Polymer, photoresist compositions including the same, and pattern formation methods

Abstract

A first repeating unit comprising a sulfone group directly bonded to a group of the chemical formula -C(Ra)(Rb)-; The present invention provides a polymer comprising a second repeating unit comprising an acid-unstable group, a base-degradable group, a polar group, or a combination thereof, wherein Ra and Rb are each independently hydrogen, a halogen, a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C3-30 cycloalkyl, a substituted or unsubstituted C3-30 heterocycloalkyl, a substituted or unsubstituted C2-30 alkenyl, a substituted or unsubstituted C3-30 cycloalkenyl, a substituted or unsubstituted C3-30 heterocycloalkenyl, a substituted or unsubstituted C6-30 aryl, a substituted or unsubstituted C7-30 arylalkyl, a substituted or unsubstituted C7-30 alkylaryl, a substituted or unsubstituted C2-30 heteroaryl, a substituted or unsubstituted C3-30 heteroarylalkyl, or a substituted or unsubstituted C3-30 alkylheteroaryl, provided that at least one of Ra and Rb is hydrogen.

Description

Technology Field

[0001] The present invention relates to a polymer for a photoresist composition and a method for forming a pattern using such a photoresist composition. The present invention can be applied 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. To increase the integration density of semiconductor devices and enable the formation of structures with dimensions in the nanometer range, high-resolution photoresists and photolithography processing tools have been developed and are continuously being developed.

[0003] Chemically amplified photoresists are typically used for high-resolution processing. Such resists typically utilize a polymer containing acid-unstable groups, a photogenerative agent, and an acid-quenching material. When exposed to active radiation in a patterned manner through a photomask, the acidgenerative agent forms an acid, which cleaves the acid-unstable groups in the exposed areas of the polymer during post-exposure baking. Often, an acid-quenching material is added to the photoresist composition to control the diffusion of acid into unexposed areas in order to improve contrast. As a result of the lithography process, a difference in solubility characteristics is created between the exposed and unexposed areas of the resist in the developer solution. In the positive tone development (PTD) process, the exposed areas of the photoresist layer become soluble in the developer and are removed from the substrate surface, while the unexposed areas, which are insoluble in the developer, remain after development to form a positive image. The generated relief image enables selective processing of the substrate.

[0004] Despite advancements in resist technology, there is still a need for photoresist compositions that address one or more issues related to the current level of technology. In particular, there is a continuing demand for photoresist compositions with excellent sensitivity, including those capable of achieving higher contrast and low line width roughness (LWR) for line / space patterns. means of solving the problem

[0005] One embodiment is the chemical formula -C(R a )(R b A polymer is provided comprising: a first repeating unit comprising a sulfone group directly bonded to a )- group; and a second repeating unit comprising an acid-unstable group, a base-degradable group, a polar group, or a combination thereof, wherein R a and R b Each is 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, wherein R a and R b At least one of them is hydrogen.

[0006] Chemical formula -C(R a )(R b A first polymer comprising a first repeating unit comprising a sulfone group directly bonded to the )- group, wherein Ra and R b Each is 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, wherein R a and R b A photoresist composition is also provided, comprising a first polymer, at least one of which is hydrogen; and a solvent.

[0007] Another aspect provides a method for forming a pattern, comprising the steps of: applying a layer of a photoresist composition onto a substrate to form a photoresist composition layer; exposing the photoresist composition layer in a patterned manner using active radiation to form an exposed photoresist composition layer; and developing the exposed photoresist composition layer.

[0008] The aforementioned features and other features are exemplified by the detailed description below. Specific details for implementing the invention

[0009] Exemplary embodiments will now be described in detail, and examples thereof are illustrated in this description. In this regard, these exemplary embodiments may take different forms and should not be interpreted as being limited to the description provided herein. Accordingly, exemplary embodiments are described below with reference to the drawings merely to illustrate the aspects of this description. As used herein, the term "and / or" includes any combination of one or more of the related enumerated items and all combinations. Expressions such as "at least one of" used following a list of elements modify the entire list of elements, not the individual elements of the list.

[0010] As used herein, the singular form is not to indicate a limitation of quantity unless otherwise specified herein or is clearly contradictory in the context, and should be interpreted to include both singular and plural forms. Unless otherwise clearly specified, "or" means "and / or." The modifier "about" used in relation to quantity includes the mentioned value and has a contextual meaning (e.g., including the degree of error associated with the measurement of a specific quantity). All ranges disclosed herein include endpoints, which may be combined with one another independently. The suffix "(s)" is intended to include at least one of the terms in which it is used, including both the singular and plural forms. "Optional" or "optional" means that an event or situation described subsequently may or may not occur, and that the description includes cases where the event occurs and cases where the event does not occur. In this document, terms "first," "second," etc., are used not to indicate order, quantity, or importance, but to distinguish one element from another. Where one element is referred to as being "on" another element, these elements may be in direct contact with each other or an intervening element may exist between them. In contrast, where one element is referred to as being "directly" on another element, no intervening element exists. It should be understood that the described components, elements, limitations, and / or features of the embodiments may be combined in any suitable manner in various embodiments.

[0011] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly 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 a meaning consistent with their meaning in the context of the relevant technology and the present disclosure, and it will also be understood that they should not be interpreted in an ideal or overly formal sense unless explicitly defined so herein.

[0012] As used herein, “chemical rays” or “radiation” means, for example, the emission spectrum of a mercury lamp, far ultraviolet rays produced by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, particle rays, such as electron beams and ion beams, etc. Additionally, in this invention, “light” means chemical rays or radiation. A krypton fluoride laser (KrF laser) is a specific type of excimer laser, which is sometimes referred to as an exciplex laser. “Excimer” is an abbreviation for “excited dimer,” and “exciplex” is an abbreviation for “excited complex.” An excimer laser uses a mixture of an inert gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine), which emits coherent excitation radiation (laser light) in the ultraviolet range under suitable conditions of electrical stimulation and high pressure. In addition, unless otherwise specified, “exposure” in this specification includes not only exposure by far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light), etc., produced by mercury lamps or excimer lasers, but also writing by particle beams, such as electron beams and ion beams.

[0013] As used herein, “organic group” comprises one or more carbon atoms, for example, 1 to 60 carbon atoms. The term “hydrocarbon” 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 straight-chain or branched-chain saturated hydrocarbon group having a specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence 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 chemical formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a straight-chain or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond; and "alkenoxy" refers to "alkenyl-O-"; "Alkenylene" refers to an alkenyl group having a valence of 2; "Cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least one carbon-carbon double bond and 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 satisfying Huckel's rule, containing a carbon atom within the ring, and optionally containing one or more heteroatoms selected from N, O, and S instead of a carbon atom within the ring; "Aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which all ring members are carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; and "Aryllene" refers to an aryl group having a valence of 2; "Alkylaryl" refers to an aryl group substituted with an alkyl group; "arylkyl" refers to an alkyl group substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "aryltio" refers to "aryl-S-".

