Polymer, photoresist composition containing same, and pattern formation method

Abstract

To provide polymers, photoresist compositions comprising the same, and pattern formation methods.SOLUTION: A polymer comprises: a first repeating unit derived from a first monomer represented by the formula (1); a second repeating unit comprising an acid-labile group, a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof. In the formula (1): P is a polymerizable group including an ethylenically unsaturated carbon-carbon double bond; L1 is a single bond or a linking group; Ar is a substituted or unsubstituted C6-30 aromatic group, or a substituted or unsubstituted C4-30 heteroaromatic group; X is O or S; A is a group selected from among -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -C(S)-, and -N(Ra)-; and Ra is hydrogen or a non-hydrogen substituent. The first and second repeating units are structurally different.SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

[0004] [Patent Document 1] U.S. Patent No. 8,431,325 [Patent Document 2] U.S. Patent No. 4,189,323 [Non-patent literature]

[0005] [Non-Patent Document 1] Wallow,T.et al Proc.SPIE 6921,69211F,2008 Summary of the Invention [Problem to be solved by the invention]

[0006] Despite advances in resist technology, there remains a need for photoresist compositions that address one or more of the problems associated with the prior art. In particular, there is a continuing need for photoresist compositions that can be used at increased pattern densities, including photoresist compositions that can achieve lower photospeeds and lower LWR for line / space patterns. [Means for solving the problem]

[0007] One embodiment is a compound represented by formula (1) [ka] and a second repeat unit comprising an acid labile group, a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof, wherein in formula (1), P is a polymerizable group comprising an ethylenically unsaturated carbon-carbon double bond, and L 1 is a single bond or a linking group, and Ar is a substituted or unsubstituted C 6~30 Aromatic group or substituted or unsubstituted C 4~30 A is a heteroaromatic group, X is O or S, and A is -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -C(S)-, or -N(R a )-, and R ais hydrogen or a non-hydrogen substituent, and R 1 and R 2 are each independently hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 2~30 Heteroalkenyl, substituted or unsubstituted C 2~30 Heteroalkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Cycloalkynyl, substituted or unsubstituted C3-C 10 Heterocycloalkenyl, substituted or unsubstituted C3-C 10 Heterocycloalkynyl, substituted or unsubstituted C 6~50 Aryl, substituted or unsubstituted C 7~50 Aryl alkyl, substituted or unsubstituted C 7~50 Alkylaryl, substituted or unsubstituted C 6~50 Aryloxy, substituted or unsubstituted C 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Alkylheteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 heteroaryloxy, and R 1 and R 2 are optionally linked together to form a substituted or unsubstituted ring, and R 1 and R 2 each independently optionally further comprises one or more divalent linking groups as part of its structure, and the first repeat unit and the second repeat unit are structurally distinct.

[0008] A photoresist composition containing a polymer and a solvent is also provided.

[0009] Another aspect also provides a method of forming a pattern, the method including applying a layer of a photoresist composition onto a substrate to form a photoresist composition layer, patternwise exposing the photoresist composition layer to activating radiation to form an exposed photoresist composition layer, and developing the exposed photoresist composition layer.

[0010] Yet another aspect is a method of forming a pattern, comprising applying a layer of a photoresist composition onto a substrate to form a photoresist composition layer, patternwise exposing the photoresist composition layer to activating radiation to form an exposed photoresist composition layer, and developing the exposed photoresist composition layer, wherein the photoresist composition comprises a polymer and a solvent, and the polymer is a compound represented by Formula (1): [ka] wherein formula (1) is as defined herein. DETAILED DESCRIPTION OF THE INVENTION

[0011] 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.

[0012] As used herein, the terms "a," "an," and "the" do not denote quantitative limitations and should be construed to include both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. The modifier "about," used in connection with a quantity, is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measuring the particular quantity). All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independent and inclusive of each other. The suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including at least one of that term. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where the event does not occur. The terms "first," "second," etc., as used herein, do not denote order, quantity, or importance, but rather are used to distinguish one element from another. When an element is said to be "on" another element, it may be in direct contact with the other element, or intervening elements may be present between them. In contrast, when an element is said to be "directly on" another element, there are no intervening elements present. It should be understood that the described components, elements, limitations, and / or features of the embodiments can be combined in any suitable manner in the various embodiments.

[0013] 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.

[0014] As used herein, "actinic rays" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, or particle rays such as electron beams and ion beams. Furthermore, in the present invention, "light" refers to actinic rays or radiation. A krypton fluoride laser (KrF laser) is a specific type of excimer laser and is sometimes called an exciplex laser. "Excimer" is an abbreviation for "exciplex," and "exciplex" is an abbreviation for "excimer complex." An excimer laser uses a mixture of a rare gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine), which emits coherent stimulating radiation (laser light) in the ultraviolet range under suitable conditions of electrical stimulation and high pressure. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using far ultraviolet light such as that from a mercury lamp or an excimer laser, X-rays, or extreme ultraviolet light (EUV light), but also writing using particle beams such as electron beams and ion beams.

[0015] As used herein, an "organic group" contains one or more carbon atoms, for example, 1 to 60 carbon atoms. The term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom. The term "alkyl" refers to a straight- or branched-chain saturated hydrocarbon radical having the specified number of carbon atoms and a valence of one; "alkylene" refers to an alkyl radical having a valence of two; "hydroxyalkyl" refers to an alkyl radical substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid" refer to groups having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent radical having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl radical having a valence of two; "alkenyl" refers to a straight- or branched-chain monovalent hydrocarbon radical having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl radical having a valence of two; and "cycloalkenyl" refers to a radical having at least one carbon-carbon double bond. "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system that satisfies Huckel's rule and contains carbon in the ring and may optionally contain one or more heteroatoms selected from N, O, and S in place of carbon atoms in the ring; "arylene" 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 more heteroatoms) in place of a carbon atom, where each heteroatom is independently N, O, S, Si, or P; a "heteroatom-containing group" refers to a substituent that contains at least one heteroatom; a "heteroalkyl group" refers to an alkyl group having from 1 to 4 or more heteroatoms in place of carbon; a "heterocycloalkyl group" refers to a cycloalkyl group having from 1 to 4 or more heteroatoms in place of carbon as ring members; a "heterocycloalkylene group" refers to a heterocycloalkyl group having a valence of 2; a "heteroaryl group" refers to an aryl group having from 1 to 4 or more heteroatoms in place of carbon as ring members; and a "heteroarylene group" refers to a heteroaryl group having a valence of 2.

[0017] Unless expressly specified otherwise, each of the foregoing substituents can be optionally substituted. For example, if a group is listed without specifying whether it is substituted or unsubstituted, the group includes both unsubstituted and substituted groups. The term "optionally substituted" refers to substituted or unsubstituted.

[0018] "Substituted" means that at least one hydrogen atom of the chemical structure is replaced with another terminal substituent, typically monovalent, provided that the normal valence of the designated atom is not exceeded. When the substituent is oxo (i.e., =0), two geminal hydrogen atoms on the carbon atom are replaced with the terminal oxo group. Combinations of substituents or variables are permissible. Exemplary substituents that may be present at a "substituted" position include nitro (-NO), cyano (-CN), hydroxyl (-OH), oxo (=0), amino (-NH), mono- or di-(C 1~6 ) alkylamino, alkanoyl (acyl, etc. C 2~6 alkanoyl group, etc.), formyl (-C(=O)H), carboxylic acid or its alkali metal salt or ammonium salt;C 2~6Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7~13 Esters (including acrylates, methacrylates and lactones) such as aryl esters (-C(=O)O-aryl or -OC(=O)-aryl); amides (-C(=O)NR2 where R is hydrogen or C 1~6 alkyl), carboxamide (-CHC(=O)NR (wherein R is hydrogen or C 1~6 Alkyl), halogen, thiol (-SH), C 1~6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1~6 Alkyl, C 2~6 Alkenyl, C 2~6 Alkynyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, C with at least one aromatic ring 6~12 Aryl (e.g., phenyl, biphenyl, or naphthyl, each ring of which may be substituted or unsubstituted aromatic), C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms 7~19 arylalkyl, arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Includes, but is not limited to, arylsulfonyl, (-S(=O)2-aryl) or tosyl (CH3C6H4SO2-).

