Polymer, photoresist composition containing the same, and pattern forming method

Abstract

Provided are a polymer, a photoresist composition containing the same, and a patterning method. 【Solution means】 A polymer comprising a first repeating unit containing a sulfone group directly bonded to a group of formula -C(R a )(R b ), and a second repeating unit containing an acid labile group, a base decomposable group, a polar group, or a combination thereof, wherein R a and R b are each independently hydrogen, halogen, substituted or unsubstituted C 1~30 alkyl, substituted or unsubstituted C 3~30 cycloalkyl, substituted or unsubstituted C 3~30 heterocycloalkyl, substituted or unsubstituted C 2~30 alkenyl, substituted or unsubstituted C 3~30 cycloalkenyl, substituted or unsubstituted C 3~30 heterocycloalkenyl, substituted or unsubstituted C 6~30 aryl, substituted or unsubstituted C 7~30 arylalkyl, 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 alkylheteroaryl, provided that at least one of R a and R b is hydrogen.

Description

[Technical Field]

[0001] This invention relates to polymers for photoresist compositions and to a patterning method using such photoresist compositions. The invention finds applicability to lithography applications in the semiconductor manufacturing industry. [Background technology]

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

[0003] Traditionally, chemically amplified photoresists have been used for high-resolution processing. Such resists typically utilize polymers with acid-unstable groups, photoacid generators, and acid-deactivating materials. Pattern-like exposure to activating radiation through a photomask causes the acid generator to form acid, which, during post-exposure baking, causes cleavage of the acid-unstable groups in the exposed regions of the polymer. Acid-deactivating materials are often added to the photoresist composition to control acid diffusion into unexposed regions and improve contrast. The result of the lithography process is the creation of a difference in solubility between the exposed and unexposed regions of the resist in the developer. In a positive-type 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, insoluble in the developer, remain after development to form 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

Non-Patent Document

[0005]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Despite the evolution of resist technology, there remains a need for photoresist compositions that address one or more problems associated with the prior art. In particular, there is a continuing need for photoresist compositions having good sensitivity, including photoresist compositions capable of achieving higher contrast and low line width roughness (LWR) for line / space patterns.

Means for Solving the Problems

[0007] One aspect provides a polymer comprising a first repeating unit containing a sulfone group directly bonded to a group of formula -C(R a )(R b )-, and a second repeating unit containing an acid-labile group, a base-labile group, a polar group, or a combination thereof, wherein R a and R b are each independently hydrogen, halogen, substituted or unsubstituted C 1~30 alkyl, substituted or unsubstituted C 3~30 cycloalkyl, substituted or unsubstituted C 3~30 heterocycloalkyl, substituted or unsubstituted C 2~30 alkenyl, substituted or unsubstituted C 3~30 cycloalkenyl, substituted or unsubstituted C 3~30 heterocycloalkenyl, substituted or unsubstituted C 6~30 aryl, substituted or unsubstituted C 7~30 arylalkyl, substituted or unsubstituted C 7~30Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is an alkyl heteroaryl, but R a and R b At least one of them is hydrogen.

[0008] Also, formula -C(R a )(R b )- base (in the formula, R a and R b These are, independently, hydrogen, halogen, substituted or unsubstituted C. 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Heterocycloalkyl, substituted, or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl, but R a and R b A photoresist composition is also provided, comprising a first polymer containing a first repeating unit having a sulfone group directly bonded to (at least one of which is hydrogen), and a solvent.

[0009] Another embodiment provides a method for forming a pattern, comprising: coating a layer of photoresist composition on a substrate to form a photoresist composition layer; exposing the photoresist composition layer to a pattern with activating radiation to form an exposed photoresist composition layer; and developing the exposed photoresist composition layer.

[0010] The above and other features are illustrated by the following detailed explanation. [Modes for carrying out the invention]

[0011] Here, exemplary embodiments are described in detail, and examples of them are illustrated in this description. In this regard, these exemplary embodiments may take different forms and should not be construed as being limited to the descriptions expressed herein. Accordingly, exemplary embodiments are described below only by reference to the figures in order to illustrate the aspects of this description. As used herein, the terms “and / or” encompass any and all combinations of one or more of the enumerated items relating to them. Expressions such as “at least one” qualify the entire list of elements, but not the individual elements of the list, when preceding a list of elements.

[0012] As used herein, the terms “one (a),” “one (an),” and “it” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically indicated herein or the context clearly contradicts this. “Or” means “and / or” unless otherwise specified. The modifying phrase “about” used in relation to quantity includes the expressed value and has meaning determined by the context (e.g., including the degree of error associated with the measurement of a particular quantity). All scopes disclosed herein include endpoints, which can be independently combined with one another. The suffix “(s)” includes both singular and plural forms of the term it modifies and is intended to include at least one of those terms. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes both cases in which the event occurs and cases in which the event does not occur. The terms “first,” “second,” etc., used herein do not imply 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 an intervening element may exist between them. In contrast, when an element is said to be “directly on” another element, no intervening element exists. It should be understood that the components, elements, limitations, and / or features described in the embodiments may be combined in any preferred manner in various embodiments.

[0013] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning in relation to the relevant art and this disclosure, and it will be further understood that unless explicitly defined herein, they should not be interpreted in an ideal or overly formal sense.

[0014] As used herein, "chemical beam" or "emission" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, or particle beams such as electron beams and ion beams. Furthermore, in this invention, "light" means chemical beam or emission. 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 "excitation diplex," and "exciplex" is an abbreviation for "excitation complex." An excimer laser uses a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine) and 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 mercury lamps, excimer lasers, or other far-ultraviolet, X-ray, or extreme ultraviolet (EUV) light, but also writing using particle beams such as electron beams and ion beams.

[0015] As used herein, "organic group" refers to an organic compound or organic group having at least one carbon atom and at least one hydrogen atom. The term "alkyl" refers to a linear or branched saturated hydrocarbon group having a specified number of carbon atoms and a valency of 1; "alkylene" refers to an alkyl group with a valency of 2; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid group" refer to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group with a valency of 2; "alkenyl" refers to a linear or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group with a valency of 2; "cycloalkenyl" refers to a group having at least one carbon-carbon double bond "Aromatic group" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms; "Alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic ring system that satisfies Huckel's rule, contains carbon in the ring, and may optionally contain one or more heteroatoms selected from N, O, and S instead of carbon atoms in the ring; "Aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which all ring members are carbon and may contain an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "Arylene" refers to an aryl group having a valency 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 a compound or group contains at least one constituent atom that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) instead of a carbon atom, where each heteroatom is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent containing at least one heteroatom; "heteroalkyl group" refers to an alkyl group having 1 to 4 or more heteroatoms instead of carbon; "heterocycloalkyl group" refers to a cycloalkyl group having 1 to 4 or more heteroatoms as ring members instead of carbon; "heterocycloalkylene group" refers to a heterocycloalkyl group with a valency of 2; "heteroaryl group" refers to an aryl group having 1 to 4 or more heteroatoms as ring members instead of carbon; and "heteroarylene group" refers to a heteroaryl group with a valency of 2.

[0017] Unless explicitly specified otherwise, each of the aforementioned substituents may be optionally substituted. For example, if a group is listed without explicitly stating whether it is substituted or unsubstituted, that group includes both unsubstituted and substituted groups. The term "optionally substituted" refers to being substituted or unsubstituted.

[0018] "Substitution" means that at least one hydrogen atom in a chemical structure is substituted by another terminal substituent, typically monovalent, provided that the valence of the specified atom is not exceeded. If the substituent is oxo (i.e., =O), two geminal hydrogen atoms on the carbon atom are substituted by the terminal oxo group. Combinations of substituents or variables are permitted. Exemplary substituents that may be present at the "substituted" position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C) 1~6 ) Alkylamino, alkanoyl (acyl, etc.) 2~6 Alkanoyl groups, for example, formyl (-C(=O)H), carboxylic acids or their alkali metal salts or ammonium salts; C 2~6Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7~13 Esters such as aryl esters (-C(=O)O-aryl or -OC(=O)-aryl) (including acrylates, methacrylates, and lactones); amides (-C(=O)NR2 (wherein R is hydrogen or C 1~6 Alkyl carboxamide (-CH2C(=O)NR2 (wherein R is hydrogen or C 1~6 Alkyl, halogen, thiol (-SH), C 1~6 Alkylthio(-S-alkyl), thiocyano(-SCN), C 1~6 Alkyl, C 2~6 Alkenil, C 2~6 Alkinyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, a C2 molecule having at least one aromatic ring. 6~12 Aryl (for example, phenyl, biphenyl, or naphthyl, where each ring is either substituted or unsubstituted aromatic), C having 1 to 3 separate rings or a fused ring and 6 to 18 ring carbon atoms. 7~19 Arylalkyls, arylalkoxys having 1 to 3 separate rings or fused rings and 6 to 18 ring carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 This includes, but is not limited to, arylsulfonyls, (-S(=O)2-aryl), or tosyls (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 instead of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or a fluoro group alone may be present.