[0014] The prefix "hetero" means that the compound or group comprises at least one member (e.g., 1, 2, 3, or 4 or more heteroatom(s)) that is a heteroatom instead of a carbon atom, wherein each heteroatom(s) is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent comprising at least one heteroatom; "heteroalkyl group" refers to an alkyl group having 1 to 4 or more heteroatoms instead of a carbon; "heterocycloalkyl group" refers to a cycloalkyl group having 1 to 4 or more heteroatoms as ring members instead of a carbon; "heterocycloalkylene group" refers to a heterocycloalkyl group having a valence of 2; and "heteroaryl group" refers to an aryl group having 1 to 4 or more heteroatoms as ring members instead of a carbon; "Heteroarylene group" refers to a heteroaryl group having a valence of 2.

[0015] Each of the aforementioned substituents may be optionally substituted unless explicitly provided otherwise. For example, where a group is cited without specifying whether it is substituted or unsubstituted, said group includes both groups without substituents and groups with substituents. The term "optionally substituted" refers to being substituted or unsubstituted.

[0016] "Substituted" means that at least one hydrogen atom in the chemical structure is replaced by another terminal substituent, typically monovalent, provided that the normal valence of the specified atom does not exceed the valence of the specified atom. If the substituent is oxo (i.e., =O), two identical hydrogen atoms on the carbon atom are replaced by terminal oxo groups. Combinations of substituents or variables may be permitted. Exemplary substituents that may be present in the "substituted" position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di- (C 1-6 )alkylamino, alkanoyyl (e.g., C such as acyl) 2-6alkanoyl group), formyl (-C(=O)H), carboxylic acid or its alkali metal or ammonium salt; ester (including acrylates, methacrylates, and lactones), e.g., C 2-6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7-13 Aryl ester (-C(=O)O-aryl or -OC(=O)-aryl), amido (-C(=O)NR2, where R is hydrogen or C 1-6 alkyl), carboxymid (-CH2C(=O)NR2, where R is hydrogen or C 1-6 alkyl), halogen, thiol (-SH), C 1-6 Alkylthio(-S-alkyl), thiocyano(-SCN), C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 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, C having at least one aromatic ring 6-12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring being a substituted or unsubstituted aromatic), C having 1 to 3 individual or fused rings and 6 to 18 cyclic carbon atoms 7-19 Arylalkyl, arylalkoxy having 1 to 3 individual or fused rings and 6 to 18 cyclic carbon atoms, C 7-12 Alkylaryl, C 3-12 Heterocycloalkyl, C 3-12 Heteroaryl, C 1-6 Alkyl sulfonyl(-S(=O)2-alkyl), C 6-12 arylsulfonyl (-S(=O)2-aryl), or tosyl (CH3C6H4SO2-) are included, but not limited thereto.

[0017] 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 containing one or more of fluoro, chloro, bromo, or iodo substituents in place of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) may exist, or only fluoro groups may exist.

[0018] As used herein, "acid instability group" refers to a group that forms a polar group, such as a carboxylic acid or alcohol group, in the polymer as the bond is cleaved by the action of an acid, optionally and typically with heat treatment, and the moiety connected to the cleaved bond is optionally and typically separated from the polymer. In other systems, a non-polymerized compound may contain an acid instability group capable of forming a polar group, such as a carboxylic acid or alcohol group, in the cleaved portion of the non-polymerized compound as the action of an acid. Such an acid is typically a photo-generated acid in which bond cleavage occurs during post-exposure baking (PEB), but embodiments are not limited thereto, for example, such an acid may be thermally generated. Acid instability group is also generally referred to in the art as an "acid-cleaving group," "acid-cleaving protector," "acid instability protector," "acid-leaving group," "acid-degrading group," and "acid-sensitive group."

[0019] As used herein, unless otherwise provided, "divalent linkers" are -O-, -S-, -Te-, -Se-, -C(O)-, -N(R b )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocycloalkylene, substituted or unsubstituted C 6-30Aryllene, substituted or unsubstituted C 3-30 Refers to a divalent group comprising one or more of a heteroarylene or a combination thereof, wherein R b is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 Aryl, or substituted or unsubstituted C 3-30 It is a heteroaryl. Typically, the divalent linker 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 Aryllene, substituted or unsubstituted C 3-30 It comprises one or more of heteroarylenes or combinations thereof, wherein 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 It is an alkylheteroaryl. More typically, the divalent linker is -O-, -C(O)-, -C(O)O-, -N(R b )-, -C(O)N(R b )-, substituted or unsubstituted C1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocycloalkylene, substituted or unsubstituted C 6-10 Aryllene, substituted or unsubstituted C 3-10 It comprises at least one of heteroarylene or a combination thereof, wherein R b is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted, or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 Aryl, or substituted or unsubstituted C 3-10 It is a heteroaryl.

[0020] The present disclosure relates to a polymer having repeating units comprising sulfone groups, wherein the sulfone group is directly covalently bonded to a divalent carbon atom, and the divalent carbon atom is bonded to at least one hydrogen atom. The direct covalent attachment of the sulfone group to the divalent carbon atom makes the attached proton more acidic, making it susceptible to deprotonation in the presence of a strong base, such as tetramethylammonium hydroxide, a common developer used in lithography processes. Without being bound by any specific theory, it is believed that the polymer of the present invention, when used in a photoresist composition, can reduce defects by generating a more hydrophilic group in the exposed area as a result of the reaction of the base-reactive group during the alkaline development step. Additionally, an increase in the solubility of the alkaline developer can help reduce bridge defects and / or pattern collapse.

[0021] One embodiment is the chemical formula -C(R a )(R b A polymer is provided comprising: a first repeating unit comprising a sulfone group (-S(=O)2-) directly bonded to the )- group; and a second repeating unit comprising an acid-unstable group, a base-degradable group, a polar group, or a combination thereof.

[0022] Chemical formula -C(R a )(Rb In the basis of )-, R a and R b Each is 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, wherein R a and R b At least one of them is hydrogen. Typically, R a and R b Each is 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 alkylheteroaryl, provided that R a and R bAt least one of them is hydrogen. Preferably, R a and R b Each is 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 heteroaryl, but R a and R b At least one of them is hydrogen.

[0023] In some embodiments, the first repeating unit may be derived from the first monomer represented by Formula 1:

[0024] [Chemical Formula 1]

[0025]

[0026] In Chemical Formula 1, X a is a polymerizable group containing an ethylene-based unsaturated carbon-carbon double bond. Typically, X a is substituted or unsubstituted C 2-20 It may be selected from alkenyl groups, substituted or unsubstituted norvonyl 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 substituted or unsubstituted C 2-20 It is an alkenyl, substituted or unsubstituted norvonyl, substituted or unsubstituted (meth)acrylic, or substituted or unsubstituted vinyl aromatic.