[0019] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one or more fluoro, chloro, bromo, or iodo substituents in place of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or only fluoro groups can be present.

[0020] As used herein, the term "acid labile group" refers to a group formed on a polymer whose bond is cleaved by the action of an acid, optionally and typically accompanied by thermal treatment, resulting in the formation of a polar group, such as a carboxylic acid group or an alcohol group; the moiety linked to the cleaved bond is then separated from the polymer, optionally and typically. In another system, a non-polymeric compound may contain an acid labile group that can be cleaved by the action of an acid, resulting in the formation of a polar group, such as a carboxylic acid group or an alcohol group, at the cleaved portion of the non-polymeric compound. Such an acid is typically a photogenerated acid, in which bond cleavage occurs during post-exposure bake (PEB). However, embodiments are not limited thereto; for example, such an acid may be thermally generated. 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."

[0021] As used herein, unless otherwise specified, a "divalent linking group" includes -O-, -S-, -Te-, -Se-, -C(O)-, -N(R b )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 R refers to a divalent group containing one or more of: b is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C1~20 Heteroalkyl, substituted or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 Typically, the divalent linking group is -O-, -S-, -C(O)-, -N(R b )-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof; R b is hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 More typically, the divalent linking group is —O—, —C(O)—, —C(O)O—, —N(R b )-, -C(O)N(R b )-, substituted or unsubstituted C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 heteroarylene, or a combination thereof; R bis hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 1~10 Heteroalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 It is heteroaryl.

[0022] The present disclosure relates to polymers derived from 1,4-benzodioxine monomers, which optionally contain a second repeat unit and / or optional repeat units derived from other monomers that contain an acid labile group, a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof. The polymers can be particularly useful in photoresist compositions for increasing pattern density, for example, by decreasing photospeed and reducing line width roughness (LWR).

[0023] The polymer includes a first repeat unit derived from a first monomer represented by formula (1). [ka]

[0024] In formula (1), P is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond. Typically, P is a substituted or unsubstituted C2- 20 The polymerizable group can be selected from an alkenyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted (meth)acrylic group, a substituted or unsubstituted vinyl ether group, a substituted or unsubstituted vinyl ketone group, a substituted or unsubstituted vinyl ester group, or a substituted or unsubstituted vinyl aromatic group. Preferably, the polymerizable group is a substituted or unsubstituted C2- 20 It is an alkenyl, a substituted or unsubstituted norbornyl, a substituted or unsubstituted (meth)acrylic, or a substituted or unsubstituted vinyl aromatic.

[0025] In formula (1), L 1 is a single bond or a linking group. Typically, the linking group is -O-, -S-, -C(O)-, -C(O)O-, -N(Rb )-, -C(O)N(R b )-, -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 may include one or more of: b is hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 Preferably, the linking group is -O-, -C(O)-, -C(O)O-, -N(R b )-, -C(O)N(R b )-, substituted or unsubstituted C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 heteroarylene, or a combination thereof; R b is hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 It can be alkylheteroaryl.

[0026] In formula (1), Ar is C 6~30 Aromatic group or C 4~30 Heteroaromatic groups, which may be substituted or unsubstituted. 6~30 Aromatic groups and / or C 4~30 Heteroaromatic groups can be monocyclic or non-fused polycyclic or fused polycyclic. 6~30 Aromatic groups and / or C 4~30 When the heteroaromatic group is polycyclic, the rings or ring groups can be fused (such as naphthyl), non-fused, or combinations thereof. 6~30 Aromatic groups and / or C 4~30 When the heteroaromatic group is non-fused, the rings or ring groups can be directly linked (such as biaryl or biphenyl) or bridged by a heteroatom (such as triphenylamino or diphenylene ether). 6~30 Aromatic groups and / or C 4~30 Heteroaromatic groups may include combinations of fused and directly bonded rings (such as binaphthyl, etc.). 6~30 Aromatic groups and / or C 4~30 The heteroaromatic group may be a substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl, substituted or unsubstituted C 3~30 Alkylheteroaryl, -OR c 、 -or-NR c R e and R c and R e are each independently a 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 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 5~30 It is alkylheteroaryl.

[0027] In formula (1), X is O or S. Preferably, X is O.

[0028] In formula (1), A is -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -C(S)-, or -N(R a )-, and R a is hydrogen or a non-hydrogen substituent. Typically, A is —O—, —S—, or —N(R a )-, R a is hydrogen or a non-hydrogen substituent. For example, R a is hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 It can be alkylheteroaryl.

[0029] In formula (1), R 1 and R 2 are each independently hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 2~30 Heteroalkenyl, substituted or unsubstituted C 2~30 Heteroalkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Cycloalkynyl, substituted or unsubstituted C3-C 10 Heterocycloalkenyl, substituted or unsubstituted C3-C 10 Heterocycloalkynyl, substituted or unsubstituted C 6~50 Aryl, substituted or unsubstituted C 7~50 Aryl alkyl, substituted or unsubstituted C 7~50 Alkylaryl, substituted or unsubstituted C 6~50 Aryloxy, substituted or unsubstituted C4~30 Heteroaryl, substituted or unsubstituted C 5~30 Alkylheteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 Typically, R 1 and R 2 are each independently hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, 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 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Alkylheteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 It may be heteroaryloxy.

[0030] In formula (1), R 1 and R 2 are optionally linked together to form a substituted or unsubstituted ring. For example, R 1 and R 2 R can be linked via a single bond or a divalent linking group. 1 and R 2 When are linked to form a ring, the ring can be substituted or unsubstituted. Exemplary substituents include substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl, substituted or unsubstituted C 3~30 Alkylheteroaryl, -OR c 、 -or-NR c R e One or more of the following may be mentioned: R c and R e are each independently a 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 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 5~30 It is alkylheteroaryl.

[0031] R 1 and R 2 each independently optionally further comprises one or more divalent linking groups as part of its structure. Exemplary divalent linking groups are -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R b )-, -C(O)N(R b )-, 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 may be selected from heteroarylene, heteroaryl, or combinations thereof; b is hydrogen, substituted or unsubstituted C1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 It can be alkylheteroaryl.

[0032] In some embodiments, the first monomer can be represented by formula (1a): [ka]

[0033] In formula (1a), P is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond as defined in formula (1). Preferably, the polymerizable group is a substituted or unsubstituted C2- 20 It is an alkenyl, a substituted or unsubstituted norbornyl, a substituted or unsubstituted (meth)acrylic, or a substituted or unsubstituted vinyl aromatic.

[0034] In formula (1a), L 1 is a single bond or a linking group as defined in formula (1). Preferably, the linking group is -O-, -C(O)-, -C(O)O-, -N(R b )-, -C(O)N(R b )-, 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 C3~10 heteroarylene, or a combination thereof; R b is hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 1~10 Heteroalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 It may be heteroaryl.

[0035] In formula (1a), Ar is C 6~30 Aromatic group or C 4~30 A heteroaromatic group. Typically, Ar is C 6~10 Aryl group or C 4~10 It may be a heteroaryl group. Preferably, Ar may be a phenyl (benzene) group.

[0036] In formula (1a), A is O, S, SO, SO2, or NR a and R a is hydrogen or a non-hydrogen substituent as defined in formula (1). Typically, A is O, S or NR a R a is hydrogen or a non-hydrogen substituent as defined in formula (1). Preferably, A can be O.

[0037] In formula (1a), R 1 and R 2 are each independently hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 2~30 Heteroalkenyl, substituted or unsubstituted C 2~30 Heteroalkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10Cycloalkenyl, substituted or unsubstituted C3-C 10 Cycloalkynyl, substituted or unsubstituted C3-C 10 Heterocycloalkenyl, substituted or unsubstituted C3-C 10 Heterocycloalkynyl, substituted or unsubstituted C 6~50 Aryl, substituted or unsubstituted C 7~50 Aryl alkyl, substituted or unsubstituted C 7~50 Alkylaryl, substituted or unsubstituted C 6~50 Aryloxy, substituted or unsubstituted C 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Alkylheteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 Preferably, R 1 and R 2 are each independently a non-hydrogen substituent.