[0020] As used herein, “acid-unstable group” refers to a group whose bond cleaves upon the action of an acid, optionally and typically with heat treatment, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group, which is formed on a polymer, and the site linked to the cleaved bond is optionally and typically detached from the polymer. In another system, a nonpolymer compound may contain an acid-unstable group that can be cleaved upon the action of an acid, and a polar group such as a carboxylic acid group or an alcohol group is formed on the cleaved portion of the nonpolymer compound. Such acids are typically photocatalytic acids in which bond cleavage occurs during post-exposure baking (PEB). However, embodiments are not limited thereto, and such acids may be thermally produced, for example. Acid-unstable groups are also commonly referred to in the art as “acid-cleavable groups,” “acid-cleavable protecting groups,” “acid-unstable protecting groups,” “acid-leaving groups,” “acid-degradable groups,” and “acid-sensitive groups.”

[0021] As used herein, unless otherwise specified, "divalent linking group" refers to -O-, -S-, -Te-, -Se-, -C(O)-, -N(R b )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substitution or non-substitution 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 heteroarylenes or combinations thereof. b C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C1~20 heteroalkyl, substituted or unsubstituted C 6~30 aryl or substituted or unsubstituted C 3~30 heteroaryl. 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 one or more combinations thereof, and 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 arylalkyl, 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 alkylheteroaryl. 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 ​​C is hydrogen, substituted or unsubstituted. 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 a heteroaryl compound.

[0022] This disclosure relates to a polymer having repeating units containing a sulfone group, wherein the sulfone group is directly covalently bonded to a divalent carbon atom, which is bonded to at least one hydrogen atom. When the sulfone group is directly covalently bonded to a divalent carbon atom, the proton bonded to it becomes more acidic and more readily deprotonated in the presence of a strong base, such as tetramethylammonium hydroxide, a common developer used in lithography processes. Although not bound by any particular theory, it is believed that when used in a photoresist composition, the polymer of the present invention can reduce defects by generating more hydrophilic groups in the exposed area as a result of the reaction of the base-reactive group during the alkaline development process. Furthermore, increasing the solubility in the alkaline developer may help reduce bridge defects and / or pattern collapse.

[0023] One embodiment is given by formula -C(R a )(R b The present invention provides a polymer comprising a first repeating unit containing a sulfone group (-S(=O)2-) directly bonded to a )- group, and a second repeating unit containing an acid-unstable group, a base-degradable group, a polar group, or a combination thereof.

[0024] Formula-C(R a )(R b Under the condition of ), R a and R b These are, independently, hydrogen, halogen, substituted or unsubstituted C. 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 3~30Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl, but R a and R b At least one of them is hydrogen. Typically, R a and R b These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~24 Aryl, substituted, or unsubstituted C 7~25 Arylalkyl, substituted, or unsubstituted C 7~25 Alkylaryl, substituted, or unsubstituted C 2~20 Heteroaryl, substituted, or unsubstituted C 3~20 Heteroarylalkyl, or substituted or unsubstituted C 3~20 It may be an alkyl heteroaryl, but R a and R b At least one of them is hydrogen. Preferably, R a and R b These are, 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 C 6~24 Aryl, or substituted or unsubstituted C 2~20 It may be a heteroaryl, but Ra and R b At least one of them is hydrogen.

[0025] In some embodiments, the first repeating unit may be derived from a first monomer represented by formula (1): [ka]

[0026] In equation (1), X a X is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond. Typically, X a is a substitution or non-substitution C 2~20 The following can be selected: alkenyl groups, substituted or unsubstituted norbornyl groups, substituted or unsubstituted (meth)acrylic groups, substituted or unsubstituted vinyl ether groups, substituted or unsubstituted vinyl ketone groups, substituted or unsubstituted vinyl ester groups, or substituted or unsubstituted vinyl aromatic groups. Preferably, X a is a substitution or non-substitution C 2~20 The compounds are alkenyls, substituted or unsubstituted norbornyls, substituted or unsubstituted (meth)acrylics, or substituted or unsubstituted vinyl aromatics.

[0027] In equation (1), L 1 These are single bonds or linking groups. Typically, linking groups are -O-, -S-, -C(O)-, -C(O)O-, -N(R c )-,-C(O)N(R c )-, -S(O)-, -S(O)2-, substitution or non-substitution 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 It may contain one or more heteroarylenes or combinations thereof, R c C is hydrogen, substituted or unsubstituted. 1~30 Alkyl, substituted, or unsubstituted C 1~30Heteroalkyl, 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 may be an alkyl heteroaryl. Preferably, the linking group is -O-, -C(O)-, -C(O)O-, -N(R c )-,-C(O)N(R c )-, substitution or non-substitution 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 includes at least one heteroarylene or a combination thereof, R c C is hydrogen, substituted or unsubstituted. 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 may be an alkyl heteroaryl.

[0028] In formula (1), n is an integer from 1 to 5. Typically, n may be 1, 2, or 3. Preferably, n may be 1 or 2.

[0029] L 1 When L is a linking group, 1 L has a valence of n + 1. For example, when n is 1, L 1 is a divalent group, or when n is 2, L 1 is a trivalent group, or when n is 3, L 1 is a tetravalent group, or when n is 4, L 1 is a pentavalent group, or when n is 5, L 1 is a hexavalent group.

[0030] In formula (1), each L 2 is independently a single bond, a substituted or unsubstituted C 1~30 alkylene, or a substituted or unsubstituted C 3~30 cycloalkylene. Typically, L 2 is a single bond, a substituted or unsubstituted C 1~20 alkylene, or a substituted or unsubstituted C 3~20 cycloalkylene. Preferably, L 2 is a substituted or unsubstituted C 1~10 alkylene or a substituted or unsubstituted C 3~10 cycloalkylene.

[0031] In formula (1), L 1 and L 2 must not both be single bonds at the same time. In other words, at least one of L 1 and L 2 is not a single bond.

[0032] In formula (1), each R 1 is independently a substituted or unsubstituted C 1~30 alkyl, a substituted or unsubstituted C 3~30 cycloalkyl, a substituted or unsubstituted C3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl. Typically, each R 1 These are independently substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 They may be alkyl heteroaryls. Preferably, each R 1 These are independently substituted or unsubstituted C 1~10 Alkyl, substituted, or unsubstituted C 3~10 Cycloalkyl, substituted, or unsubstituted C 3~10 Heterocycloalkyl, substituted or unsubstituted C 6~24 Aryl, substituted, or unsubstituted C 7~25 Arylalkyl, substituted, or unsubstituted C 7~25 Alkylaryl, substituted, or unsubstituted C 2~20 Heteroaryl, substituted, or unsubstituted C 3~20 Heteroarylalkyl, or substituted or unsubstituted C 3~20 It may be an alkyl heteroaryl.

[0033] In equation (1), each R 1 Each R may independently further include a divalent linking group as part of its structure. For example, each R 1 These are independently -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R) c )-, or -C(O)N(R c )- may further include one or more groups selected from R c C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It is heterocycloalkyl.

[0034] In equation (1), at least one L 2 or at least one R 1 This is the equation -C(R) that is directly bonded to -S(=O)2-. a )(R b )- includes the base. In other words, if n is 1, L 2 and R 1 At least one of them is directly coupled to the formula -C(R) a )(R b )- Includes the base. However, if n is 2 or greater, at least one L 2 or at least one R 1 This is the equation -C(R) that is directly bonded to -S(=O)2-. a )(R b The formula -C(R) contains the base - and as a result, at least one unit represented by n is directly bonded to -S(=O)2- a )(R b )- containing the group L 2 and R 1 It must include at least one of the following, while other units represented by n do not need to satisfy this restriction. For example, at least one L 2 This is the equation -C(R) that is directly bonded to -S(=O)2-. a )(R b )- may include the group R. For example, at least one R 1 This is the equation -C(R) that is directly bonded to -S(=O)2-.a )(R b )- may contain a group. Alternatively, for example, one L 2 or one R 1 is directly bonded to -S(=O)2- and may contain a group of formula -C(R a )(R b ).

[0035] In some embodiments, when n is 1, the first repeating unit may be derived from the first monomer represented by formula (2):

Chemical formula

[0036] In formula (2), X b is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond. Typically, X b is selected from a substituted or unsubstituted C 2~20 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, X b is a substituted or unsubstituted C2- 20 alkenyl, a substituted or unsubstituted norbornyl, a substituted or unsubstituted (meth)acrylic, or a substituted or unsubstituted vinyl aromatic.