[0027] In Chemical Formula 1, L 1 is a single bond or linker. Typically, linkers are -O-, -S-, -C(O)-, -C(O)O-, -N(R c )-, -C(O)N(R c)-, -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 Aryllene, substituted or unsubstituted C 3-30 It may include one or more of heteroarylenes or combinations thereof, where R c 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 It may be an alkylheteroaryl. Preferably, the linking group is -O-, -C(O)-, -C(O)O-, -N(R c )-, -C(O)N(R c )-, 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 Aryllene, substituted or unsubstituted C 3-10 It comprises at least one of heteroarylene or a combination thereof, wherein R c is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted, or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C3-30 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 It can be an alkyl heteroaryl.

[0028] In Chemical Formula 1, n is an integer from 1 to 5. Typically, n can be 1, 2, or 3. Preferably, n can be 1 or 2.

[0029] L 1 In the case of this connection, L 1 is a group with a valence of n + 1. For example, L 1 If n is 1, then 2 is finite or L 1 If n is 2, then 3 is finite or L 1 If n is 3, then 4 is , or L 1 If n is 4, then 5 is , or L 1 When n is 5, 6 is .

[0030] In Chemical Formula 1, each L 2 is independently a single bond, substituted, or unsubstituted C 1-30 Alkylene, or substituted or unsubstituted C 3-30 It is a cycloalkylene. Typically, L 2 is a single bond, substituted, or unsubstituted C 1-20 Alkylene, or substituted or unsubstituted C 3-20 It may be a cycloalkylene. Preferably, L 2 is substituted or unsubstituted C 1-10 Alkylene, or substituted or unsubstituted C 3-10It can be cycloalkylene.

[0031] In Chemical Formula 1, L 1 and L 2 may not simultaneously be a single bond. In other words, L 1 and L 2 At least one of them is not a single bond.

[0032] In Chemical Formula 1, each R 1 C that is independently substituted or unsubstituted 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 alkylheteroaryl. Typically, each R 1 C that is independently substituted or unsubstituted 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 It may be an alkylheteroaryl. Preferably, each R 1 C that is independently substituted or unsubstituted 1-10Alkyl, 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 can be an alkyl heteroaryl.

[0033] In Chemical Formula 1, each R 1 It may independently include an additional 2-linker as part of its structure. For example, each R 1 is independently as part of its structure -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R c )- or -C(O)N(R c It may additionally include one or more groups selected from )-, where R c is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 It is a heterocycloalkyl.

[0034] In Chemical Formula 1, at least one L 2 or at least one R 1 The chemical formula -C(R) that is directly bonded to -S(=O)2- a )(R b It includes the group of )-. In other words, when n is 1, L 2 and R 1 At least one of the chemical formula -C(R) is directly bonded to -S(=O)2-. a )(R b It includes the group of ). However, if n is 2 or greater, at least one unit represented by n is L 2 and R 1Chemical formula -C(R₀) in which at least one of them is directly bonded to -S(=O)2- a )(R b At least one L, including the unit of )- but such that other units represented by n do not need to satisfy these restrictions. 2 or at least one R 1 The chemical formula -C(R) that is directly bonded to -S(=O)2- a )(R b Includes the group of )-. For example, at least one L 2 -C(R) is a chemical formula directly bonded to -S(=O)2-. a )(R b It may include the group of ). For example, at least one R 1 The chemical formula -C(R) that is directly bonded to -S(=O)2- a )(R b It may include the group of )-. Or, for example, one L 2 or one R 1 The chemical formula -C(R) that is directly bonded to -S(=O)2- a )(R b It may include the energy of )-.

[0035] In some embodiments, when n is 1, the first repeating unit can be derived from the first monomer represented by Formula 2:

[0036] [Chemical Formula 2]

[0037]

[0038] In Chemical Formula 2, X b is a polymerizable group containing an ethylene-based unsaturated carbon-carbon double bond. Typically, X b is substituted or unsubstituted C 2-20It may be selected from alkenyl groups, substituted or unsubstituted norvonyl 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 b is substituted or unsubstituted C 2-20 It is an alkenyl, substituted or unsubstituted norvonyl, substituted or unsubstituted (meth)acrylic, or substituted or unsubstituted vinyl aromatic.

[0039] In Chemical Formula 2, L 3 is a single bond or a divalent linker. Typically, L 3 is a single bond, or -O-, -C(O)-, -C(O)O-, -N(R c )-, -C(O)N(R c )-, 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 Aryllene, substituted or unsubstituted C 3-10 It may be a linking group comprising at least one of a heteroarylene or a combination thereof, wherein R c 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 3-30Heteroarylalkyl, or substituted or unsubstituted C 3-30 It can be an alkyl heteroaryl.

[0040] In Chemical Formula 2, R 2 R in Chemical Formula 1 1 It is as defined for. Typically, R 2 is substituted or unsubstituted C 1-30 Alkyl, substituted, or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 3-30 Heterocycloalkyl, substituted or unsubstituted C 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 alkylheteroaryl. Preferably, R 2 is 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 6-24 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 can be an alkyl heteroaryl.

[0041] In some embodiments, R 2 It may additionally include a 2-linker as part of its structure. For example, R 2is as part of that structure -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R c )- or -C(O)N(R c It may additionally include one or more groups selected from )-, where R c is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 It is a heterocycloalkyl.

[0042] In some embodiments, when n is 2, the first repeating unit can be derived from the first monomer represented by Formula 3:

[0043] [Chemical Formula 3]

[0044]

[0045] In Chemical Formula 3, X c is a polymerizable group containing an ethylene-based unsaturated carbon-carbon double bond. Typically, X c is substituted or unsubstituted C 2-20 It may be selected from alkenyl groups, substituted or unsubstituted norvonyl 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 substituted or unsubstituted C 2-20 It is an alkenyl, substituted or unsubstituted norvonyl, substituted or unsubstituted (meth)acrylic, or substituted or unsubstituted vinyl aromatic.

[0046] In Chemical Formula 3, L 4 is a single bond or a divalent linker. Typically, L 4 is a single bond, or -O-, -C(O)-, -C(O)O-, -N(R c )-, -C(O)N(R c )-, substituted or unsubstituted C1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocycloalkylene, substituted or unsubstituted C 6-10 Aryllene, substituted or unsubstituted C 3-10 It may be a linking group comprising at least one of a heteroarylene or a combination thereof, wherein R c 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 It can be an alkyl heteroaryl.

[0047] In Chemical Formula 3, R 3 and R 4 are each independently R 1 It is identical to what is defined herein. Typically, R 3 and R 4 C, each independently substituted or unsubstituted 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 C7-30 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 alkylheteroaryl. Preferably, R 3 and R 4 C, each independently substituted or unsubstituted 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 can be an alkyl heteroaryl.