[0038] In formula (1a), R 1 and R 2 are as defined in formula (1), optionally linked together to form a substituted or unsubstituted ring. For example, R 1 and R 2 can be linked via a single bond or a divalent linking group as defined in formula (1).

[0039] In formula (1a), R 1 and R 2 are as defined in formula (1), each independently optionally further comprising one or more divalent linking groups as part of its structure.

[0040] In formula (1a), each R 3 are independently hydroxy, cyano, halogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30Alkylthio, substituted or unsubstituted C 6~50 Aryl, substituted or unsubstituted C 7~50 Aryl alkyl, substituted or unsubstituted C 7~50 Alkylaryl, substituted or unsubstituted C 6~50 Aryloxy, substituted or unsubstituted C 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Alkylheteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 Typically, each R 3 are independently hydroxy, cyano, halogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C 6~20 Aryl, substituted or unsubstituted C 7~20 Aryl alkyl, substituted or unsubstituted C 7~20 Alkylaryl, substituted or unsubstituted C 6~20 Aryloxy, substituted or unsubstituted C 4~20 Heteroaryl, substituted or unsubstituted C 5~20 Alkylheteroaryl, substituted or unsubstituted C 5~20 Heteroarylalkyl or substituted or unsubstituted C 3~20 It is heteroaryloxy.

[0041] In formula (1a), n1 can be an integer of 0 to 8. Typically, n1 can be an integer of 0 to 5, and preferably, n1 can be an integer of 0 to 3. In yet another embodiment, n1 can be an integer of 0 to 2 or an integer of 0 to 1.

[0042] In some embodiments, the first monomer can be represented by formula (2): [ka]

[0043] In formula (2), P is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond as defined in formula (1). Preferably, the polymerizable group is a substituted or unsubstituted C2- 20 It is an alkenyl, a substituted or unsubstituted norbornyl, a substituted or unsubstituted (meth)acrylic, or a substituted or unsubstituted vinyl aromatic.

[0044] In equation (2), L 2 is a single bond or a linking group as defined in formula (1). Preferably, the linking group is -O-, -C(O)-, -C(O)O-, -N(R b )-, -C(O)N(R b )-, substituted or unsubstituted C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 heteroarylene, or a combination thereof; R b is hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 It is alkylheteroaryl.

[0045] In equation (2), R 4 and R 5are each independently hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 2~30 Heteroalkenyl, substituted or unsubstituted C 2~30 Heteroalkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Cycloalkynyl, substituted or unsubstituted C3-C 10 Heterocycloalkenyl, substituted or unsubstituted C3-C 10 Heterocycloalkynyl, substituted or unsubstituted C 6~50 Aryl, substituted or unsubstituted C 7~50 Aryl alkyl, substituted or unsubstituted C 7~50 Alkylaryl, substituted or unsubstituted C 6~50 Aryloxy, substituted or unsubstituted C 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Alkylheteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 Preferably, R 4 and R 5 are each independently a non-hydrogen substituent.

[0046] In formula (2), each R 6 are independently hydroxy, cyano, halogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30Alkylthio, substituted or unsubstituted C 6~50 Aryl, substituted or unsubstituted C 7~50 Aryl alkyl, substituted or unsubstituted C 7~50 Alkylaryl, substituted or unsubstituted C 6~50 Aryloxy, substituted or unsubstituted C 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Alkylheteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 It is heteroaryloxy.

[0047] In formula (2), n2 can be an integer of 0 to 3. Typically, n2 can be an integer of 0 to 2 or an integer of 0 to 1.

[0048] In some embodiments, the first monomer can include a (meth)acrylic group or a vinyl aromatic group. In other words, in some embodiments, the polymerizable group P can be a (meth)acrylic group or a vinyl aromatic group.

[0049] Non-limiting examples of the first monomer include: [ka] [ka] [ka] [ka]

[0050] The first repeat unit of the polymer is typically present in an amount of from 5 to 50 mole %, more typically from 5 to 35 mole %, and even more typically from 10 to 25 mole %, based on the total repeat units of the polymer.

[0051] The polymer may include a second repeat unit comprising an acid labile group, a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof. For example, the polymer may include a second repeat unit comprising an acid labile group, a hydroxyaryl group, a sulfonamide group, or a fluoroalcohol group. In some embodiments, the second repeat unit comprises an acid labile group.

[0052] 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 an alkyl group and an aryl group, tertiary alkoxy groups, acetal groups, ketal groups, tertiary carbonate groups, and tertiary carbamate groups. Typically, the acid labile group can be an acetal group, a ketal group, a tertiary carbonate group, a tertiary carbamate group, or a tertiary ester group. As used herein, the term "tertiary carbamate group" includes tertiary carbamate ester groups having an alkyl group, tertiary carbamate ester groups having an aryl group, and tertiary carbamate ester groups having a combination of an alkyl group and an aryl group. As used herein, the term "tertiary carbonate group" includes tertiary carbonate ester groups having an alkyl group, tertiary carbonate ester groups having an aryl group, and tertiary carbonate ester groups having a combination of an alkyl group and an aryl group. Preferably, the acid labile group of the second repeating unit includes a tertiary ester group.

[0053] The second repeat unit of the polymer may include an acid labile group derived from one or more monomers of formula (3a), (3b), (3c), (3d) or (3e). [ka]

[0054] In formulas (3a) to (3e), each R d are independently hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl or substituted or unsubstituted C 1~10 Preferably, Rd is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It is alkyl, typically methyl.

[0055] In formula (3a), L 3 is a divalent linking group. For example, L 3 can be a divalent linking group containing at least one carbon atom, at least one heteroatom, or a combination thereof. For example, L 3 may contain 1 to 10 carbon atoms and at least one heteroatom. 3 is -OCH2-, -OCH2CH2O- or -N(R b )-, R b is hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 1~10 Heteroalkyl, substituted or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 It is heteroaryl.

[0056] In formulas (3a), (3b) and (3d), R 7 ~R 9 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 1~20 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 7 ~R 9 R 7 ~R 9 If one of is hydrogen, R 7 ~R 9 One or both of the other may be substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C4~20 provided that it is heteroaryl. Preferably, R 7 ~R 9 are each independently a substituted or unsubstituted C 1~6 Alkyl or substituted or unsubstituted C 3~10 It is cycloalkyl.

[0057] In formula (3a), R 7 ~R 9 any two of which together optionally form a ring, R 7 ~R 9 Each of the groups may contain, as part of its structure, -O-, -C(O)-, -N(R g )-, -S-, or -S(O)-; R g is hydrogen, straight or branched C 1~20 Alkyl, monocyclic or polycyclic C 3~20 Cycloalkyl or monocyclic or polycyclic C 1~20 For example, R 7 ~R 9 any one or more of the formula -CHC(=O)CH (3-n) Y n wherein each Y is independently a substituted or unsubstituted C 1~30 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 1~30 may be heterocycloalkyl, C a1 and C a2 are each independently hydrogen or a substituted or unsubstituted C 1~10 alkyl, C a1 and C a2 are optionally taken together to form a ring.

[0058] In formulas (3c) and (3e), R 10 and R 11 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20Cycloalkyl, substituted or unsubstituted C 1~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 2~20 may be heteroaryl, R 12 is a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 1~30 Optionally, R can be heterocycloalkyl. 10 or R 11 One of them is R 12 and form a heterocycle together. Preferably, R 10 and R 11 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 1~20 It may be a heterocycloalkyl.

[0059] In formulas (3d) and (3e), X a is a polymerizable group selected from vinyl and norbornyl, and L 4 and L 5 are each independently a single bond or a divalent linking group, and X a If is vinyl, L 4 and L 5 is not necessarily a single bond. 4 and L 5 are each independently a substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 3~30 In formulas (3d) and (3e), n3 and n4 may each independently be 0 or 1. When n3 or n4 is 0, the corresponding L 4 Group or L 5 It should be understood that the groups are attached directly to the respective oxygen atoms.