[0037] In formula (2), L 3 is a single bond or a divalent linking group. Typically, L 3 is a single bond, or -O-, -C(O)-, -C(O)O-, -N(R c ), -C(O)N(R c ), a substituted or unsubstituted C 1~10 alkylene, a substituted or unsubstituted C 3~10 cycloalkylene, a substituted or unsubstituted C 3~10 heterocycloalkylene, a substituted or unsubstituted C 6~10 arylene, a substituted or unsubstituted C 3~10A linking group comprising at least one heteroarylene or a combination thereof, R c C is hydrogen, substituted or unsubstituted. 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 may be an alkyl heteroaryl.

[0038] In equation (2), R 2 R in equation (1) 1 This is the same as defined herein, and typically R 2 is a substitution or non-substitution 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 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 may be an alkyl heteroaryl. Preferably, R 2 is a substitution or non-substitution C1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~24 Aryl, substituted, or unsubstituted C 7~25 Arylalkyl, substituted, or unsubstituted C 7~25 Alkylaryl, substituted, or unsubstituted C 2~20 Heteroaryl, substituted, or unsubstituted C 3~20 Heteroarylalkyl, or substituted or unsubstituted C 3~20 It may be an alkyl heteroaryl.

[0039] In some embodiments, R 2 It may further include a divalent linking group as part of its structure. For example, R 2 As part of its structure, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R c )-, or -C(O)N(R c )- may further include one or more groups selected from R c C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It is heterocycloalkyl.

[0040] In some embodiments, when n is 2, the first repeating unit may be derived from a first monomer represented by formula (3): [ka]

[0041] In equation (3), X c X is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond. Typically, X c is a substitution or non-substitution C 2~20The following can be selected: alkenyl groups, substituted or unsubstituted norbornyl groups, substituted or unsubstituted (meth)acrylic groups, substituted or unsubstituted vinyl ether groups, substituted or unsubstituted vinyl ketone groups, substituted or unsubstituted vinyl ester groups, or substituted or unsubstituted vinyl aromatic groups. Preferably, X c is either substituted or unsubstituted C2~ 20 The compounds are alkenyls, substituted or unsubstituted norbornyls, substituted or unsubstituted (meth)acrylics, or substituted or unsubstituted vinyl aromatics.

[0042] In equation (3), L 4 It is a single bond or a divalent linking group. Typically, L 4 It is either a single bond or -O-, -C(O)-, -C(O)O-, -N(R c )-,-C(O)N(R c )-, substitution or non-substitution 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 A linking group comprising at least one heteroarylene or a combination thereof, R c C is hydrogen, substituted or unsubstituted. 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 may be an alkyl heteroaryl.

[0043] In equation (3), R 3 and R 4 Each of them is independent of R 1 This is the same as defined herein. Typically, R 3 and R 4 These are, independently, substitutional or non-substitutional 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 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 may be an alkyl heteroaryl. Preferably, R 3 and R 4 These are, independently, substitutional or non-substitutional C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~24 Aryl, substituted, or unsubstituted C 7~25 Arylalkyl, substituted, or unsubstituted C 7~25 Alkylaryl, substituted, or unsubstituted C 2~20 Heteroaryl, substituted, or unsubstituted C 3~20 Heteroarylalkyl, or substituted or unsubstituted C 3~20 It may be an alkyl heteroaryl.

[0044] In some embodiments, R 3 and / or R 4It may further include a divalent linking group as part of its structure. For example, R 3 and / or R 4 These, independently, as part of their structure, are -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R c )-, or -C(O)N(R c )- may further include one or more groups selected from R c C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It is heterocycloalkyl.

[0045] In some embodiments, the first repeating unit may be derived from a first monomer containing a (meth)acryloyl group or a vinyl aromatic group. In other words, in some embodiments, polymerizable group X a , X b , and / or X c This may be a (meth)acrylic group or a vinyl aromatic group.

[0046] For example, in some embodiments, the first repeating unit may be derived from a first monomer selected from one or more of formulas (4) to (7): [ka]

[0047] In equations (4) to (7), each R j These are, independently, hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl, or substituted or unsubstituted C 1~10 It is a fluoroalkyl group. Preferably, R j C is hydrogen or substituted or unsubstituted C 1~5 Alkyl, typically methyl. 5 ~R 9 These are, independently, substitutional or non-substitutional C. 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl. Preferably, R 5 ~R 9 These are, independently, substitutional or non-substitutional C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~24 Aryl, substituted, or unsubstituted C 7~25 Arylalkyl, substituted, or unsubstituted C 7~25 Alkylaryl, substituted, or unsubstituted C 2~20 Heteroaryl, substituted, or unsubstituted C 3~20 Heteroarylalkyl, or substituted or unsubstituted C 3~20 It may be an alkyl heteroaryl.

[0048] In equations (4) to (7), R 5 ~R 9 It may further include a divalent linking group as part of its structure. For example, R 5 ~R 9 These are, independently, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, and -N(R) as part of their structure. c )-, or -C(O)N(R c )- may contain one or more groups selected from R c C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C3~20 It is a heterocycloalkyl.

[0049] Non-limiting examples of the first monomer can include one or more of the following:

Chem.

Chem.

Chem.

Chem.

[0053] The second repeating unit of the polymer may contain an acid-unstable group derived from one or more monomers of formulas (8), (9), (10), (11), and / or (12): [ka]

[0054] In equations (8) to (12), each R d These are, independently, hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl, or substituted or unsubstituted C 1~10 It is a fluoroalkyl group. Preferably, R d This is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It is alkyl, and typically methyl.

[0055] In equation (8), L 5 L is a divalent linking group. For example, L 5This may be a divalent linkage group comprising at least one carbon atom, at least one heteroatom, or a combination thereof. For example, L 5 L may contain 1 to 10 carbon atoms and at least 1 heteroatom. In one or more embodiments, L 5 is -OCH2-, -OCH2CH2O-, or -N(R c )- may be R c C is hydrogen, substituted or unsubstituted. 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 a heteroaryl compound.

[0056] In equations (8), (9), and (11), R 10 ~R 12 These are, 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 It may be a heteroaryl, but R 10 ~R 12 Only one of them may be hydrogen, R 10 ~R 12 If one of them is hydrogen, then R 10 ~R 12 One or both of the other C are substituted or unsubstituted. 6~20 Aryl or substituted or unsubstituted C 4~20 It is required that it be a heteroaryl compound. Preferably, R 10 ~R 12 These are, independently, substitutional or non-substitutional C. 1~6 Alkyl, substituted, or unsubstituted C 3~10 It is a cycloalkyl group.

[0057] In equation (8), R 10 ~R 12 Any two of them can optionally form a ring together, R 10 ~R 12 Each of them, as part of its structure, is -O-, -C(O)-, -N(R c It may optionally contain one or more groups selected from -, -S-, or -S(O)2-, R c C is hydrogen, straight chain or branched. 1~20 Alkyl, monocyclic, or polycyclic C 3~20 Cycloalkyl, or monocyclic or polycyclic C 1~20 It may be a heterocycloalkyl. For example, R 10 ~R 12 One or more of the following are independent of the formula -CH2C(=O)CH (3-n) Y n It may be a base of, where each Y is independently a substituted or unsubstituted C 1~30 It is a heterocycloalkyl group where n is 1 or 2. For example, each Y independently represents the formula -O(C a1 )(C a2 ) Substituted or unsubstituted C containing an O- group 1~30 It may be a heterocycloalkyl, C a1 and C a2 Each of these is independently hydrogen or substituted or unsubstituted C 1~10 It is alkyl, C a1 and C a2 They optionally form a ring together.

[0058] In equations (10) and (12), R 13 and R 14 These are, 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 6~20 Aryl, or substituted or unsubstituted C 2~20 It may be a heteroaryl, R 15is a substitution or non-substitution C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 1~30 It may be a heterocycloalkyl group. Optionally, R 13 or R 14 One of them is R 15 It forms a heterocycle together with R. Preferably, 13 and R 14 These are, 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 equations (11) and (12), each X d L is independently a polymerizable group selected from vinyl and norbornyl. 5 and L 6 Each of these is independently a single bond or a divalent linking group, but X d If it is vinyl, L 5 and L 6 It does not have to be a single bond. Preferably, L 5 and L 6 These are, independently, substitutional or non-substitutional C. 6~30 Arylene or substituted or unsubstituted C 3~30 It is a cycloalkylene.

[0060] In equations (11) and (12), n1 and n2 may be 0 or 1 independently. If n1 or n2 is 0, the corresponding L 5 or L 6 Please understand that the base is directly bonded to each oxygen atom.

[0061] Non-limiting examples of monomers for obtaining a second repeating unit containing an acid-unstable group include the following: [ka] [ka] [ka] (In these formulas, R d C is hydrogen, halogen, substituted or unsubstituted C 1~6 Alkyl, substituted, or unsubstituted C 3~6 (It is cycloalkyl.)

[0062] The second repeating unit may include a base-degrading group. Examples of base-degrading groups include a hydroxyaryl group, a fluoroalcohol group (e.g., -C(CF3)2OH), a sulfonamide group (e.g., -NHSO2CF3), or a combination thereof.