[0048] In some embodiments, R 3 and / or R 4 It may additionally include a 2-linker as part of its structure. For example, R 3 and / or R 4 is independently as part of its structure -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R c )- or -C(O)N(R c It may additionally include one or more groups selected from )-, where R c is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 It is a heterocycloalkyl.

[0049] In some embodiments, the first repeating unit may be derived from a first monomer comprising a (meth)acryloyl group or a vinyl aromatic group. In other words, in some embodiments, the polymerizable group X a , X b and / or X c It can be a (mat)acrylic group or a vinyl aromatic group.

[0050] 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:

[0051] [Chemical Formula 4]

[0052]

[0053] [Chemical Formula 5]

[0054]

[0055] [Chemical Formula 6]

[0056]

[0057] [Chemical Formula 7]

[0058]

[0059] In chemical formulas 4 to 7, each R j is independently hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 Alkyl, or substituted or unsubstituted C 1-10 It is a fluoroalkyl. Preferably, R j is hydrogen, or substituted or unsubstituted C 1-5 Alkyl, typically methyl. R 5 to R 9 C, each independently substituted or unsubstituted 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 C3-30 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 alkylheteroaryl. Preferably, R 5 to R 9 C, each independently substituted or unsubstituted 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 can be an alkyl heteroaryl.

[0060] In chemical formulas 4 to 7, R 5 to R 9 It may additionally include a 2-linker as part of its structure. For example, R 5 to R 9 Each is independently -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R c )- or -C(O)N(R c It may include one or more groups selected from )-, where R c is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 It is a heterocycloalkyl.

[0061] Non-limiting examples of the first monomer may include one or more of the following:

[0062]

[0063]

[0064]

[0065]

[0066] .

[0067] The first repeating unit of the polymer is present in an amount typically of 5 to 100 mol% (mol%), more typically of 5 to 50 mol%, more typically of 5 to 25 mol%, and even more typically of 5 to 15 mol%, based on the total repeating units of the polymer.

[0068] The polymer may further comprise a second repeating unit comprising an acid-unstable group, a base-degradable group, a polar group, or a combination thereof. In one or more embodiments, the second repeating unit may comprise an acid-unstable group, a hydroxyaryl group, a fluoroalcohol group, a sulfonamide group, a lactone group, or a combination thereof. For example, the polymer may comprise a second repeating unit comprising an acid-unstable group, a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a lactone group. In some embodiments, the second repeating unit comprises an acid-unstable group.

[0069] Suitable acid-unstable groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of an alkyl group and an aryl group, tertiary alkoxy groups, acetal groups, ketal groups, tertiary carbonate groups, and tertiary carbamate groups. Typically, the acid-unstable group may be an acetal group, a ketal group, a tertiary carbonate group, a tertiary carbamate group, or a tertiary ester group. As used herein, "tertiary carbamate group" includes tertiary carbamate ester groups having an alkyl group, tertiary carbamate ester groups having an aryl group, and tertiary carbamate ester groups having a combination of an alkyl group and an aryl group. As used herein, the "tertiary carbonate group" comprises a tertiary carbonate ester group having an alkyl group, a tertiary carbonate ester group having an aryl group, and a tertiary carbonate ester group having a combination of an alkyl group and an aryl group. Preferably, the acid-unstable group of the second repeating unit comprises a tertiary ester group.

[0070] The second repeating unit of the polymer may comprise an acid-unstable group derived from one or more monomers of formulas 8, 9, 10, 11 and / or 12:

[0071] [Chemical Formula 8]

[0072]

[0073] [Chemical Formula 9]

[0074]

[0075] [Chemical Formula 10]

[0076]

[0077] [Chemical Formula 11]

[0078]

[0079] [Chemical Formula 12]

[0080]

[0081] In chemical formulas 8 to 12, each R d is independently hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 Alkyl, or substituted or unsubstituted C 1-10 It is a fluoroalkyl. Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl, typically methyl.

[0082] In chemical formula 8, L 5 is a 2-fold connector. For example, L 5 may be a divalent linker comprising at least one carbon atom, at least one heteroatom, or a combination thereof. For example, L 5 It may include 1 to 10 carbon atoms and at least one heteroatom. In one or more embodiments, L 5 -OCH2-, -OCH2CH2O- or -N(R c )-can be, and here R c is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted, or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 Aryl, or substituted or unsubstituted C 3-10 It is a heteroaryl.

[0083] In chemical formulas 8, 9, and 11, R 10 to R 12 Each is 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 2-20It may be heteroaryl, but R 10 to R 12 Only one of them can be hydrogen, and R 10 to R 12 If one is hydrogen, the remaining R 10 to R 12 One or both are substituted or unsubstituted C 6-20 Aryl, or substituted or unsubstituted C 4-20 It is heteroaryl. Preferably, R 10 to R 12 C, each independently substituted or unsubstituted 1-6 Alkyl, or substituted or unsubstituted C 3-10 It is cycloalkyl.

[0084] In chemical formula 8, R 10 to R 12 Any two of them optionally form a loop together, and R 10 to R 12 Each is optionally -O-, -C(O)-, -N(R c It may include one or more groups selected from )-, -S-, or -S(O)2-, where R c is hydrogen, straight-chain or branched C 1-20 Alkyl, monocyclic, or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 1-20 It can be a heterocycloalkyl. For example, R 10 to R 12 Any one or more of the chemical formula -CH2C(=O)CH (3-n) Y n It may be a period of, where each Y is independently substituted or unsubstituted C 1-30 It is heterocycloalkyl, and n is 1 or 2. For example, each Y independently has the chemical formula -O(C a1 )(C a2 Substituted or unsubstituted C containing )O- groups 1-30 It may be a heterocycloalkyl, where C a1and C a2 Each is independently hydrogen, or substituted or unsubstituted C 1-10 It is alkyl, and C a1 and C a2 It selectively forms a ring together.

[0085] In chemical formulas 10 and 12, R 13 and R 14 Each is 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 can be heteroaryl; R 15 is substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 1-30 It may be heterocycloalkyl. Optionally, R 13 or R 14 One of them is R 15 A complex ring can be formed together with. Preferably, R 13 and R 14 Each is independently hydrogen, substituted, or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 1-20 It can be a heterocycloalkyl.

[0086] In chemical formulas 11 and 12, respectively, X d is a polymerizable group independently selected from vinyl and novonyl; L 5 and L 6 Each is independently a single bond or a divalent linkage, except X d If it is vinyl, L 5 and L 6 may not be a single bond. Preferably, L 5 and L 6Each is independently substituted or unsubstituted C 6-30 Aryllene, or substituted or unsubstituted C 3-30 It is cycloalkylene.