[0060] Non-limiting examples of monomers for providing the second repeat unit containing an acid labile group include: [ka] [ka] [ka] In these formulas, R d is hydrogen, halogen, substituted or unsubstituted C 1~6 Alkyl or substituted or unsubstituted C 3~6 It is cycloalkyl.

[0061] As described above, the second repeat unit may include a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof. For example, the second repeat unit may include a repeat unit of formula (4), (5), or a combination thereof. [ka]

[0062] In formulas (4) and (5), each R d is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It may be alkyl, typically hydrogen or methyl.

[0063] In equations (4) and (5), L 6 and L 7 may each independently be a single bond or one or more divalent linking groups. For example, L 6 and L 7 are each independently -O-, -C(O)-, -C(O)O-, -N(R b )-, -C(O)N(R b )-, substituted or unsubstituted C 1~10 Alkylene, substituted or unsubstituted C 3~10Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 heteroarylene or a combination thereof, R b is hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, 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 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl or substituted or unsubstituted C 3~30 In some embodiments, L is alkylheteroaryl. 6 and L 7 are each independently a single bond, or —C(O)O—, 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 It may be one or more groups selected from heteroarylene, heteroaryl, or combinations thereof.

[0064] In equation (4), R 15 is a substituted or unsubstituted C 1~100 Or C 1~20 Alkyl, typically C 1~12 Alkyl, substituted or unsubstituted C 3~30 Or C 3~20 Cycloalkyl or substituted or unsubstituted poly(C 1~3alkylene oxide). 1~100 or C 1~20 Alkyl, substituted C 3~30 or C 3~20 Cycloalkyl and substituted poly(C 1~3 The alkylene oxide) is substituted with one or more sulfonamide groups (eg, —NHSO2CF3) or fluoroalcohol groups (eg, —C(CF3)2OH).

[0065] In formula (5), Ar 2 is a substituted C optionally containing one or more aromatic ring heteroatoms selected from N, O, S or combinations thereof 5~60 It may be an aromatic group, and the aromatic group 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 or biphenyl) or bridged by heteroatoms (such as triphenylamino or diphenylene ether). 5~60 The aromatic group may contain a combination of fused and directly bonded rings (such as binaphthyl).

[0066] In formula (5), y can be an integer from 1 to 12, preferably from 1 to 6, and typically from 1 to 3. Each R x is at least one R x may independently be hydrogen or methyl, provided that is hydrogen.

[0067] Non-limiting examples of the second repeat unit of the polymer can include: [ka] [ka] (In the formula, R dis hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It may be alkyl, typically methyl.

[0068] When present, the second repeat unit of the polymer is typically present in an amount of 20 to 80 mole percent (mol %), more typically 25 to 75 mol %, and even more typically 30 to 70 mol %, based on the total repeat units of the polymer.

[0069] When the polymer includes both a first repeat unit and a second repeat unit, the first repeat unit and the second repeat unit are structurally different.

[0070] In one embodiment, the polymer may further include a third repeat unit different from the first repeat unit and the second repeat unit.

[0071] In one or more embodiments, the third repeat unit can include a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof.

[0072] When present, the polymer comprises the third repeat unit in an amount of 10 to 60 mol %, typically 10 to 50 mol %, more typically 10 to 40 mol %, based on the total repeat units of the polymer.

[0073] In some embodiments, the polymer may optionally further comprise one or more additional repeating units. The additional repeating units may be, for example, one or more additional units for the purpose of adjusting the properties of the photoresist composition. Exemplary additional units may include those derived from one or more of (meth)acrylate, vinyl aromatic, vinyl ether, vinyl ketone, and / or vinyl ester monomers. When one or more additional repeating units are present in the polymer, the additional repeating units may be used in an amount of up to 90 mol %, typically 3 to 50 mol %, based on the total repeating units of the polymer.

[0074] Non-limiting exemplary polymers of the present invention include: [ka] [ka] [ka] In the formula, a, b, and c each represent the mole percent of the repeating unit based on 100 mole percent of the total repeating units in the polymer.

[0075] 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 2,500 to 20,000 Da, and even more preferably 3,500 to 15,000 Da. w The PDI of the polymer is typically 1.1 to 3, more typically 1.1 to 2. The molecular weight is determined by gel permeation chromatography (GPC) using polystyrene standards.

[0076] The polymer can be prepared by any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined using a suitable solvent and initiator, or can be separately supplied and polymerized in a reactor. For example, the polymer can be obtained by polymerizing each monomer under any suitable conditions, such as heating at an effective temperature, irradiating with actinic radiation of an effective wavelength, or a combination thereof.

[0077] Also provided is a photoresist composition comprising a polymer described herein and a solvent.

[0078] The photoresist composition contains a solvent to dissolve the components of the composition and facilitate its coating on a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, and 4-methyl-2-pentanol; ethers such as propylene glycol monomethyl ether (PGME), diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone (CHO); ethyl acetate, n Examples of suitable solvents include esters such as butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyric acid 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 carbonate esters such as propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water, and combinations thereof. Among these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof. The total solvent content (i.e., the cumulative solvent content of all solvents) in a photoresist composition is typically 40 to 99 wt %, more typically 70 to 99 wt %, and even more typically 85 to 99 wt %, based on the total weight 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.

[0079] In photoresist compositions, the polymer is typically present in an amount of from 10 to 99.9 weight percent, typically from 25 to 99 weight percent, and more typically from 50 to 95 weight percent, based on the total solids content of the photoresist composition, it being understood that the total solids content includes the polymer, PAG, and other non-solvent components.

[0080] The photoresist composition may further contain a photoacid generator (PAG). The PAG may be ionic or non-ionic. The PAG may be in polymeric or non-polymeric form. In the polymeric form, the PAG may be present as a moiety in a repeat unit of a polymer derived from a polymerizable PAG monomer.

[0081] Suitable PAG compounds have the formula G + A - G + is a photoactive cation, and A - is an anion capable of generating a photoacid. The photoactive cation is preferably selected from onium cations, preferably iodonium or sulfonium cations. Particularly suitable anions include those whose conjugate acids have a pKa of -15 to 10. The anion is typically an organic anion having a sulfonate group or a non-sulfonate type group (such as a sulfonamidate, sulfonimidate, methide, or borate).

[0082] In some embodiments, the photoactive cation can be a sulfonium cation or an iodonium cation. For example, the photoactive cation can be a sulfonium cation of formula (7a) or an iodonium cation of formula (7b). [ka]

[0083] In formulas (7a) and (7b), R 16 ~R 20 are each independently a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C3~20 Cycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 6~30 Iodoaryl, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 7~20 Aryl alkyl or substituted or unsubstituted C 4~20 heteroaryl, alkyl, or a combination thereof. 16 ~R 18 may be individually or may be connected to another group R via a single bond or a divalent linking group. 16 ~R 18 can be linked to form a ring. 19 and R 20 can be individual or can be linked together via a single bond or a divalent linking group to form a ring. 16 ~R 20 may optionally include a divalent linking group as part of its structure. 16 ~R 20 may optionally include acid labile groups independently selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

[0084] Exemplary sulfonium cations of formula (7a) include one or more of the following: [ka] [ka]

[0085] Exemplary iodonium cations of formula (7b) can include one or more of the following: [ka]

[0086] Exemplary organic anions having a sulfonate group include one or more of the following: [ka]

[0087] Exemplary non-sulfonated anions include one or more of the following: [ka]

[0088] Commonly used onium salts include, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Other useful PAG compounds are known in the chemically amplified photoresist art, such as nonionic sulfonyl compounds, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonate 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)diamine; Examples of suitable photoacid generators include azomethane, glyoxime derivatives such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, sulfonate derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, and halogen-containing triazine compounds such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Suitable photoacid generators are described in detail in Patent Document 1 and Patent Document 2.

[0089] In some embodiments, the polymer may optionally further comprise repeat units comprising a PAG moiety, such as repeat units derived from one or more monomers of formula (8). [ka]

[0090] In equation (8), 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. 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-.

[0091] In equation (8), A 1 is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 2~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 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.