[0063] As used herein, “hydroxyaryl group” means an aryl group in which hydroxyl is directly bonded to a carbon atom of an aromatic ring. “Hydroxy” is understood to mean having one or more hydroxyl groups incorporated into the group. For example, C 6~12 When a hydroxyaryl group is indicated, that hydroxyaryl group may contain one or more hydroxyl groups, such as a single hydroxyl group, two hydroxyl groups, or three or more hydroxyl groups.

[0064] The second repeating unit may contain a polar group. Examples of polar groups include lactone groups, sultone groups, hydroxyaryl groups, hydroxyalkyl groups, or combinations thereof. It should be understood that some groups, such as hydroxyaryl groups, may be considered both basophilic and polar. In other words, some basophilic groups may also be polar.

[0065] For example, the second repeating unit may include repeating units of formulas (13), (14), or combinations thereof: [ka]

[0066] In equations (13) and (14), each R d This is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R d This is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically hydrogen or methyl.

[0067] In equations (13) and (14), L 7 and L 8 Each of these may independently be a single bond or one or more divalent linking groups. For example, L 7 and L 8 These are, independently, -O-, -C(O)-, -C(O)O-, and -N(R b )-,-C(O)N(R c )-, substitution or non-substitution 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 Heteroarylenes, or combinations thereof, R c C is hydrogen, substituted or unsubstituted. 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 may be an alkyl heteroaryl. In some embodiments, L 7 and L8 Each of these is 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 heteroarylenes or combinations thereof.

[0068] In equation (13), R 16 is a substitution or non-substitution C 1~100 or C 1~20 Alkyl, typically C 1~12 Alkyl, substituted, or unsubstituted C 3~30 or C 3~20 Cycloalkyl; substituted or unsubstituted poly(C) 1~3 Alkylene oxides); or monocyclic, polycyclic, or condensed polycyclic C 4~20 It may be a lactone-containing group. Substituting C 1~100 or C 1~20 Alkyl, substituted C 3~30 or C 3~20 Cycloalkyl and substituted poly(C) 1~3 Alkylene oxides are substituted with one or more of the following groups: sulfonamide group (e.g., -NHSO2CF3), hydroxyl group (-OH), or fluoroalcohol group (e.g., -C(CF3)2OH).

[0069] In equation (14), Ar 1 This is a substituted carbon atom that optionally contains one or more aromatic ring heteroatoms selected from N, O, S, or combinations thereof. 5~60 The aromatic group may be monocyclic, non-condensed polycyclic, or condensed polycyclic. 5~60 When the aromatic group is polycyclic, the ring or ring group may be condensed (e.g., naphthyl), uncondensed, or a combination thereof. Polycyclic C 5~60When the aromatic group is uncondensed, the ring or ring group can be directly linked (e.g., biaryl or biphenyl) or bridged by a heteroatom (e.g., triphenylamino or diphenylene ether). In some embodiments, polycyclic C 5~60 Aromatic groups can include combinations of fused rings and directly bonded rings (such as binaphthyl rings).

[0070] In equation (14), y may be an integer between 1 and 12, preferably between 1 and 6, typically between 1 and 3. Each R x R may be independently hydrogen or methyl, but at least one R x It is hydrogen.

[0071] Non-limiting examples of the second repeating unit of a polymer include the following: [ka] [ka] (In the formula, R d C is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 (May be alkyl). Preferably, R d This is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl, may be used.

[0072] The second repeating unit, if present, is incorporated into the polymer in amounts typically 20–80 mol%, more typically 25–75 mol%, and even more typically 30–70 mol%, relative to the total repeating units of the polymer.

[0073] It should be understood that the first and second repeating units are structurally different within the polymer.

[0074] In one embodiment, the polymer may further include a third repeating unit that is different from the first and second repeating units.

[0075] In one or more embodiments, the third repeating unit may include a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof.

[0076] If present, the polymer contains a third repeating unit in an amount of 10–60 mol%, typically 10–50 mol%, and more typically 10–40 mol%, relative to the total repeating units of the polymer.

[0077] In some embodiments, the polymer may optionally further contain one or more additional repeating units. These additional repeating units may be, for example, one or more additional units for the purpose of modifying the properties of the photoresist composition. Exemplary additional units may include those derived from one or more (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. If one or more additional repeating units are present in the polymer, the additional repeating units may be used in an amount of 90 mol% or less, typically 3 to 50 mol%, based on the total repeating units of the polymer.

[0078] Examples of non-limiting exemplary polymers of the present invention include the following: [ka] (In the formula, a, b, and c each represent the mole percent of repeating units based on 100 mole percent of the total repeating units in the polymer.)

[0079] The polymer typically has a weight-average molecular weight (M) of 1,000 to 50,000 Datons (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 polymer has a PDI of typically 1.1–3, and more typically 1.1–2. The molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.

[0080] Polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein may be combined using a suitable solvent and initiator, or supplied separately, and polymerized in a reactor. For example, polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays of an effective wavelength, or a combination thereof.

[0081] Photoresist compositions comprising the polymers and solvents described herein are also provided. For example, a photoresist composition may comprise a first polymer which is a polymer described herein, and may further comprise a second (different) polymer which is structurally different from the first polymer.

[0082] The second polymer comprises one or more repeating units described herein, such as those derived from one or more of (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. For example, the second polymer may comprise repeating units containing acid-unstable groups, hydroxyaryl groups, fluoroalcohol groups, sulfonamide groups, lactone groups, or combinations thereof.

[0083] M of the second polymer w Typically, this ranges from 1,000 to 50,000 Da, more specifically 2,000 to 30,000 Da, more specifically 3,000 to 20,000 Da, and even more specifically 3,000 to 10,000 Da. w M n The PDI of the polymer, which is the ratio to , is typically 1.1–3, more specifically 1.1–2. The molecular weight is determined by GPC using polystyrene standards.

[0084] The second polymer can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein may be combined using a suitable solvent and initiator, or supplied separately, and polymerized in a reactor. For example, the second polymer can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with a chemical beam at an effective wavelength, or a combination thereof.

[0085] If the photoresist composition contains both the first polymer and the second polymer, they may be included in a weight ratio of 1:4 to 4:1, for example, 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1.

[0086] A photoresist composition contains a solvent to dissolve the components of the composition and to 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- These solvents include esters such as butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (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. Of 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 40–99 weight percent (wt%), more typically 70–99 wt%, and even more typically 85–99 wt%, based on the total weight of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the photoresist layer to be coated and the coating conditions.

[0087] In a photoresist composition, the polymer is typically present in an amount of 10–99.9% by weight, typically 25–99% by weight, and more typically 50–95% by weight, based on the total solids content of the photoresist composition. The total solids content will be understood to include the polymer, PAG, and other non-solvent components.

[0088] The photoresist composition may further contain a photoacid generator (PAG). The PAG may be ionic or nonionic. The PAG may be in polymer or nonpolymer form. In polymer form, the PAG may exist as a moiety in repeating units of a polymer derived from polymerizable PAG monomers.

[0089] A suitable PAG compound is, formula G + A - It may be of the same type as G + A is a photoactive cation, - This is an anion capable of generating a photoacid. The photoactive cation is preferably selected from onium cations, preferably iodonium cations, or sulfonium cations. Particularly suitable anions include those whose conjugate acid has 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 sulfonamide, sulfonimidate, methide, or borate).

[0090] In some embodiments, the photoactive cation may be a sulfonium cation or an iodonium cation. For example, the photoactive cation may be a sulfonium cation of formula (15) or an iodonium cation of formula (16): [ka]

[0091] In equations (15) and (16), R 17 ~R 21 These are, independently, substitutional or non-substitutional 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 Arylalkyl, or substituted or unsubstituted C 4~20 This may be a heteroarylalkyl group or a combination thereof. Each R 17 ~R 19 These may be individual, or they may be connected to another group R via a single bond or a divalent linking group. 17 ~R 19 It can be connected to form a ring. 20 and R 21 These may be individual or may be linked to each other via single bonds or divalent linking groups to form a ring. 17 ~R 21 Each R may optionally include a divalent linking group as part of its structure. 17 ~R 21 This can independently contain, optionally, an acid-unstable group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group.

[0092] The exemplary sulfonium cations of formula (15) may include one or more of the following: [ka] [ka]

[0093] The exemplary iodonium cations in formula (16) may include one or more of the following: [ka]

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

[0095] Exemplary nonsulfonated anions may include one or more of the following: [ka]

[0096] Commonly used onium salts include, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Other useful PAG compounds known in the field of chemically amplified photoresists include, for example, nonionic sulfonyl compounds such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; and diazomethane derivatives such as bis(benzenesulfonyl)diazomethane and bis(p-toluenesulfonyl) Examples include diazomethane; glyoxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinidomethanesulfonic acid and N-hydroxysuccinidomitetrifluoromethanesulfonic acid; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Suitable photoacid generators are described in detail in (Patent Document 1) and (Patent Document 2).