[0087] In chemical formulas 11 and 12, n1 and n2 can each be independently 0 or 1. When n1 or n2 is 0, the corresponding L 5 or L 6 The energy should be understood as being directly connected to each oxygen atom.

[0088] Non-limiting examples of monomers for providing a second repeating unit comprising an acid-unstable group include the following:

[0089]

[0090]

[0091]

[0092] During the meal, R d is hydrogen, halogen, substituted or unsubstituted C 1-6 Alkyl, or substituted or unsubstituted C 3-6 It is cycloalkyl.

[0093] The second repeating unit may include a basophilic group. Exemplary basophilic groups include a hydroxyaryl group, a fluoroalcohol group (e.g., -C(CF3)2OH), a sulfonamide group (e.g., -NHSO2CF3), or a combination thereof.

[0094] As used herein, "hydroxyaryl group" refers to an aryl group in which a hydroxyl group is directly bonded to an aromatic ring carbon. "Hydroxy" is to be understood to mean that one or more hydroxyl groups are incorporated into the group. For example, C 6-12 When a hydroxy-aryl group is shown, the hydroxy-aryl group may include one or more hydroxyl groups, for example, a single hydroxyl group, two hydroxyl groups, three or more hydroxyl groups, etc.

[0095] The second repeating unit may include a polar group. Exemplary polar groups include lactone groups, sulfonate groups, hydroxyaryl groups, hydroxyalkyl groups, or combinations thereof. It should be understood that some groups, such as hydroxyaryl groups, can be considered as both basolytic groups and polar groups. In other words, some basolytic groups may also be polar groups.

[0096] For example, the second repeating unit may include a repeating unit of formulas 13, 14, or a combination thereof:

[0097] [Chemical Formula 13]

[0098]

[0099] [Chemical Formula 14]

[0100]

[0101] In chemical formulas 13 and 14, respectively R d is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 It may be alkyl. Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1-5 It can be an alkyl, typically hydrogen or methyl.

[0102] In chemical formulas 13 and 14, L 7 and L 8 Each can independently be a single linkage or one or more divalent linkages. For example, L 7 and L 8 -O-, -C(O)-, -C(O)O-, -N(R b )-, -C(O)N(R c )-, 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 Aryllene, substituted or unsubstituted C 3-10It may be heteroarylene, or a combination thereof, where R c 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 It may be an alkylheteroaryl. In some embodiments, L 7 and L 8 Each independently consists of 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 Aryllene, substituted or unsubstituted C 3-10 It may be one or more groups selected from heteroarylenes, or a combination thereof.

[0103] In chemical formula 13, R 16 is substituted or unsubstituted C 1-100 or C 1-20 Alkyl, typically C 1-12 Alkyl; substituted or unsubstituted C 3-30 or C 3-20 Cycloalkyl; substituted or unsubstituted poly(C 1-3 Alkylene oxide); or monocyclic, polycyclic, or fused polycyclic C 4-20 It may be a lactone-containing group. Substituted C 1-100 or C 1-20Alkyl, substituted C 3-30 or C 3-20 cycloalkyl, and substituted poly(C 1-3 The alkylene oxide is substituted with one or more of a sulfonamide group (e.g., -NHSO2CF3), a hydroxyl group (-OH), or a fluoroalcohol group (e.g., -C(CF3)2OH).

[0104] In chemical formula 14, Ar 1 is a substituted C optionally comprising one or more aromatic cyclic heteroatoms selected from N, O, S, or combinations thereof. 5-60 It can be an aromatic group, and the aromatic group can be monocyclic, non-fusion polycyclic, or fusion polycyclic. C 5-60 When the aromatic group is polycyclic, the ring or ring group may be a fused member (e.g., naphthyl), a non-fused member, or a combination thereof. Polycyclic C 5-60 Where the aromatic group is a non-fusion, the ring or cyclic group may be directly connected (e.g., biaryl, biphenyl, etc.) or cross-linked by a heteroatom (e.g., triphenylamino or diphenylene ether). In some embodiments, polycyclic C 5-60 Aromatic groups may include a combination of a fusion ring and a direct linkage ring (e.g., vinaphyl, etc.).

[0105] In Chemical Formula 14, y may be an integer of 1 to 12, preferably 1 to 6, and typically 1 to 3. Each R x can independently be hydrogen or methyl, provided that at least one R x is hydrogen.

[0106] Non-limiting examples of the second repeating unit of the polymer may include the following:

[0107]

[0108]

[0109] During the meal, R dis hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 It may be alkyl. Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1-5 It can be alkyl, typically methyl.

[0110] The second repeating unit, if present, is incorporated into the polymer in an amount typically from 20 to 80 mol%, more typically from 25 to 75 mol%, and even more typically from 30 to 70 mol% based on the total repeating units of the polymer.

[0111] The first repeating unit and the second repeating unit should be understood as structurally different in the polymer.

[0112] In one embodiment, the polymer may further include a third repeating unit, and the third repeating unit is different from the first repeating unit and the second repeating unit.

[0113] In one or more embodiments, the third repeating unit may include a hydroxyaryl group, a sulfonamide group, a fluoroalcohol group, or a combination thereof.

[0114] Where present, the polymer is typically 10 to 60 mol%, typically 10 to 50, based on the total repeating units of the polymer. It includes a third repeating unit in an amount of mol%, more typically 10 to 40 mol%.

[0115] In some embodiments, the polymer may optionally further comprise one or more additional repeating units. The additional repeating units may be one or more additional units for adjusting the properties of the photoresist composition, for example. Exemplary additional units may include units derived from one or more of (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. Where one or more additional repeating units are present in the polymer, they may be used in an amount of up to 90 mol%, typically 3 to 50 mol%, based on the total repeating units of the polymer.

[0116] Non-limiting exemplary polymers of the present invention may include the following:

[0117]

[0118] In the formula, a, b, and c each represent the mole% of repeating units based on 100 mole% of total repeating units in the polymer.

[0119] Polymers typically have a weight-average molecular weight (M w The molecular weight is 1,000 to 50,000 daltons (Da), preferably 2,000 to 30,000 Da, more preferably 2,500 to 20,000 Da, and even more preferably 3,500 to 15,000 Da. The PDI of the polymer is typically 1.1 to 3, more typically 1.1 to 2. The molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.

[0120] The polymer may be prepared using any suitable method(s) in the art. For example, one or more monomers corresponding to the repeating unit described herein may be combined using suitable solvent(s) and initiators, or supplied individually and polymerized in a reactor. For example, the polymer may be obtained by polymerizing each monomer under any suitable conditions, for example, by heating at an effective temperature, chemical radiation of an effective wavelength, or a combination thereof.

[0121] A photoresist composition comprising a polymer and a solvent as described herein is also provided. For example, the photoresist composition may comprise a first polymer which is a polymer as described herein and may further comprise a second (different) polymer which is structurally different from the first polymer.

