), or (9): 【Chemistry 2】 (In formulas (6), (7), and (9), Ar ２ , and Ar ３ are each independently substituted or unsubstituted C ６～３０ is an arylene, Ar ４ is a substituted or unsubstituted C ６～３０ is aryl, R １０ and R １１ are each independently substituted or unsubstituted C １～３０ is alkyl, and * and *' in formulas (6), (7), and (9) indicate the points of attachment to the respective adjacent oxygen atoms. is represented by one of Each L １ are independently a single bond or a substituted or unsubstituted C １～３０ Alkylene, substituted or unsubstituted C ３～３０ Cycloalkylene, substituted or unsubstituted C １～３０ Heterocycloalkylene, substituted or unsubstituted C ６～３０ Arylene, or substituted or unsubstituted C １～３０ is a divalent linking group consisting of heteroarylene, Each L ２ represents a single bond, or —O— and / or substituted or unsubstituted C １～３０ A linking group consisting of alkylene, provided that L ２ When L contains —O—, one or more other additional groups may be present in L to prevent the formation of peroxo (—O—O—) with the adjacent acetal or ketal oxygen. ２ exists in Each Ar １ are independently substituted or unsubstituted C ６～３０ arylene, and the substituent C ６～３０ The arylene may be selected from halogen, C １～３０ Alkyl, C １～３０ Alkoxy, C ４～３０ Cycloalkyl, C ３～３０ Heterocycloalkyl, C ２～３０ Alkenyl, C ２～３０ Alkynyl, C ６～３０ Aryl, C ７～３０ Aryl alkyl, C ７～３０ Alkylaryl, C ６～３０ Aryloxy, C ３～３０ Heteroaryl, C ４～３０ Alkylheteroaryl, C ４～３０ Heteroarylalkyl or C ３～３０ substituted with at least one heteroaryloxy; Each R １ are independently an organic group containing an acid labile group, and R １ is represented by formula (2a) or formula (2b): 【Chemistry 3】 (In formula (2a) and formula (2b), R ４ ~R ６ 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 ２～２０ Heteroaryl, but R ４ ~R ６ No more than one selected from R ４ ~R ６ When one of R is hydrogen, ４ ~R ６ At least one of the other is substituted or unsubstituted C ６～２０ Aryl or substituted or unsubstituted C ３～２０ is heteroaryl, R ７ and R ８ 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 ６～２０ Aryl or substituted or unsubstituted C ２～２０ is heteroaryl, R ９ is a substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C ３～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２０ Aryl or substituted or unsubstituted C ３～２０ is heteroaryl, R ４ ~R ６ Any two of these may optionally be a single bond, or —O—, —S—, —C(O)—, —C(O)O—, 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 may form a ring together via a divalent linking group consisting of heteroarylene or a combination thereof, R ７ and R ８ is optionally a single bond, or —O—, —S—, —C(O)—, —C(O)O—, 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 may form a ring together via a divalent linking group consisting of heteroarylene or a combination thereof, R ７ or R ８ Any one or more of the following may optionally be a single bond, or —O—, —S—, —C(O)—, —C(O)O—, substituted or unsubstituted C １～３０ Alkylene, substituted or unsubstituted C ３～３０ Cycloalkylene, substituted or unsubstituted C ３～３０ Heterocycloalkylene, substituted or unsubstituted C ６～３０ Arylene, substituted or unsubstituted C ３～３０ R via a divalent linking group consisting of heteroarylene or a combination thereof ９ may form a ring together with * and *' in formulas (2a) and (2b) respectively represent L １ represents the binding site for and having a structure represented by one of: R ２ and R ３ are each independently hydrogen or substituted or unsubstituted C １～３０ is alkyl, R ２ and R ３ is optionally a single bond, or —O—, —S—, —C(O)—, —C(O)O—, 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 a ring is formed together with a divalent linking group consisting of heteroarylene or a combination thereof; L １ , L ２ , Ar ２ , Ar ３ , Ar ４ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ In the formula (I), the substituents of the substituted alkyl, the substituted cycloalkyl, the substituted heterocycloalkyl, the substituted alkenyl, the substituted cycloalkenyl, the substituted heterocycloalkenyl, the substituted aryl, the substituted heteroaryl, the substituted alkylene, the substituted cycloalkylene, the substituted heterocycloalkylene, the substituted arylene, and the substituted heteroarylene are nitro; cyano; hydroxyl; oxo; amino, mono- or di-(C １～６ ) alkylamino, C ２～６ Alkanoyl group, formyl, carboxylic acid or alkali metal salt or ammonium salt thereof; C ２～６ Alkyl esters (—C(O)O-alkyl or —OC(O)-alkyl); C ７～１３ Aryl esters (—C(O)O-aryl or —OC(O)-aryl); amides (—C(O)NR ２ , where R is hydrogen or C １～６ alkyl); carboxamide (-CH ２ C(O)NR ２ , where R is hydrogen or C １～６ alkyl); halogen; thiol; C １～６ Alkylthio; Thiocyano; 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; C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms ７～１９ Arylalkyl; arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms; C ７～１２ Alkylaryl; C ３～１２ Heterocycloalkyl; C ３～１２ Heteroaryl; C １～６ Alkylsulfonyl; C ６～１２ arylsulfonyl; or tosyl; m is 1 or 2; k is 1, r is 2) and is not a polymer.

2. R １ The compound of claim 1 , having a structure represented by formula (2a).

3. R １ The compound of claim 1 , having a structure represented by formula (2b).

4. Ar ２ , Ar ３ , and Ar ４ is each independently substituted with 1 to 4 iodine atoms.

5. 5. The compound of claim 1, wherein each subunit represented by the integer r is the same.

6. A compound according to any one of claims 1 to 5; Solvent and A photoresist composition comprising:

7. The photoresist composition of claim 6 further comprising a polymer.

8. The photoresist composition of claim 7 wherein the polymer is acid-sensitive.

9. The photoresist composition of any one of claims 6 to 8, further comprising a photoacid generator.

10. A coated substrate, (a) a substrate having one or more layers to be patterned on a surface thereof; (b) a layer formed from the photoresist composition of any one of claims 6 to 9 disposed on the one or more layers to be patterned.

11. 1. A method of forming a pattern, comprising: applying a layer of a compound according to any one of claims 1 to 5 onto a substrate to provide a photoresist layer; patternwise exposing the photoresist layer to activating radiation to provide an exposed photoresist layer; and developing the exposed photoresist layer to provide a photoresist pattern.

12. 1. A method of forming a pattern, comprising: applying a layer of the photoresist composition of any one of claims 6 to 9 onto a substrate to provide a photoresist composition layer; patternwise exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer to provide a photoresist pattern.

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