[0097] In some embodiments, the first polymer may optionally further include repeating units containing PAG moieties, for example, repeating units derived from one or more monomers of formula (8): [ka]

[0098] In equation (8), R m C is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R m This is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl. Q 1 Q may be a single bond or a divalent linking group. Preferably, 1 It may contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0099] In equation (8), A 1 is a substitution or non-substitution 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 It may be one or more heteroarylenes. Preferably, A 1 This is a divalent C that is optionally substituted. 1~30 It may be a perfluoroalkylene group.

[0100] In equation (8), Z - This is the anionic moiety, and its conjugate acid typically has a pKa of -15 to 1. - The anionic moiety may be a sulfonate, carboxylate, sulfonamide anion, sulfonimide anion, or methide anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonates and fluorinated sulfonimides.

[0101] In equation (8), G + is an organic cation as defined above. In some embodiments, G +This refers to 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.

[0102] Examples of monomers for formula (8) include the following: [ka] (In the formula, G + (It is an organic cation).

[0103] The polymer may contain repeating units containing PAG moieties in amounts of 1 to 15 mol%, typically 1 to 8 mol%, and more typically 2 to 6 mol%, relative to the total repeating units in the polymer.

[0104] Typically, when a photoresist composition contains non-polymeric PAGs, the PAGs are present in the photoresist composition in an amount of 0.1 to 55% by weight, more typically 1 to 25% by weight, based on the total solids content of the photoresist composition. When present in polymeric form, the PAGs are typically present in the polymer in an amount of 1 to 25 mol%, more typically 1 to 8 mol%, or 2 to 6 mol%, based on the total repeating units in the polymer.

[0105] In some embodiments, the anions and / or cations of PAG do not contain, or are absent from, -F, -CF3, or -CF2- groups. “Absent from -F, -CF3, or -CF2- groups” should be understood as meaning that groups such as -CH2CF3 and -CH2CF2CH3 are excluded from the anions and / or cations of PAG. In yet another embodiment, the anions and / or cations of PAG are fluorine-free (i.e., they do not contain fluorine atoms and are not substituted with fluorine-containing groups). In some embodiments, the photoacid generator is fluorine-free (i.e., both the photoactive cation and anion are fluorine-free).

[0106] In some embodiments, the photoresist composition may further include a substance containing one or more base-unstable groups ("base-unstable substance"). As referred to herein, a base-unstable 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 baking steps to provide polar groups such as hydroxyl, carboxylic acid, sulfonic acid, etc. The base-unstable group will not react significantly (e.g., not undergo bond cleavage) before the development step of the photoresist composition containing the base-unstable group. Therefore, for example, the base-unstable 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-unstable group (or site) decomposes, cleaves, or reacts during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-unstable group reacts under typical photoresist development conditions using an aqueous alkaline photoresist developer, such as an aqueous solution of 0.26 N (N) tetramethylammonium hydroxide (TMAH). For example, a 0.26N TMAH aqueous solution can be used for single-paddle development or dynamic development, and the 0.26N TMAH developer is distributed to the imaged photoresist layer for an appropriate time, such as 10 to 120 seconds (s). Exemplary base-unstable groups are ester groups, typically fluorinated ester groups. Preferably, the base-unstable substance is substantially miscible with the polymer and other solid components of the photoresist composition and has a lower surface energy than them. When coated onto a substrate, the base-unstable substance can thereby be separated from the other solid components of the photoresist composition to the upper surface of the formed photoresist layer.

[0107] In some embodiments, the base-unstable material may be a polymeric material, also referred to herein as a base-unstable polymer, and the base-unstable polymer may comprise one or more repeating units containing one or more base-unstable groups. For example, the base-unstable polymer may comprise repeating units containing two or more identical or different base-unstable groups. A preferred base-unstable polymer comprises at least one repeating unit containing two or more base-unstable groups, for example, a repeating unit containing two or three base-unstable groups.

[0108] Base-unstable polymers can be prepared using any suitable method in the art. For example, base-unstable polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays at an effective wavelength, or a combination thereof. In addition or alternatively, one or more base-unstable groups can be grafted onto the polymer's main chain using a suitable method.

[0109] In some embodiments, the base-unstable substance is a single molecule comprising one or more base-unstable ester groups, preferably one or more fluorinated ester groups. The base-unstable substance, being a single molecule, typically has a molecular weight in the range of 50 to 1,500 Da.

[0110] If present, the base-unstable substance is typically present in the photoresist composition in an amount of 0.01 to 10% by weight, and typically 1 to 5% by weight, based on the total solid content of the photoresist composition.

[0111] In addition to or instead of the base-unstable polymers, the photoresist composition may further include one or more polymers different from those described above. For example, the photoresist composition may include additional polymers, such as those described above but with different compositions. In addition or instead, one or more additional polymers may be selected from those well known in photoresist technology, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene polymers, polyvinyl alcohols, or combinations thereof.

[0112] The photoresist composition may further contain one or more additional optional additives. For example, optional additives may include chemical dyes and contrast agents, striation inhibitors, plasticizers, rate accelerators, sensitizers, photodegradable deactivators (PDQ) (also known as photodegradable bases), basic deactivators, thermoacid generators, surfactants, etc., or combinations thereof. If present, the optional additives are typically present in the photoresist composition in an amount of 0.01 to 10% by weight based on the total solids content of the photoresist composition.

[0113] PDQ generates a weak acid when irradiated. The acid generated from the photodegradable inactivator is not strong enough to react rapidly with acid-unstable groups present in the resist matrix. Exemplary photodegradable inactivators include, for example, photodegradable cations, preferably, for example, C 1~20 Carboxylic acid or C 1~20 This includes compounds useful for preparing strong acid-generating compounds paired with anions of weak acids (pKa>1), such as sulfonic acid anions. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In preferred embodiments, the photodegradable deactivator is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0114] PDQ may be in a non-polymeric or polymer-bound form. Polymer units containing the photodegradable deactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0115] Examples of basic deactivators include linear 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-diyrbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol and 2,2',2''-nitrilotriethanol; 1-(tert- Cyclic aliphatic amines such as butoxycarbonyl)-4-hydroxypiperidine, tert-butyl1-pyrrolidinecarboxylate, tert-butyl2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate and N-(2-acetoxyethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3Examples include linear and cyclic amides and their derivatives such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl1,3-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; diazines such as optionally substituted pyrazines, piperazines, and phenazines; diazoles such as optionally substituted pyrazoles, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0116] The basic deactivator may be in a non-polymeric or polymer-bound form. If in a polymeric form, the deactivator may be present within the repeating units of the polymer. Repeating units containing the deactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, relative to the total repeating units of the polymer.

[0117] Exemplary surfactants include fluorinated and non-fluorinated surfactants, which may be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656 and PF-6520 fluorosurfactants from Omnova. In some embodiments, the photoresist composition further comprises a surfactant polymer containing fluorine-containing repeating units.

[0118] Methods for forming patterns are also provided. In one embodiment, the method for forming a pattern includes: coating a layer of photoresist composition onto a substrate to form a photoresist composition layer; exposing the photoresist composition layer to activating radiation in a patterned manner to form an exposed photoresist composition layer; and developing the exposed photoresist composition layer. The photoresist composition comprises a polymer and a solvent as described herein. In some embodiments, the polymer of the photoresist composition comprises a first repeating unit derived from a first monomer represented by formula (1). In some embodiments, the polymer of the photoresist composition comprises a first repeating unit derived from a first monomer represented by formula (1) and a second repeating unit comprising an acid-unstable group, a hydroxyaryl group, or a fluoroalcohol group. In yet another embodiment, the polymer of the photoresist composition comprises a first repeating unit derived from a first monomer represented by formula (1), a second repeating unit comprising an acid-unstable group, a hydroxyaryl group, or a fluoroalcohol group, and a third repeating unit as provided herein.

[0119] Patterning using the photoresist composition of the present invention will now be described. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates, such as semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multi-chip modules; flat panel display substrates; substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), 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 may 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 may be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), but wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that optionally contain the active or operable portion of the device to be formed.

[0120] Typically, one or more lithography layers, such as a hard mask layer (e.g., spin-on carbon (SOC), amorphous carbon, or metallic hard mask layer), a CVD layer (e.g., 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 with the photoresist composition of the present invention. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0121] Optionally, a layer of adhesion promoter may be applied to the substrate surface before coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, and hexamethyldisilazane, or aminosilane couplers such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from DuPont Electronics & Industrial (Marlborough, Massachusetts) under the names AP® 3000, AP® 8000, and AP® 9000S.