[0122] 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 comprising acid instability groups, hydroxyaryl groups, fluoroalcohol groups, sulfonamide groups, lactone groups, or combinations thereof.

[0123] The second polymer is typically M w Ga is 1,000 to 50,000 Da, 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. M n M regarding w The PDI of the polymer is typically 1.1 to 3, specifically 1.1 to 2. The molecular weight is determined by GPC using a polystyrene standard.

[0124] The second polymer may 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 suitable solvent(s) and initiators, supplied individually, or polymerized in a reactor. For example, the second polymer may be obtained by polymerizing each monomer under any suitable conditions, for example, by heating at an effective temperature, chemical radiation of an effective wavelength, or a combination thereof.

[0125] When the photoresist composition comprises 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.

[0126] The photoresist composition comprises a solvent for dissolving the components of the composition and facilitating coating onto a substrate. Preferably, the solvent is an organic solvent commonly used in the manufacture of electronic devices. Suitable solvents include, for example, the following: aliphatic hydrocarbons, e.g., hexane and heptane; aromatic hydrocarbons, e.g., toluene and xylene; halogenated hydrocarbons, e.g., dichloromethane, 1,2-dichloroethane and 1-chlorohexane; alcohols, e.g., methanol, ethanol, 1-propanol, iso-propanol, tert-butanol, 2-methyl-2-butanol and 4-methyl-2-pentanol; propylene glycol monomethyl ether (PGME); ethers, e.g., diethyl ether, tetrahydrofuran, 1,4-dioxane and anisole; Ketones, e.g., acetone, methyl ethyl ketone, methyl iso-butyl ketone, 2-heptanone and cyclohexanone (CHO); esters, e.g., ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM) and ethyl acetoacetate; lactones, e.g., gamma-butyrolactone (GBL) and epsilon-caprolactone; lactams, e.g., N-methylpyrrolidone; nitriles, e.g., acetonitrile and propionitrile; cyclic or acyclic carbonate esters, e.g., propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate and propylene carbonate; polar aprotic solvents, e.g., dimethyl sulfoxide and dimethyl formamide; water; and combinations thereof. Preferred solvents among these are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof. The total solvent content in the photoresist composition (i.e., cumulative solvent content for all solvents) is typically 40 to 99 wt%, more typically 70 to 99 wt%, and even more typically 85 to 99 wt% based on the total weight of the photoresist composition.The desired solvent content will vary depending, for example, the desired thickness of the coated photoresist layer and the coating conditions.

[0127] In the photoresist composition, the polymer is typically present in the photoresist composition in an amount of 10 to 99.9 weight%, typically 25 to 99 weight%, and more typically 50 to 95 weight% based on the total solids of the photoresist composition. It will be understood that the total solids comprise the polymer, PAG, and other non-solvent components.

[0128] The photoresist composition may further comprise a photogenerator (PAG). The PAG may be in an ionic or non-ionic form. The PAG may be in a polymeric or non-polymeric form. In the polymeric form, the PAG may exist as a moiety in repeating units of a polymer derived from polymerizable PAG monomers.

[0129] Suitable PAG compounds are those with the chemical formula G + A - It can have, and here G + is a photoactive cation, and A - is an anion capable of generating a photovoltaic cation. The photoactive cation is preferably selected from onium cations, preferably iodonium or sulfonium cations. Particularly suitable anions include those having a pKa of conjugate acid of -15 to 10. The anion is typically an organic anion having a sulfonate group or a non-sulfonate type group, such as sulfonamidate, sulfonimidate, methide, or borate.

[0130] 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:

[0131] [Chemical Formula 15]

[0132]

[0133] [Chemical Formula 16]

[0134]

[0135] In chemical formulas 15 and 16, R 17 to R 21 Each is independently substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 6-30 Iodoaryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 7-20 Arylalkyl, or substituted or unsubstituted C 4-20 It may be a heteroarylalkyl, or a combination thereof. R 17 to R 19 Each is separate, or different R through a single connection or a bivalent connector. 17 to R 19 It can be connected to form a ring. R 20 and R 21 They can be separated, or connected to each other through single bonds or divalent linkers to form a ring. R 17 to R 21 Each may optionally include a bivalent connector as part of its structure. R 17 to R 21 Each may independently optionally include 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.

[0136] An exemplary sulfonium cation of Chemical Formula 15 may include one or more of the following:

[0137] .

[0138] An exemplary iodine cation of Chemical Formula 16 may include one or more of the following:

[0139] .

[0140] Exemplary organic anions having a sulfonate group may include one or more of the following:

[0141] .

[0142] Exemplary non-sulfonated anions may include one or more of the following:

[0143] .

[0144] Commercially available onium salts may 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 camphosulfonate. Other useful PAG compounds are known in the field of chemically amplified photoresists, for example, non-ionic sulfonyl compounds, for example, 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; Sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, e.g., bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime, and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, e.g., N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester; and halogen-containing triazine compounds, e.g., 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine are included. Suitable photogenerators are further described in U.S. Patent Applications No. 8,431,325 and No. 4,189,323.

[0145] In some embodiments, the first polymer may optionally further comprise repeating units comprising a PAG moiety, for example, repeating units derived from one or more monomers of Formula 8:

[0146] [Chemical Formula 8]

[0147]

[0148] In chemical formula 8, R m Silver is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 It may be alkyl. Preferably, R m It is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl, typically methyl. Q 1 It can be a single bond or a divalent linker. Preferably, Q 1 It may include 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0149] In chemical formula 8, A 1 is substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Aryllene, or substituted or unsubstituted C 3-30 It may be one or more of heteroarylenes. Preferably, A 1 is an optionally substituted divalent C 1-30 It can be a perfluoroalkylene group.

[0150] In chemical formula 8, Z - is an anionic moiety, and its conjugate acid typically has a pKa of -15 to 1. Z - It may be a sulfonate, carboxylate, sulfonamide anion, sulfonimide anion, or methide anion. Particularly preferred anionic moiety is fluorinated alkyl sulfonate and fluorinated sulfonimide.

[0151] In chemical formula 8, G + is an organic cation as defined above. In some embodiments, G +is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups.

[0152] Exemplary monomers of Chemical Formula 8 include the following:

[0153]

[0154] Among foods, G + is an organic cation.

[0155] The polymer may contain repeating units containing PAG moiety in an amount of 1 to 15 mol%, typically 1 to 8 mol%, and more typically 2 to 6 mol% based on the total repeating units in the polymer.

[0156] Typically, when the photoresist composition comprises a non-polymeric PAG, the PAG is present in the photoresist composition in an amount of 0.1 to 55 weight%, more typically 1 to 25 weight%, based on the total solids of the photoresist composition. When present in a polymeric form, the PAG is typically included 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.