[0092] In equation (8), Z - is an anionic moiety, and its conjugate acid typically has a pKa of -15 to 1. Z - can be a sulfonate, carboxylate, anion of a sulfonamide, anion of a sulfonimide, or a methide anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonates and fluorinated sulfonimides.

[0093] In equation (8), G + is an organic cation as defined above. In some embodiments, G +is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of an alkyl group and an aryl group, or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of an alkyl group and an aryl group.

[0094] Exemplary monomers of formula (8) include: [ka] In the formula, G + is an organic cation.

[0095] The polymer may contain repeat units containing PAG moieties in an amount of 1 to 15 mol %, typically 1 to 8 mol %, more typically 2 to 6 mol %, based on all repeat units in the polymer.

[0096] Typically, when the photoresist composition includes a non-polymeric PAG, the PAG is present in the photoresist composition in an amount of from 0.1 to 55 weight percent, more typically from 1 to 25 weight percent, based on the total solids content of the photoresist composition. When present in polymeric form, the PAG is typically included in the polymer in an amount of from 1 to 25 mole percent, typically from 1 to 8 mole percent or 2 to 6 mole percent, based on the total repeat units in the polymer.

[0097] In some embodiments, the anion and / or cation of the PAG does not contain or is free of -F, -CF3, or -CF2- groups. "Free of -F, -CF3, or -CF2- groups" should be understood to mean that groups such as -CH2CF3 and -CH2CF2CH3 are excluded from the anion and / or cation of the PAG. In yet other embodiments, the anion and / or cation of the PAG does not contain fluorine (i.e., does not contain fluorine atoms and is not substituted with fluorine-containing groups). In some embodiments, the photoacid generator does not contain fluorine (i.e., both the photoactive cation and the anion do not contain fluorine).

[0098] 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 photoresist composition to the top surface of the formed photoresist layer.

[0099] 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 repeat units containing one or more base-labile groups. For example, a base-labile polymer can include repeat units containing two or more base-labile groups, which can be the same or different. Preferred base-labile polymers include at least one repeat unit containing two or more base-labile groups, for example, repeat units containing two or three base-labile groups.

[0100] 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.

[0101] 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 a molecular weight in the range of 50 to 1,500 Da.

[0102] 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 of the photoresist composition.

[0103] In addition to or instead of the base-labile polymer, the photoresist composition can further include one or more polymers different from the photoresist polymers described above. For example, the photoresist composition can include an additional polymer as described above, but with a different composition. Additionally or alternatively, the one or more additional polymers can include those well known in the photoresist art, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornenes, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrenic polymers, polyvinyl alcohols, or combinations thereof.

[0104] 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.

[0105] 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.

[0106] PDQ can be in a non-polymeric form or in a polymer-bound form. Polymerized units containing a photodegradable quencher are typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, and more preferably 1 to 2 mol %, based on the total repeat units of the polymer.

[0107] 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 3linear and cyclic amides and derivatives thereof, such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines, such as primary and secondary aldimines and ketimines; optionally substituted diazines, such as pyrazines, piperazines, and phenazines; optionally substituted diazoles, such as pyrazoles, thiadiazoles, and imidazoles, and optionally substituted pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0108] 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.

[0109] Exemplary surfactants include fluorinated and non-fluorinated surfactants and can be ionic or non-ionic, with non-ionic surfactants being preferred. Exemplary fluorinated non-ionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation, and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In some embodiments, the photoresist composition further comprises a surfactant polymer comprising a fluorine-containing repeating unit.

[0110] A method for forming a pattern is also provided. According to one aspect, the method for forming a pattern includes applying a layer of a photoresist composition to a substrate to form a photoresist composition layer, patternwise exposing the photoresist composition layer to activating radiation to form an exposed photoresist composition layer, and developing the exposed photoresist composition layer. The photoresist composition includes a polymer described herein and a solvent. In some embodiments, the polymer of the photoresist composition includes a first repeat unit derived from a first monomer represented by Formula (1). In some embodiments, the polymer of the photoresist composition includes a first repeat unit derived from the first monomer represented by Formula (1) and a second repeat unit comprising an acid labile group, a hydroxyaryl group, or a fluoroalcohol group. In yet another embodiment, the polymer of the photoresist composition includes a first repeat unit derived from a first monomer represented by Formula (1), a second repeat unit comprising an acid labile group, a hydroxyaryl group, or a fluoroalcohol group, and a third repeat unit provided herein.

[0111] 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 variety of electronic device substrates, such as semiconductor wafers, polycrystalline silicon substrates, packaging substrates such as multichip modules, flat panel display substrates, and substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), can be used in the present invention, with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), although wafers with smaller and larger diameters can be suitably used in accordance with the present invention. The substrate may include one or more layers or structures that may optionally include active or operable portions of the device to be formed.

[0112] Typically, one or more lithographic layers, such as a hard mask layer, e.g., a spin-on carbon (SOC), amorphous carbon, or metal hard mask layer, a CVD layer such as a silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer, an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of the substrate before coating the photoresist composition of the invention. Such layers, together with an overcoated photoresist layer, form a lithographic material stack.

[0113] Optionally, a layer of adhesion promoter can be applied to the substrate surface before coating with the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films can be used, such as a silane, typically an organosilane such as trimethoxyvinylsilane, triethoxyvinylsilane, or hexamethyldisilazane, or an aminosilane coupler such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names AP™ 3000, AP™ 8000, and AP™ 9000S, available from DuPont Electronics & Industrial (Marlborough, Massachusetts).

[0114] The photoresist composition can be coated onto a substrate by any suitable method, such as spin coating, spray coating, dip coating, or doctor blading. For example, application of a photoresist layer can be achieved by spin-coating the photoresist in a solvent using a coating truck, in which the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically spun at a speed of up to 4,000 revolutions per minute (rpm), e.g., 200 to 3,000 rpm, e.g., 1,000 to 2,500 rpm, for a time period of 15 to 120 seconds, resulting in a layer of photoresist composition on the substrate. Those skilled in the art will appreciate that the thickness of the coated layer can be adjusted by varying the spin speed and / or the total solids content of the composition. Photoresist composition layers formed from the compositions of the present invention typically have a dry layer thickness of 3 to 30 micrometers (μm), preferably greater than 5 to 30 μm, and more preferably 6 to 25 μm.

[0115] The photoresist composition is typically then soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. Soft-baking can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft-baking temperature and time will depend, for example, on the photoresist composition and thickness. The soft-baking temperature is typically 80 to 170°C, more typically 90 to 150°C. The soft-baking time is typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and even more typically 1 minute to 2 minutes. The heating time can be easily determined by one skilled in the art based on the components of the composition.

[0116] The photoresist layer is then patternwise exposed to activating radiation to create a solubility differential between exposed and unexposed regions. References herein to exposing a photoresist composition to radiation that activates the composition indicate that the radiation can form a latent image in the photoresist composition. Exposure is typically carried out through a patterned photomask having optically transparent and optically opaque regions corresponding to the exposed and unexposed regions of the resist layer, respectively. Alternatively, such exposure can be carried out without a photomask in a direct-write process, typically used for electron beam lithography. Activating radiation typically has a wavelength of less than 400 nm, less than 300 nm, or less than 200 nm, with 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV) wavelengths, or electron beam lithography being preferred. Preferably, the activating radiation is 248 nm radiation. This method is utilized in immersion or dry (non-immersion) lithography techniques. Exposure energies are typically between 1 and 200 millijoules per square centimeter (mJ / cm), depending on the exposure tool and the components of the photoresist composition. 2 ), preferably 10 to 100 mJ / cm 2 , more preferably 20 to 50 mJ / cm 2 is.

[0117] After the photoresist layer is exposed, a post-exposure bake (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for PEB will depend, for example, on the photoresist composition and layer thickness. PEB is typically performed at a temperature of 70-150°C, preferably 75-120°C, for 30-120 seconds. A latent image defined by polarity-switching regions (exposed regions) and non-switching regions (unexposed regions) is formed in the photoresist.