[0122] 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, the application of a photoresist layer can be achieved by spin coating the photoresist in a solvent using a coating track, in which case the photoresist is distributed onto a rotating wafer. During distribution, the wafer is typically rotated for 15 to 120 seconds 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, to obtain a layer of the photoresist composition on the substrate. It will be well understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and / or the total solid content of the composition. The photoresist composition layer formed from the composition of the present invention typically has a dry layer thickness of 3 to 30 micrometers (μm), preferably more than 5 to 30 μm, and more preferably 6 to 25 μm.

[0123] Photoresist compositions are typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The temperature and time of soft baking will depend, for example, on the photoresist composition and thickness. Soft baking temperatures are typically 80–170°C, more typically 90–150°C. Soft baking times are typically 10 seconds–20 minutes, more typically 1 minute–10 minutes, and even more typically 1 minute–2 minutes. The heating time can be easily determined by those skilled in the art based on the composition's components.

[0124] The photoresist layer is then pattern-exposed to activation radiation to create a difference in solubility between exposed and unexposed areas. The herein reference to exposure of a photoresist composition to radiation that activates the composition indicates that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions, respectively, corresponding to the exposed and unexposed regions of the resist layer. Such exposure can instead be performed without a photomask in a direct writing method, typically used for electron beam lithography. The activation radiation typically has a wavelength of less than 400 nanometers (nm), less than 300 nm, or less than 200 nm, with wavelengths of 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV), or electron beam lithography being preferred. Preferably, the activation radiation is 248 nm. This method is utilized in immersion or dry (non-immersion) lithography techniques. The exposure energy depends on the components of the exposure tool and photoresist composition, and is typically 1 to 200 millijoules (mJ / cm²) per square centimeter. 2 ), preferably 10 to 100 mJ / cm² 2 More preferably 20-50 mJ / cm² 2 That is the case.

[0125] After exposure of the photoresist layer, post-exposure baking (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 to 150°C, preferably 75 to 120°C, and for 30 to 120 seconds. A latent image is formed in the photoresist, defined by polarity switching regions (exposed regions) and non-switching regions (unexposed regions).

[0126] The exposed photoresist layer is then developed with a developer suitable for selectively removing the soluble regions of the layer, while the remaining insoluble regions form the resulting photoresist pattern relief image. In a positive development (PTD) process, the exposed regions of the photoresist layer are removed during development, leaving the unexposed regions. Conversely, in a negative development (NTD) process, the exposed regions of the photoresist layer remain, and the unexposed regions are removed during development. The application of the developer can be achieved by any preferred method as described above for the application of the photoresist composition, with spin coating being a typical example. The development time is an effective period for removing the soluble regions of the photoresist, typically ranging from 5 to 60 seconds. Development is typically carried out at room temperature.

[0127] Suitable developers for the PTD process include aqueous base developers, such as quaternary ammonium hydroxide solutions like 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 systems, meaning that the cumulative content of organic solvents 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.

[0128] A coated substrate may be formed from the photoresist composition of the present invention. Such a coated substrate comprises (a) a substrate having one or more layers patterned on its surface; and (b) a layer of the photoresist composition on one or more patterned layers.

[0129] A photoresist pattern can be used, for example, as an etching mask, thereby enabling the transfer of the pattern to one or more consecutive underlying layers by known etching techniques, typically dry etching such as reactive ion etching. A photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, which in turn can be used as an etching 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, photoresist compositions can be used to manufacture semiconductor devices and other electronic devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, etc.

[0130] The present invention is further illustrated by the following non-limiting embodiments. [Examples]

[0131] Synthesis Examples The synthesis reaction was carried out in an anhydrous nitrogen atmosphere. All chemicals were used as received from commercial suppliers and without further purification. Proton nuclear magnetic resonance ( 1 The 1H-NMR spectrum was obtained using a 499 megahertz (MHz) NMR spectrometer. Chemical shifts are reported in δ (parts per million, ppm) relative to the internal standard tetramethylsilane or deuterated peak. Multiplicity is indicated as singlet (s), doublet (d), triplet (t), multiplet (m), doublet-doublet (dd), triplet-doublet (dt), triplet-triplet (tt), or broad singlet (br).

[0132] Synthesis of monomer MS1 [ka] To a solution of 4-vinylbenzoic acid (8.0 g, 54.0 mmol) in tetrahydrofuran (THF, 100 mL), 1,1'-carbonyldiimidazole (CDI) (8.75 g, 54.0 mmol) was gradually added. The resulting reaction mixture was stirred at room temperature for 15 minutes. The temperature of the reaction mixture was then raised to 60°C, and 2-(phenylsulfonyl)ethane-1-ol (10.0 g, 53.70 mmol) was added. The resulting mixture was heated at 60°C for 16 hours. The reaction mixture was then allowed to cool to room temperature. The solvent was removed under reduced pressure to obtain the crude product as an oily residue. The crude product was dissolved in dichloromethane (150 mL), and the solution was washed twice with aqueous ammonium chloride solution (30 mL, saturated solution), followed by two washes with deionized (DI) water (30 mL). The organic phase was separated, and the solvent was removed under reduced pressure to obtain MS1 ​​as a white solid. Yield: 12.8 g (75.3%). 1H NMR(δ,acetone-d6):8.02 ppm(d,2H,3ArH),7.73 ppm(m,3H,3ArH),7.63 ppm(m,2H,2ArH),7.53 ppm(d,2H,2ArH),6.84 ppm(m,1H,CH=CH2),5.92 ppm(d,1H,CH=CH2), 5.43 ppm(d,1H,CH=CH2), 4.68 ppm(t,2H,CH2O), and 3.83 ppm(t,2H,CH2SO2).

[0133] Synthesis of monomer MS2 [ka] To a solution of 4-vinylbenzoic acid (10.0 g, 67.5 mmol) in THF (100 mL), 1,1'-carbonyldiimidazole (CDI) (11.0 g, 67.8 mmol) was gradually added. The resulting mixture was stirred at room temperature for 15 hours. The temperature of the reaction mixture was then raised to 60°C, and 2-(methylsulfonyl)ethane-1-ol (8.4 g, 69.13 mmol) was added. The resulting mixture was stirred and heated at 60°C for 16 hours. The reaction mixture was then allowed to cool to room temperature. The solvent was removed under reduced pressure to obtain the crude product as an oily residue. The crude product was dissolved in dichloromethane (150 mL), and the solution was washed twice with aqueous ammonium chloride solution (30 mL, saturated solution), followed by two washes with deionized (DI) water (30 mL). The organic phase was separated, and the solvent was removed under reduced pressure to obtain MS2 as a white solid. Yield: 15.85g (92.3%). 1 H NMR(δ,acetone-d6):8.03 ppm(d,2H,3ArH),7.62 ppm(d,2H,2ArH),6.84 ppm(m,1H,CH=CH2),5.99 ppm(d,1H,CH=CH2),5.44 ppm(d,1H,CH=CH2),4.76 ppm(t,2H,CH2O), 3.65 ppm(t,2H,CH2SO2), and 3.1 ppm(s,3h SO2CH3).

[0134] Synthesis of monomer MS3 [ka] To a methanol (150 mL) solution of potassium hydroxide (8.36 g, 149.3 mmol), 2-propanethol (12.5 mL, 134.6 mmol) was slowly added. After reacting for 30 minutes, 1,3-dichloropropan-2-ol (7.53 g, 58.4 mmol) was added dropwise, and the reaction mixture was stirred at room temperature for 16 hours. The intermediate product MS3-i was isolated by extraction from water using methyl t-butyl ether, followed by washing with a dilute potassium hydroxide aqueous solution and then brine. The resulting intermediate product was dried under vacuum to obtain a clear oil. Yield: 11.71 g (96%).

[0135] Intermediate product MS3-i (11.1 g, 53.3 mmol) and triethylamine (TEA, 20 mL, 143.5 mmol) were mixed with 150 mL of methyl t-butyl ether to obtain a solution. Methacryloyl chloride (7 mL, 71.7 mmol) was added dropwise to this solution while stirring at room temperature, and the reaction mixture was then stirred for a further 4 hours. Intermediate product MS3-ii was isolated by extraction using methyl t-butyl ether and water. The obtained product was washed twice with dilute hydrochloric acid aqueous solution, once with dilute potassium hydroxide aqueous solution, and then once with brine aqueous solution. The obtained product was dried under reduced pressure to obtain intermediate product MS3-ii as a clear oil. Yield: 11.60 g (79%).

[0136] The intermediate product MS3-ii (11.23 g, 40.6 mmol) was dissolved in a mixture of methanol (250 mL) and deionized water (250 mL). Oxone (60 g, 97.5 mmol) was added to this mixture in five separate additions, and the resulting reaction mixture was stirred at room temperature for a further 1 hour. The crude product was isolated by extraction using methyl t-butyl ether and water. The product was further purified by crystallization from the minimum amount of heptane to obtain MS3 as a waxy solid. Yield: 5.37 g (39%). 1H-NMR(δ,acetone-d6):6.18 ppm(d,1H,CH=CHH),5.83 ppm(tt,1H,OCH),5.72 ppm(p,1H,CH=CHH),3.73 ppm(qd,4H,SO2CH2),3.32 ppm(p,2H,SO2CH),1.95 ppm(s,3H,CCH3), and 1.37 ppm(dd,12H,CHCH3).