[0157] In some embodiments, the anions and / or cations of the PAG do not contain -F, -CF3, or -CF2- groups and are absent. It should be understood that "absent -F, -CF3, or -CF2- groups" means that groups such as -CH2CF3 and -CH2CF2CH3 are excluded from the anions and / or cations of the PAG. In another embodiment, the anions and / or cations of the PAG are fluorine-free (i.e., do not contain fluorine atoms and are not substituted by fluorine-containing groups). In some embodiments, the photogenerator is fluorine-free (i.e., fluorine is absent in both the photoactive cations and anions).

[0158] In some embodiments, the photoresist composition may further comprise a material comprising one or more base-unstable groups ("base-unstable material"). As described herein, the base-unstable group is a functional group capable of providing a polar group, such as a hydroxyl, carboxylic acid, sulfonic acid, etc., in the presence of an aqueous alkali developer after the exposure and post-exposure baking steps, through a cleavage reaction. The base-unstable group will not significantly react prior to the development step of the photoresist composition comprising the base-unstable group (e.g., will not undergo a bond-breaking reaction). Thus, for example, the base-unstable group will be substantially inactive during the pre-exposure soft baking, exposure, and post-exposure baking steps. "Substantially inactive" means that 5% or less, typically 1% or less, of the base-unstable group (or moiety) will decompose, cleave, or react during the pre-exposure soft baking, exposure, and post-exposure baking steps. The base-unstable group is reactive under typical photoresist development conditions using an aqueous alkali photoresist developer, such as, for example, an aqueous solution of 0.26 N tetramethylammonium hydroxide (TMAH). For example, an aqueous solution of 0.26 N TMAH may be used for single puddle development or dynamic development (e.g., when dispensing the 0.26 N TMAH developer onto the imaged photoresist layer for a suitable time, such as 10 to 120 seconds). An exemplary base-unstable group is an ester group, typically a fluorinated ester group. Preferably, the base-unstable material is substantially miscible with the polymer and other solid components of the photoresist composition and has a lower surface energy than them. Consequently, when coated onto a substrate, the base-unstable material can be separated from the other solid components of the photoresist composition to the top surface of the formed photoresist layer.

[0159] In some embodiments, the base-unstable material may be a polymeric material (also referred to herein as a base-unstable polymer) that may comprise one or more repeating units comprising one or more base-unstable groups. For example, the base-unstable polymer may comprise repeating units comprising two or more identical or different base-unstable groups. A preferred base-unstable polymer comprises at least one repeating unit comprising two or more base-unstable groups, for example, a repeating unit comprising two or three base-unstable groups.

[0160] Basicly unstable polymers can be prepared using any suitable method in the art. For example, basicly unstable polymers can be obtained by polymerizing each monomer under any suitable conditions, such as heating at an effective temperature, chemical radiation of an effective wavelength, or a combination thereof. Additionally, or alternatively, one or more basicly unstable groups can be grafted onto the backbone of the polymer using a suitable method.

[0161] In some embodiments, the base-unstable material is a single molecule comprising one or more base-unstable ester groups, preferably one or more fluorinated ester groups. The single molecule base-unstable material typically has a molecular weight in the range of 50 to 1,500 Da.

[0162] When present, the basic unstable material is typically present in the photoresist composition in an amount of 0.01 to 10 weight%, typically 1 to 5 weight%, based on the total solids of the photoresist composition.

[0163] In addition to or alternatively to the base-unstable polymer, the photoresist composition may further comprise one or more polymers that are different from and in addition to the polymers described above. For example, the photoresist composition may comprise additional polymers or polymers that are as described above but have a different composition. In addition to or alternatively, one or more additional polymers may comprise those well known in the field of photoresists, for example, polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene-based polymers, polyvinyl alcohols, or combinations thereof.

[0164] The photoresist composition may further comprise one or more additional optional additives. For example, the optional additives may comprise chemical line dyes and contrast dyes, anti-striation agents, plasticizers, rate enhancers, sensitizers, photo-decomposable quenchers (PDQ) (and, also known as photodecomposable bases), basic quenchers, thermal acid generators, surfactants, etc., or combinations thereof. Where present, the optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 weight percent based on the total solids of the photoresist composition.

[0165] PDQ generates a weak acid upon irradiation. The acid generated from the photodegradable quencher is not strong enough to rapidly react with acid-unstable groups present in the resist matrix. An exemplary photodegradable quencher includes, for example, a photodegradable cation, and preferably, for example, C 1-20 Carboxylic acid or C 1-20It includes those that are also useful for preparing strong acid-generating compounds that are 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 a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0166] PDQ may be in a non-polymeric or polymer-bonded form. The polymerized units containing the photodegradable quencher are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0167] Exemplary basic quenchers include, for example, linear aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(2-hydroxypropyl)ethylenediamine, N-tert-butyldiethanolamine, tris(2-acetoxy-ethyl)amine, 2,2',2",2'''-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2"-nitrilotriethanol; Cyclic aliphatic amines, e.g., 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidine carboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N-(2-acetoxy-ethyl)morpholine; aromatic amines, e.g., pyridine, di-tert-butylpyridine, and pyridinium; linear and cyclic amides and their derivatives, e.g., N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3- Tetrabutylmalonamide, 1-methylasepan-2-one, 1-allylasepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts, e.g., quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines, e.g., primary and secondary aldimines and ketimines; diazines, e.g., optionally substituted pyrazines, piperazines, and phenazines; diazoles, e.g., optionally substituted pyrazols, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones, e.g., 2-pyrrolidone and cyclohexylpyrrolidone are included.

[0168] The basic quencher may be in a non-polymeric or polymeric form. In the case of a polymeric form, the quencher may be present in the repeating units of the polymer. The repeating units containing the quencher are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0169] Exemplary surfactants include fluorinated surfactants and non-fluorinated surfactants, which may be ionic or non-ionic, and non-ionic surfactants are preferred. Exemplary fluorinated non-ionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In one embodiment, the photoresist composition further comprises a surfactant polymer comprising fluorine-containing repeating units.

[0170] A method for forming a pattern is also provided. According to one embodiment, the method for forming a pattern comprises the steps of: applying a layer of a photoresist composition onto a substrate to form a layer of the photoresist composition; exposing the layer of the photoresist composition to active radiation in a patterned manner to form an exposed layer of the photoresist composition; and developing the exposed layer of the photoresist composition. 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 another embodiment, 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; and includes a third repeating unit as provided herein.

[0171] A patterning method using the photoresist composition of the present invention will now be described. Suitable substrates to which the photoresist composition can be coated include electronic device substrates. Various electronic device substrates such as semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multichip modules; flat panel display substrates; and substrates for light-emitting diodes (LEDs), including organic light-emitting diodes (OLEDs), may 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, integrated optical circuits, and LEDs. Such substrates may be of any suitable size. While wafers of smaller and larger diameters may be suitably used according to the present invention, a typical wafer substrate diameter is 200 to 300 millimeters (mm). The substrate may include one or more layers or structures that may optionally include an active or operable portion of the device being formed.