[0118] 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 a resulting photoresist pattern relief image. In a positive-tone development (PTD) process, the exposed areas of the photoresist layer are removed during development, leaving the unexposed areas. Conversely, in a negative-tone development (NTD) process, the exposed areas of the photoresist layer remain, while the unexposed areas are removed during development. Application of the developer can be accomplished by any suitable method, such as those described above with respect to application of the photoresist composition; spin coating is typical. The development time is a period effective to remove the soluble areas of the photoresist, typically between 5 and 60 seconds. Development is typically performed at room temperature.

[0119] Suitable developers for the PTD process include aqueous base developers, such as quaternary ammonium hydroxide solutions such as TMAH, preferably 0.26N TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent-based, meaning that the cumulative content of organic solvent in the developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0120] Coated substrates can be formed from the photoresist compositions of the invention. Such coated substrates include (a) a substrate having one or more layers to be patterned on its surface, and (b) a layer of a photoresist composition over the one or more layers to be patterned.

[0121] The 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.

[0122] The present invention is further illustrated by the following non-limiting examples. [Example]

[0123] Synthesis Examples The synthesis reactions were carried out under an anhydrous nitrogen atmosphere. All chemicals were used as received from commercial suppliers and without further purification. Proton nuclear magnetic resonance (NMR) of all compounds was performed. 1 H-NMR spectra were obtained on a 499 megahertz (MHz) NMR spectrometer. Chemical shifts are reported in δ (parts per million, ppm) relative to the internal standard tetramethylsilane. Multiplicities are indicated as singlet (s), doublet (d), triplet (t), multiplet (m), doublet of doublets (dd), triplet of doublets (dt), triplet of triplets (tt), or broad singlet (br).

[0124] Synthesis of intermediate I-1 [ka] A multi-necked round-bottom flask was charged with 2,6-dihydroxybenzoic acid (38.5 grams (g), 1 equivalent) and 4-pyrrolidinopyridine (1.85 g, 0.05 equivalents). The atmosphere was purged with anhydrous nitrogen, and the solid material was suspended in dichloromethane (350 milliliters (mL)). The mixture was cooled to 0°C, and cyclopentanone (27.3 g, 1.3 equivalents) and thionyl chloride (23.6 mL, 1.3 equivalents) were added sequentially to the mixture with stirring. The reaction was allowed to warm to room temperature with stirring for 5 hours (h). The reaction was quenched by pouring the contents into saturated aqueous sodium bicarbonate (1 L). The biphasic mixture was separated, and the aqueous layer was extracted with ethyl acetate (3 × 150 mL). The organic layers were combined, washed with deionized (DI) water (3 × 100 mL), dried, and concentrated under reduced pressure. The crude mixture was loaded onto a pad of silica gel, and the product was eluted with 25% v / v ethyl acetate in heptane. The filtrate was concentrated under reduced pressure to give intermediate I-1 as a colorless oil (25.2 g, 46%). 1H-NMR(δ, CDCl3)10.28ppm(s,1H),7.40ppm(t,J=8.3Hz,1H),6.63ppm(dd,J=8.5,1.0H z, 1H), 6.46ppm (dd, J=8.2, 1.0Hz, 1H), 2.23-2.11ppm (m, 4H) and 1.93-1.76ppm (m, 4H).

[0125] Synthesis of Monomer M-4 [ka] Intermediate I-1 (15.0 g, 1 equiv.) was suspended in dichloromethane (250 mL). Methacryloyl chloride (8.54 g, 1.2 equiv.) and triethylamine (10.3 g, 1.5 equiv.) were added sequentially to the reaction mixture. The reaction was stirred at room temperature for 16 h. Saturated aqueous sodium bicarbonate (100 mL) was added, and the mixture was vigorously stirred for 5 min. The biphasic mixture was separated, and the organic layer was washed with deionized water (5 × 50 mL). The organic layer was dried and concentrated under reduced pressure to give Monomer M-4 as a colorless oil (17.5 g, 89%). 1 H-NMR(δ, CDCl3)7.52ppm(t,J=8.2Hz,1H),6.91ppm(t,J=8.8Hz,1H),6.84ppm(d,J=8.1Hz,1H) ,6.39ppm(s,1H),5.78ppm(s,1H),2.24-2.10ppm(m,4H),2.09(s,3H) and 1.89-1.75ppm(m,4H).

[0126] Synthesis of intermediate I-2 [ka] A multi-necked round-bottom flask was charged with 2,6-dihydroxybenzoic acid (15.41 g, 1 equiv.) and 4-pyrrolidinopyridine (741 g, 0.05 equiv.). The atmosphere was purged with anhydrous nitrogen, and the solid material was suspended in dichloromethane (150 mL). The mixture was cooled to 0°C, and 4-methoxyacetophenone (13.5 g, 0.9 equiv.) and thionyl chloride (9.42 mL, 1.3 equiv.) were added sequentially to the reaction mixture with stirring. The reaction mixture was then allowed to warm to room temperature with stirring for 5 hours. The reaction was quenched by pouring the reaction mixture into saturated aqueous sodium bicarbonate (400 mL). The biphasic mixture was separated, and the aqueous layer was extracted with ethyl acetate (3 × 150 mL). The organic layers were combined, washed with deionized water (3 × 100 mL), diluted with heptane (2 ×), and filtered through a pad of silica gel. The filtrate was concentrated under reduced pressure, and the product was purified by flash chromatography on silica gel (gradient of 0 to 30% v / v ethyl acetate in heptane) to give intermediate I-2 (9.44 g, 35%) as a white solid. 1 H-NMR (δ, CDCl3) 10.15ppm(s,1H), 7.42-7.32ppm(m,3H), 6.82ppm(d,J=9.0Hz,2H), 6.55-6.49ppm(m,2H), 3.76ppm(s,3H) and 1.97ppm(s,3H).

[0127] Synthesis of Monomer M-5 [ka] Intermediate I-2 (9.44 g, 1 equiv.) was suspended in dichloromethane (100 mL). Methacryloyl chloride (4.18 g, 1.2 equiv.) and triethylamine (5.06 g, 1.5 equiv.) were added sequentially to the reaction mixture. The reaction mixture was stirred at room temperature for 16 h. Saturated aqueous sodium bicarbonate (100 mL) was added to the reaction mixture, and the resulting mixture was vigorously stirred for 5 min. The biphasic mixture was separated, and the organic layer was washed with deionized water (5 × 50 mL). The organic layer was filtered over a silica pad and washed with 50% v / v ethyl acetate in heptane. The filtrate was collected and concentrated under reduced pressure to give Monomer M-5 as a colorless oil (8.6 g, 85%). 1 H-NMR(δ, CDCl3)7.47ppm(t,J=8.2Hz,1H),7.38ppm(d,J=8.6Hz,2H),6.94ppm(d,J=8.4Hz,1H),6.83ppm(d,J=8.6Hz,2H) ,6.73ppm(d,J=8.1Hz,1H),6.34ppm(s,1H),5.75ppm(q,J=1.7Hz,1H),3.75ppm(s,3H),2.06ppm(s,3H) and 1.95ppm(s,3H).

[0128] Synthesis of intermediate I-3 [ka] A multi-necked round-bottom flask was charged with 2,6-dihydroxybenzoic acid (15.41 g, 1 equiv.) and 4-pyrrolidinopyridine (741 mg, 0.05 equiv.). The atmosphere was purged with anhydrous nitrogen, and the solid material was suspended in dichloromethane (150 mL). The mixture was cooled to 0 °C, and acetone (9.42 mL, 1.3 equiv.) and thionyl chloride (4.6 mL, 1.3 equiv.) were added sequentially with stirring. The reaction mixture was allowed to warm to room temperature with stirring for 5 hours. The reaction was quenched by pouring the reaction mixture into saturated aqueous sodium bicarbonate (400 mL). The resulting biphasic mixture was separated, and the aqueous layer was extracted with ethyl acetate (3 × 100 mL). The organic layers were combined, washed with deionized water (3 × 100 mL), dried, and concentrated under reduced pressure. The crude mixture was loaded onto a pad of silica gel, and the product was eluted with 25% v / v ethyl acetate in heptane. The filtrate was concentrated under reduced pressure to give intermediate I-3 as a white solid (7.5 g, 39%). 1 H-NMR (δ, CDCl3) 10.34ppm(s,1H), 7.41ppm(t,J=8.3Hz,1H), 6.63ppm(d,J=8.5Hz,1H), 6.44ppm(d,J=8.1Hz,1H) and 1.75ppm(s,6H).