[0137] Synthesis of monomer MS4 [ka] To a solution of potassium hydroxide (8.42 g, 150.1 mmol) in methanol (200 mL), 1-hexanethiol (21 mL, 148.8 mmol) was slowly added. After stirring the contents at room temperature for 30 minutes, 1,3-dibromopropan-2-ol (14.39 g, 65.6 mmol) was added dropwise. The resulting reaction mixture was stirred at room temperature for a further 15 minutes. The intermediate product MS4-i was isolated by extraction using methyl t-butyl ether and water, followed by washing with a dilute solution of aqueous potassium hydroxide, and then brine. The resulting product was dried under reduced pressure to obtain a clear oil. Yield: 19.60 g, with residual hexyl disulfide from the starting material.

[0138] The intermediate product MS4-i (9.61 g, 32.8 mmol) and TEA (12 mL, 86.1 mmol) were mixed with methyl t-butyl ether (120 mL) to obtain a solution. Methacryloyl chloride (5 mL, 51.2 mmol) was added dropwise to this solution while stirring at room temperature. The reaction mixture was stirred further at room temperature for 4 hours. The intermediate product MS4-ii was isolated by extraction using methyl t-butyl ether and water. The obtained product was washed twice with dilute hydrochloric acid aqueous solution, once with dilute potassium hydroxide aqueous solution, and then once with brine aqueous solution. The obtained product was dried under reduced pressure to obtain intermediate product MS4-ii as a clear oil. Yield: 12.07 g, containing residual hexyl disulfide and methacrylic anhydride. Impurities were carried over but did not affect the next step.

[0139] The intermediate product MS4-ii (5.83 g, 16.2 mmol) was dissolved in a mixture of methanol (200 mL) and water (100 mL). Oxone (35.2 g, 57.2 mmol) was added to this mixture in five separate additions, and the resulting reaction mixture was stirred at room temperature for a further 1 hour. The crude product was isolated by extraction using methyl t-butyl ether and water. The product was further purified by crystallization from the minimum amount of heptane to obtain MS4 as a waxy solid. Yield: 4.29 g (62%). 1 ¹H-NMR (δ, chloroform-d1): 6.24 ppm (s, 1H, CH=CHH), 5.72 ppm (m, 2H, CH=CHH and OCH), 3.59 ppm (qd, 4H, SO2CH2CH), 3.08 ppm (m, 4H, SO2CH2CH2), 1.99 ppm (s, 3H, CCH3), 1.87 ppm (m, 4H, SO2CH2CH2), 1.46 ppm (p, 4H, SO2CH2CH2CH2), 1.34 ppm (m, 4H, CH3CH2CH2), 1.34 ppm (m, 4H, CH3CH2CH2 and CH3CH2), and 0.92 ppm (t, 6H, CH2CH3).

[0140] Polymer synthesis Polymers P1-P6 and comparative polymers CP1-CP4 were prepared using the following monomers. [ka]

[0141] Synthesis of polymer P1 Polymer P1 was prepared from monomers MA1, MB2, and MS1 in a molar supply ratio of 45:45:10. A supply solution was prepared by dissolving MA1 (8.24 g, 42.8 mmol), MB2 (8.75 g, 42.8 mmol), and MS1 (3.01 g, 9.50 mmol) in propylene glycol monomethyl acetate (PGMEA, 20.0 g). An initiator solution was separately prepared by dissolving 2.32 g of dimethyl 2,2'-azobis(2-methylpropionate) (obtained from Wako Pure Chemical Industries, Ltd. as V-601) as an azo initiator in 6.43 g of a 1:1 (w / w / ) PGMEA / tetrahydrofuran mixture.

[0142] Polymerization was carried out in a three-necked round-bottom flask equipped with a water condenser and a thermometer to monitor the reaction inside the flask. 10.0 g of PGMEA was placed in the reactor and heated to 75°C. The feed solution and initiator solution were supplied to the reactor separately using syringe pumps over 4 hours. After addition, the contents were stirred for a further 2 hours. The contents were then cooled to room temperature and diluted with 20 g of PGMEA to produce a crude polymer solution. Subsequently, the acetal groups in the repeating units derived from monomer MA1 were removed as follows. An acidic ion exchange resin was added to the crude polymer solution, and the mixture was stirred at room temperature for 24 hours. The ion exchange resin was removed by filtration, and the solvent was removed under reduced pressure. The obtained crude polymer was dissolved in acetone (25 g). The acetone polymer solution was slowly added to a large excess of deionized water to precipitate the polymer. The obtained polymer precipitate was isolated by filtration and then washed with deionized water. The polymer product was then dried under reduced pressure at 35°C.

[0143] Synthesis of polymers P2-P5 and comparative polymers CP1-CP4 Each polymer in Table 1 was prepared using the same procedure as described above for the preparation of polymer P1, except that the monomers and molar supply ratios (mol%) based on a total of 100 mol% were used as listed in Table 1.

[0144] [Table 1]

[0145] Information on lithographically evaluated formulations The photoresist compositions were prepared by dissolving the solid components in a solvent using the materials and amounts shown in Tables 2 and 3. The amounts are expressed as weight percent based on 100% of the total weight of the solids. The total solid content of the photoresist composition was 2.5% by weight. The solvent system contained PGMEA (50% by weight) and methyl-2-hydroxyisobutyric acid (50% by weight). Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disc filter with a pore size of 0.2 microns.

[0146] Lithography-based patterning and data analysis Lithography was performed using the CLEAN TRAC ACT8 (TEL, Tokyo Electron Co.) wafer track. A 200nm wafer for photolithography testing was coated with AR(trademark)3 BARC (DuPont Electronics & Industrial) and soft-baked at 205°C for 60 seconds to obtain a 60nm film. Next, a coating of AR(trademark)40A BARC (DuPont Electronics & Industrial) was placed on top of the AR(trademark)3 layer and soft-baked at 215°C for 60 seconds to form a second BARC layer with a thickness of approximately 80nm. Then, a photoresist composition was 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 70nm.

[0147] A wafer was exposed to 248 nm radiation using a Canon FPA-5000 ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57) with a mask having a 1:1 L / S pattern (120 nm linewidth). After exposure, the wafer was baked at 100°C for 60 seconds, developed with MF(trademark) CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with deionized water, and spin-dried. The limiting dimension (CD) linewidth of the formed pattern was measured using a Hitachi S-9380 CD-SEM. The linewidth roughness (LWR) value was determined by top-down SEM with an acceleration voltage of 800 volts (V), a probe current of 8.0 picoamperes (pA), a digital zoom of 1.0, a magnification of 200Kx, and a frame rate of 64. The LWR was measured over a line length of 2 μm in 40 nm steps and reported as the average LWR of the measured region. Sizing energy (E size The line width roughness (LWR) and the line width roughness of the lines were determined based on CD measurements.

[0148] The pseudo-Z factor is reported below. It was determined according to Equation 1: Pseudo Z-factor = (E size )×(LWR) 2 (Formula 1) (In the formula, E size This is millijoules per square centimeter (mJ / cm²). 2 The values ​​are reported in units of ) and LWR is reported in nanometers (nm), and the pseudo-Z factor is mJ × 10⁻⁶. -11 (Reported in units of 1). The pseudo-Z factor is a modified measure of photoresist performance based on the Z factor, which is an index of known parameters indicating RLS (resolution, line edge roughness, sensitivity) photoresist performance (see, for example, Non-Patent Literature 1). The pseudo-Z factor is calculated at a constant resolution (CD size).

[0149] Line Space (L / S) Patterning The photoresist compositions in Table 2 were evaluated for L / S patterning using the bright-field mask pattern under the aforementioned KrF exposure (248 nm). size The LWR of the space was determined based on CD measurements. size This was determined as the irradiation energy amount at which the target 120 nm L / S pattern was resolved. size The LWR and pseudo-Z-factor data are shown in Table 2. The quantities are specified as weight percentages based on total solids.

[0150] [Table 2]

[0151] The structures of PAG-A, PAG-B, Q1, and Q2 are shown below. [ka]

[0152] As shown in Table 2, photoresist compositions PR-1 to PR-6 are compared to comparative examples PR-7 and PR-8 in terms of E size As is evident from the small LWR, improved sensitivity was achieved. The improved sensitivity of photoresist compositions PR-1 to PR-6 did not impair line / space feature roughness, as is evident from the equivalent or improved LWR compared to comparative compositions PR-7 to PR-9. In each case, the pseudo-Z factors of photoresist compositions PR-1 to PR-6 were smaller than those of the comparative photoresist compositions PR-7 to PR-9.