[0129] Synthesis of Monomer M-6 [ka] Intermediate I-3 (7.35 g, 1 equiv.) was suspended in dichloromethane (150 mL). Methacryloyl chloride (4.75 g, 1.2 equiv.) and triethylamine (7.9 mL, 1.5 equiv.) were added sequentially to the reaction mixture. The reaction mixture was stirred at room temperature for 16 h. Deionized water (100 mL) was then added, and the resulting mixture was vigorously stirred for 5 min. The biphasic mixture was separated, and the organic layer was washed with deionized water (5 × 50 mL). The organic layer was dried and concentrated under reduced pressure to give monomer M-6 as a white solid (7.23 g, 73%). 1H-NMR(δ, CDCl3)7.53ppm(t,J=8.2Hz,1H),6.88ppm(dd,J=8.4,1.1Hz,1H),6.83ppm(dd,J=8.2,1 .0Hz,1H), 6.38ppm(s,1H), 5.78ppm(t,J=1.5Hz,1H), 2.08ppm(t,J=1.3Hz,3H) and 1.73ppm(s,6H).

[0130] Synthesis of Monomer M-7 [ka] To a mixture of intermediate I-1 (10.0 g, 1 equiv.) and 1-(chloromethyl)-4-vinylbenzene (6.26 g, 0.9 equiv.) in N,N-dimethylformamide (100 mL) was added sodium iodide (675 mg, 0.1 equiv.) and potassium carbonate (12.6 g, 2 equiv.). The reaction mixture was heated to 70 °C (external temperature) with stirring for 4 h. The reaction mixture was then cooled to room temperature and diluted with deionized water (500 mL). The resulting aqueous mixture was extracted with dichloromethane (4 × 150 mL), and the combined organic layers were washed with deionized water (5 × 100 mL), dried, and concentrated under reduced pressure over a pad of basic alumina. This material was loaded onto a pad of silica gel, and the stationary phase was washed with 10% v / v ethyl acetate in heptane. The filtrate was discarded, and the product was eluted with dichloromethane. Fractions containing pure product were isolated and concentrated under reduced pressure to give monomer M-7 as a white solid (9.8 g, 71%). 1 H-NMR(δ,acetone-d6)7.59ppm(d,J=8.0Hz,2H),7.53ppm(t,J=8.3Hz,1H),7.49ppm(d,J=8.1Hz,2H),6.89ppm(d,J=8.5Hz,1H),6.77ppm(dd,J=17.6,11.0H z,1H),6.65ppm(d,J=8.3Hz,1H),5.82ppm(d,J=17.7Hz,1H),5.26ppm(s,2H ), 5.23ppm(d,J=11.0Hz,1H), 2.14-2.06ppm(m,4H) and 1.87-1.72ppm(m,4H).

[0131] Polymer synthesis The following monomers were used to prepare polymers P-1, P-2, P-3, P-4, P-5 and CP-1. [ka]

[0132] Synthesis of polymer P-1 Polymer P-1 was prepared from monomers M-1, M-3, and M-4 in a molar feed ratio of 45 / 45 / 10. A feed solution was prepared by dissolving monomer M-1 (15.68 g, 96.8 mmol), monomer M-3 (18.59 g, 102.0 mmol), and monomer M-4 (5.76 g, 20.0 mmol) in 40 g of PGMEA. Separately, an initiator solution was prepared by dissolving 4.18 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (obtained as V-65 from Wako Pure Chemical Industries, Ltd.).

[0133] 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 reactor was charged with 20 g of PGMEA and heated to 75°C. The feed solution and initiator solution were each separately fed into the reactor over 6 hours using a syringe pump. After the addition, the contents were stirred for an additional 2 hours. The contents were then cooled to room temperature and precipitated into 1 liter (L) of heptane. The resulting product was isolated by filtration and dried overnight under reduced pressure at 35°C. The product was then dissolved in methanol (250 mL) and combined with a 30 wt% solution of sodium methoxide in methanol (0.3 g). The reaction mixture was heated at 67°C until the reaction was complete. The reaction mixture was allowed to cool to room temperature and then neutralized by the addition of acidic ion exchange resin C381H (available from Evoqua Water Technologies LLC). This reaction converts the repeating units derived from 4-acetoxystyrene (M-1) to the repeating units derived from 4-hydroxystyrene, as shown below. [ka]

[0134] Partial structure of repeating units derived from M-1 The polymer solution was precipitated in deionized water to isolate a white solid (approximately 26.3 g) (Mw = 6.5 kilodaltons (kDa), PDI = 1.53), which was further dried under vacuum at 35° C. The molecular weight was determined by gel permeation chromatography (GPC) using polystyrene standards.

[0135] Synthesis of polymers P-2, P-3, P-4, P-5 and CP-1 Each polymer in Table 1 was prepared using a procedure similar to that described above for the preparation of polymer P-1, except that the monomers and molar feed ratios listed in Table 1 were used.

[0136] [Table 1]

[0137] Lithography evaluation Formulation Information Photoresist compositions were prepared by dissolving the solid components in a solvent using the materials and amounts shown in Tables 2 and 3. Amounts are expressed in weight percent, based on 100% total weight of solids. The total solids content of the photoresist compositions was 2.5% by weight. The solvent system included PGMEA (50% by weight) and methyl-2-hydroxyisobutyrate (50% by weight). Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disk filter with a 0.2 micron pore size.

[0138] Lithographic patterning and data analysis Lithography was performed using a CLEAN TRAC ACT8 (TEL, Tokyo Electron Co.) wafer track. 200 nm wafers for photolithography testing were coated with AR™ 3 BARC (DuPont Electronics & Industrial) and soft-baked at 205°C for 60 seconds to obtain a 60 nm film. A coating of AR™ 40A BARC (DuPont Electronics & Industrial) was then placed on the AR™ 3 layer and soft-baked at 215°C for 60 seconds to form a second BARC layer with a thickness of approximately 80 nm. A photoresist composition was then coated onto the dual BARC stack and soft-baked at 110°C for 60 seconds to obtain a photoresist film layer with a thickness of approximately 70 nm.

[0139] Wafers were 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 the features described herein. The wafers were post-exposure baked at 100°C for 60 seconds, developed in MF™ CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with deionized water, and dried. Critical dimension (CD) linewidth measurements of the resulting patterns were performed using a HITACHI S-9380 CD-SEM. LWR values ​​were determined by top-down SEM using an accelerating voltage of 800 volts (V), a probe current of 8.0 picoamperes (pA), a 200Kx magnification with a digital zoom of 1.0, and a frame count setting of 64. LWR was measured in 40 nm steps over a 2 μm line length and reported as the average LWR over the measured area. Sizing Energy (E size ) and line width roughness (LWR) of the lines were determined based on CD measurements.

[0140] The pseudo-Z-factor is reported below and was determined according to Equation 1: Pseudo Z factor = (E size )×(LWR) 2 (Formula 1) (In the formula, E size is millijoules per square centimeter (mJ / cm 2 ), LWR is reported in nanometers (nm), and pseudo Z-factor is mJ×10 -11 (The pseudo-Z factor is reported in units of 1 / 2.5). The pseudo-Z factor is a modified measure of photoresist performance based on the Z factor, which is an index of a known parameter that indicates RLS (Resolution, Line Edge Roughness, Sensitivity) photoresist performance (see, for example, (Non-Patent Document 1)). The pseudo-Z factor is calculated at a constant resolution (CD size).

[0141] Line / Space (L / S) Patterning The photoresist compositions in Table 2 were evaluated for L / S patterning using bright field mask patterns under KrF exposure (248 nm) as described above. size The LWR of the space was determined based on the CD measurement. size was determined as the amount of irradiation energy required to resolve the target 120 nm L / S pattern. size , LWR and pseudo Z-factor data are shown in Table 2.

[0142] [Table 2]

[0143] The structures of PAG-1 and additive Q1 are shown below. [ka]

[0144] As can be seen in Table 2, photoresist compositions PR-1 to PR-5 achieved improved pseudo Z-factors (reduced pseudo Z-factor values) in L / S patterning under KrF exposure compared to comparative photoresist composition PR-6*.

[0145] Trench (TR) patterning The photoresist compositions in Table 3 were evaluated for TR patterning using dark field mask patterns under KrF exposure as described above. size The LWR of the space was determined based on the CD measurement. size was determined from the irradiation energy at which the target 120 nm TR pattern was resolved. size The LWR and pseudo Z-factor data are shown in Table 3. Note that photoresist compositions PR-7 to PR-11 were the same as photoresist compositions PR-1 to PR-5, and comparative photoresist composition PR-12 was the same as comparative photoresist composition PR-6.

[0146] [Table 3]

[0147] As can be seen in Table 3, photoresist compositions PR-7, PR-8, PR-10, and PR-11 achieved improved pseudo Z-factors (decreased pseudo Z-factor values) compared to comparative photoresist composition PR-12* in TR patterning under KrF exposure. Although photoresist composition PR-9 did not achieve an improved pseudo Z-factor relative to comparative photoresist composition PR-12*, photoresist composition PR-9 still exhibited superior photospeed compared to comparative photoresist composition PR-12* in TR patterning under KrF exposure.

[0148] 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) 【Chemistry 1】 a first repeat unit derived from a first monomer represented by: a second repeat unit comprising an acid labile group, a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof; A polymer comprising: In formula (1), P is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond selected from a substituted or unsubstituted norbornyl group, a substituted or unsubstituted (meth)acrylic group, a substituted or unsubstituted vinyl ether group, a substituted or unsubstituted vinyl ketone group, a substituted or unsubstituted vinyl ester group, and a substituted or unsubstituted vinyl aromatic group; L １ is a single bond or a linking group, Ar is a substituted or unsubstituted C ６～３０ Aromatic group or substituted or unsubstituted C ４～３０ is a heteroaromatic group, X is O or S; A is -O-, -S-, -S(O)-, -S(O) ２ -, -C(O)-, -C(S)- or -N(R ａ )- is a group selected from R ａ is hydrogen or a non-hydrogen substituent, R １ and R ２ are each independently hydrogen, substituted or unsubstituted C １～３０ Alkyl, substituted or unsubstituted C ３～３０ Cycloalkyl, substituted or unsubstituted C ３～３０ Heterocycloalkyl, substituted or unsubstituted C ２～３０ Alkenyl, substituted or unsubstituted C ２～３０ Alkynyl, substituted or unsubstituted C ２～３０ Heteroalkenyl, substituted or unsubstituted C ２～３０ Heteroalkynyl, substituted or unsubstituted C １ ~C ３０ Alkoxy, substituted or unsubstituted C １ ~C ３０ Alkylthio, substituted or unsubstituted C ３ ~C １０ Cycloalkenyl, substituted or unsubstituted C ３ ~C １０ Cycloalkynyl, substituted or unsubstituted C ３ ~C １０ Heterocycloalkenyl, substituted or unsubstituted C ３ ~C １０ Heterocycloalkynyl, substituted or unsubstituted C ６～５０ Aryl, substituted or unsubstituted C ７～５０ Aryl alkyl, substituted or unsubstituted C ７～５０ Alkylaryl, substituted or unsubstituted C ６～５０ Aryloxy, substituted or unsubstituted C ４～３０ Heteroaryl, substituted or unsubstituted C ５～３０ Alkylheteroaryl, substituted or unsubstituted C ５～３０ Heteroarylalkyl or substituted or unsubstituted C ３～３０ heteroaryloxy, R １ and R ２ are optionally joined together to form a substituted or unsubstituted ring, and R １ and R ２ each independently optionally further includes one or more divalent linking groups as part of its structure; The polymer, wherein the first repeat unit and the second repeat unit are structurally different.

2. The first monomer has the formula (2): 【Chemistry 2】 is represented by In formula (2), P is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond selected from a substituted or unsubstituted norbornyl group, a substituted or unsubstituted (meth)acrylic group, a substituted or unsubstituted vinyl ether group, a substituted or unsubstituted vinyl ketone group, a substituted or unsubstituted vinyl ester group, and a substituted or unsubstituted vinyl aromatic group; L ２ is a single bond or a linking group, R ４ and R ５ are each independently hydrogen, substituted or unsubstituted C １～３０ Alkyl, substituted or unsubstituted C ３～３０ Cycloalkyl, substituted or unsubstituted C ３～３０ Heterocycloalkyl, substituted or unsubstituted C ２～３０ Alkenyl, substituted or unsubstituted C ２～３０ Alkynyl, substituted or unsubstituted C ２～３０ Heteroalkenyl, substituted or unsubstituted C ２～３０ Heteroalkynyl, substituted or unsubstituted C １ ~C ３０ Alkoxy, substituted or unsubstituted C １ ~C ３０ Alkylthio, substituted or unsubstituted C ３ ~C １０ Cycloalkenyl, substituted or unsubstituted C ３ ~C １０ Cycloalkynyl, substituted or unsubstituted C ３ ~C １０ Heterocycloalkenyl, substituted or unsubstituted C ３ ~C １０ Heterocycloalkynyl, substituted or unsubstituted C ６～５０ Aryl, substituted or unsubstituted C ７～５０ Aryl alkyl, substituted or unsubstituted C ７～５０ Alkylaryl, substituted or unsubstituted C ６～５０ Aryloxy, substituted or unsubstituted C ４～３０ Heteroaryl, substituted or unsubstituted C ５～３０ Alkylheteroaryl, substituted or unsubstituted C ５～３０ Heteroarylalkyl or substituted or unsubstituted C ３～３０ heteroaryloxy, Each R ６ are independently hydroxy, cyano, halogen, substituted or unsubstituted C １～３０ Alkyl, substituted or unsubstituted C ３～３０ Cycloalkyl, substituted or unsubstituted C ３～３０ Heterocycloalkyl, substituted or unsubstituted C １ ~C ３０ Alkoxy, substituted or unsubstituted C １ ~C ３０ Alkylthio, substituted or unsubstituted C ６～５０ Aryl, substituted or unsubstituted C ７～５０ Aryl alkyl, substituted or unsubstituted C ７～５０ Alkylaryl, substituted or unsubstituted C ６～５０ Aryloxy, substituted or unsubstituted C ４～３０ Heteroaryl, substituted or unsubstituted C ５～３０ Alkylheteroaryl, substituted or unsubstituted C ５～３０ Heteroarylalkyl or substituted or unsubstituted C ３～３０ heteroaryloxy, and 2. The polymer of claim 1, wherein n2 is an integer from 0 to 3.

3. 3. The polymer of claim 1, wherein the second repeat unit comprises an acid labile group.

4. 3. The polymer of claim 1 or 2, wherein the second repeat unit comprises a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof.

5. The polymer of any one of claims 1 to 4, wherein the first monomer comprises a (meth)acrylic group or a vinyl aromatic group.

6. R １ and R ２ are linked to form a substituted or unsubstituted ring, and R ４ and R ５ are linked to form a substituted or unsubstituted ring.

7. 7. The polymer of any one of claims 1 to 6, comprising the first repeat unit in an amount of 5 mole percent to 50 mole percent, based on a total of 100 mole percent of repeat units in the polymer.

8. The polymer of claim 1 , wherein the second repeat unit comprises a hydroxyaryl group, a fluoroalcohol group, or a combination thereof.

9. A polymer according to any one of claims 1 to 8; Solvent and A photoresist composition comprising:

10. The photoresist composition of claim 9 further comprising a photoacid generator.

11. 1. A method of forming a pattern, comprising: Applying a layer of the photoresist composition of claim 9 or 10 onto a substrate to form a photoresist composition layer; patternwise exposing the photoresist composition layer to activating radiation to form an exposed photoresist composition layer; and developing the exposed photoresist composition layer. A method comprising:

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