[0153] Line Space (L / S) Patterning The photoresist compositions shown in Table 3 were prepared in the same manner as in the previous example, and their line / space patterning under KrF exposure was evaluated. On a TEL Clean Track ACT 8 wafer track, 200 mm silicon wafers overcoated with a BARC stack (80 nm thick AR40A anti-reflective material laminated with a 60 nm thick AR3 anti-reflective material (DuPont Electronics & Industrial)) were spin-coated with each photoresist composition, and soft-baked at 110°C for 60 seconds to obtain a photoresist layer approximately 120 nm thick. Each wafer was exposed to 248 nm radiation using a CANNON FPA-5000 ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57) with a mask having a 120 nm line / space (l / s) pattern. The wafers were exposed to light at 100°C for 60 seconds, baked, developed with MF-CD26 TMAH developer (DuPont Electronics & Imaging) for 60 seconds, rinsed with deionized water, and dried. The limiting dimension (CD) of the formed l / s pattern was measured using a Hitachi S-9380 CD SEM. The target linewidth roughness (LWR) in a 120 nm space was determined based on the CD measurement. The results are shown in Table 3, with quantities specified as weight percentages relative to total solids.

[0154] [Table 3]

[0155] As shown in Table 3, photoresist compositions PR-10 and PR-11 achieved improved LWR compared to the comparative photoresist composition PR-12.

[0156] While this disclosure has been described in conjunction with what are currently considered to be practical and exemplary embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to encompass a variety of modifications and equivalent configurations that fall within the spirit and scope of the appended claims. The present invention may include the following embodiments 1 to 15: [Aspect 1] Formula-C(R a )(R b A polymer comprising a first repeating unit containing a sulfone group directly bonded to the base of )-, and a second repeating unit containing an acid-unstable group, a base-degradable group, a polar group, or a combination thereof, wherein R in the formula a and R b However, each is independent of hydrogen, halogen, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl, but R a and R b A polymer in which at least one of the elements is hydrogen. [Aspect 2] The first repeating unit is given by equation (1): [ka] (In equation (1), X a It is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond; L 1 is a single bond or linking group; Each L 2 These are independently single-bonded, substituted, or unsubstituted C atoms. 1~30 Alkyl, or substituted or unsubstituted C 3~30 It is a cycloalkyl; Each R 1 These are independently 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 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl, but has at least one L 2 or at least one R 1 This is the equation -C(R) that is directly bonded to -S(=O)2-. a )(R b )-Includes the base; (n is an integer between 1 and 5) The polymer according to embodiment 1, derived from a first monomer represented by . [Aspect 3] at least one L 2 However, the formula -C(R) is directly bonded to -S(=O)2- a )(R b A polymer according to embodiment 2, comprising the group )-. [Aspect 4] The at least one R 1 However, the formula -C(R) is directly bonded to -S(=O)2- a )(R b A polymer according to embodiment 2 or 3, comprising the group )-. [Aspect 5] The first repeating unit is given by equation (2) or (3): [ka] (In equations (2) and (3), X b and X c Each of these is independently a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond; L 3 and L 4 Each of these is independently either a single bond or a divalent linking group; R 2 , R 3 , and R 4 These are, independently, substitutional or non-substitutional 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 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl) A polymer according to any one of embodiments 1 to 4, derived from a first monomer represented by . [Aspect 6] The polymer according to any one of embodiments 2 to 5, wherein the first monomer comprises a (meth)acroyl group or a vinyl aromatic group. [Aspect 7] The polymer according to any one of embodiments 1 to 5, wherein the second repeating unit contains an acid-unstable group. [Aspect 8] Formula-C(R a )(R b A first polymer comprising a first repeating unit containing a sulfone group directly bonded to the base of )- (In the formula, R a and R b These are, independently, hydrogen, halogen, substituted or unsubstituted C. 1~30Alkyl, 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 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30 Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl, but R a and R b (At least one of them is hydrogen) Solvent and, A photoresist composition containing the following: [Aspect 9] The first repeating unit is given by equation (1): [ka] (In equation (1), X a It is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond; L 1 is a single bond or linking group; Each L 2 These are independently single-bonded, substituted, or unsubstituted C 1~30 Alkyl, or substituted or unsubstituted C 3~30 It is a cycloalkyl; Each R 1 These are independently 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 3~30 Cycloalkenyl, substituted or unsubstituted C 3~30Heterocycloalkenyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, 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 an alkyl heteroaryl, but has at least one L 2 or at least one R 1 This is the equation -C(R) that is directly bonded to -S(=O)2-. a )(R b )-Includes the base; n is an integer between 1 and 5. A photoresist composition according to embodiment 8, derived from a first monomer represented by . [Aspect 10] The photoresist composition according to embodiment 8 or 9, wherein the polymer further comprises a second repeating unit, the second repeating unit comprising an acid-unstable group, a base-degradable group, a polar group, or a combination thereof. [Aspect 11] The photoresist composition according to any one of embodiments 8 to 10, wherein the second repeating unit contains an acid-unstable group. [Aspect 12] A photoresist composition according to any one of embodiments 8 to 11, further comprising a photoacid generator. [Aspect 13] A photoresist composition according to any one of embodiments 8 to 12, further comprising a second polymer structurally different from the first polymer. [Aspect 14] The photoresist composition according to embodiment 13, wherein one or both of the first polymer and the second polymer include repeating units comprising an acid-unstable group, a base-degradable group, a polar group, or a combination thereof. [Aspect 15] A method for forming a pattern, Forming a photoresist composition layer on a substrate by coating a layer of the photoresist composition described in any one of embodiments 8 to 14; Forming an exposed photoresist composition layer by pattern exposure of the photoresist composition layer with activation radiation; and Developing the aforementioned exposure photoresist composition layer; A method that includes this.

Claims

1. Formula-C(R ａ ) (Caution ｂ A polymer for a photoresist composition comprising: a first repeating unit containing a sulfone group directly bonded to the group of; and a second repeating unit containing an acid-unstable group, a basic-degradable group, a hydroxyaryl group, or a combination thereof, selected from a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, a ketal group, a tertiary carbonate group and a tertiary carbamate group, and a tertiary carbamate group, R in the formula ａ and R ｂ are each independently hydrogen, halogen, substituted or unsubstituted C １～３０ alkyl, substituted or unsubstituted C ３～３０ cycloalkyl, substituted or unsubstituted C ３～３０ heterocycloalkyl, substituted or unsubstituted C ２～３０ alkenyl, substituted or unsubstituted C ３～３０ cycloalkenyl, substituted or unsubstituted C ３～３０ heterocycloalkenyl, substituted or unsubstituted C ６～３０ aryl, substituted or unsubstituted C ７～３０ arylalkyl, 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 alkylheteroaryl, provided that at least one of R ａ and R ｂ is hydrogen, The first repeating unit is given by equation (1): 【Chemistry 1】 (In equation (1), X ａ It is a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond; L １ is a single bond or linking group; Each L ２ These are independently single-bonded, substituted, or unsubstituted C atoms. １～３０ Alkyl, or substituted or unsubstituted C ３～３０ It is a cycloalkyl; Each R １ These are independently 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 ３～３０ Cycloalkenyl, substituted or unsubstituted C ３～３０ Heterocycloalkenyl, substituted or unsubstituted C ６～３０ Aryl, substituted, or unsubstituted C ７～３０ Arylalkyl, 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 an alkyl heteroaryl, at least one L ２ or at least one R １ is -S (=O) ２ - Directly coupled to the formula -C(R ａ ) (Caution ｂ ) - including the base; n is an integer between 1 and 5. A polymer for a photoresist composition, derived from a first monomer represented by .

2. at least one L ２ However, -S (=O) ２ - Directly coupled to the formula -C(R ａ ) (Caution ｂ The polymer according to claim 1, comprising the group )-.

3. The at least one R １ However, -S (=O) ２ - Directly coupled to the formula -C(R ａ ) (Caution ｂ The polymer according to claim 1 or 2, comprising the group )-.

4. The first repeating unit is given by formula (2) or (3): 【Chemistry 2】 (In equations (2) and (3), X ｂ and X ｃ Each of these is independently a polymerizable group containing an ethylenically unsaturated carbon-carbon double bond; L ３ and L ４ Each of these is independently either a single bond or a divalent linking group; R ２ , R ３ , and R ４ These are, independently, substitutional or non-substitutional 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 ３～３０ Cycloalkenyl, substituted or unsubstituted C ３～３０ Heterocycloalkenyl, substituted or unsubstituted C ６～３０ Aryl, substituted, or unsubstituted C ７～３０ Arylalkyl, 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 an alkyl heteroaryl.) A polymer according to any one of claims 1 to 3, derived from a first monomer represented by .

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

6. The polymer according to any one of claims 1 to 4, wherein the second repeating unit contains an acid-unstable group.

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