[0172] Typically, before coating the photoresist composition of the present invention, one or more lithography layers, such as a hard mask layer, such as spin-on-carbon (SOC), amorphous carbon, or a metal hard mask layer, a CVD layer, such as a silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer, an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of a substrate. Such layers form a lithography material stack together with the overcoated photoresist layer.

[0173] Optionally, a layer of adhesion promoter may be applied to the substrate surface before coating the photoresist composition. If an adhesion promoter is required, any adhesion promoter suitable for polymer films, such as silanes, typically organic silanes, such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane couplers, such as gamma-aminopropyltriethoxysilane, may be used. Particularly suitable adhesion promoters include those sold under the names AP™ 3000, AP™ 8000, and AP™ 9000S, available from DuPont Electronics & Industrial (Marlborough, Massachusetts, USA).

[0174] The photoresist composition may be coated onto a substrate by any suitable method including spin coating, spray coating, dip coating, doctor blade, etc. For example, the application of a layer of photoresist may be achieved by spin-coating the photoresist in a solvent using a coating track, wherein the photoresist is dispensed onto a spinning wafer. During dispensing, a layer of the photoresist composition on the substrate is obtained by spinning the wafer at a speed of up to 4,000 rpm (revolutions per minute), e.g., 200 to 3,000 rpm, e.g., 1,000 to 2,500 rpm, for a period typically of 15 to 120 seconds. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by varying the spin speed and / or the total solids of the composition. A layer of the photoresist composition formed from the composition of the present invention typically has a dried layer thickness of 3 to 30 micrometers (μm), preferably greater than 5 to 30 μm, and more preferably 6 to 25 μm.

[0175] Next, the photoresist composition is typically soft-baked to minimize the solvent content within 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 soft-baking temperature and time will vary, for example, depending on the photoresist composition and thickness. The soft-baking temperature is typically 80 to 170°C, more typically 90 to 150°C. The soft-baking time is typically 10 seconds to 20 minutes, more typically 1 to 10 minutes, and even more typically 1 to 2 minutes. The heating time can be easily determined by a person skilled in the art based on the components of the composition.

[0176] Next, the photoresist layer is exposed to active radiation in a patterned manner to create a solubility difference between the exposed and unexposed areas. References herein to exposing the photoresist composition to radiation that is active to the composition indicate that the radiation may form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions corresponding to the areas to be exposed and unexposed of the resist layer, respectively. Alternatively, such exposure may be performed without a photomask using a direct lighting method typically used in electron beam lithography. The active radiation typically has a wavelength of less than 400 nanometers (nm), less than 300 nm, or less than 200 nm, and 248 nm (KrF), 193 nm (ArF), and 13.5 nm (EUV) wavelengths or electron beam lithography are preferred. Preferably, the active radiation is 248 nm radiation. This method is used in immersion or dry (non-immersion) lithography techniques. The exposure energy is typically 1 to 200 mJ / cm², depending on the components of the exposure tool and the photoresist composition. 2(millijoules per square centimeter), preferably 10 to 100 mJ / cm² 2 , more preferably 20 to 50 mJ / cm² 2 am.

[0177] After the 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. Conditions for PEB will vary, for example, depending on the photoresist composition and layer thickness. PEB is typically performed for a time of 30 to 120 seconds at a temperature of 70 to 150°C, preferably 75 to 120°C. A latent image is formed on the photoresist, defined by polarity-switched regions (exposed regions) and non-switched regions (unexposed regions).

[0178] The exposed photoresist layer is then developed with a suitable developer to selectively remove regions of the layer soluble in the developer, while the remaining insoluble regions form the generated photoresist pattern relief image. In the case of a positive-tone development (PTD) process, the exposed regions of the photoresist layer are removed during development, and the unexposed regions remain. Conversely, in a negative-tone 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 suitable method as described above for the application of the photoresist composition, and spin coating is typical. The development time is the period effective for removing the soluble regions of the photoresist, and a time of 5 to 60 seconds is typical. Development is typically performed at room temperature.

[0179] Developers suitable for the PTD process include aqueous basic developers, for example, quaternary ammonium hydroxide solutions, such as TMAH, preferably 0.26 N TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Developers suitable for the NTD process are organic solvent-based, meaning that the cumulative content of the organic solvent in the developer is 50 wt% or more, typically 95 wt% or more, 98 wt% or more, or 100 wt% based on the total weight of the developer. Organic solvents suitable for the NTD developer include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0180] A substrate coated from the photoresist composition of the present invention may be formed. Such a coated substrate comprises: (a) a substrate having one or more layers to be patterned on a surface; and (b) a layer of the photoresist composition on one or more layers to be patterned.

[0181] A photoresist pattern can be used, for example, as an etching mask, thereby allowing the pattern to be transferred to one or more sequential underlying layers by dry etching, typically such as reactive ion etching, by known etching techniques. The photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, and the hard mask layer is consequently 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, the photoresist pattern can be removed from the substrate by known techniques, for example, oxygen plasma ashing. The photoresist composition can be used to manufacture semiconductor devices, such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices when used in one or more such patterning processes.

[0182] The present invention is further explained by the following non-limiting embodiments.

[0183] Examples

[0184] Synthetic example

[0185] The synthesis reaction was carried out under an anhydrous nitrogen atmosphere. All chemicals were used exactly as obtained from commercial suppliers without further purification. Proton nuclear magnetic resonance for all compounds ( 1 H-NMR spectra were obtained using a 499 megahertz (MHz) NMR spectrometer. Chemical shifts are recorded in δ units (parts per million, ppm) for the internal tetramethylsilane standard or deuteration peak. Multiplicity is indicated as a single (s), double (d), triple (t), multiple (m), double of double (dd), double of triple (dt), triple of triple (tt), or broad single (br).

[0186] Synthesis of Monomer MS1

[0187]

[0188] 1,1'-carbonyldiimidazole (CDI) (8.75 g, 54.0 mmol) was added in portions to a solution of 4-vinylbenzoic acid (8.0 g, 54.0 mmol) in tetrahydrofuran (THF, 100 mL). The resulting reaction mixture was stirred at room temperature for 15 minutes. Subsequently, the temperature of the reaction mixture was increased to 60°C, 2-(phenylsulfonyl)ethanol-1-ol (10.0 g, 53.70 mmol) was added, the resulting mixture was stirred, and heated at 60°C for 16 hours. Subsequently, the reaction mixture was allowed to cool to room temperature. The solvent was removed under reduced pressure to produce a crude product as an oil residue. The crude product was dissolved in dichloromethane (150 mL), the solution was washed twice with aqueous ammonium chloride (30 mL, saturated solution), and then washed twice with deionized water (DI) (30 mL). The organic phase was separated, and the solvent was removed under reduced pressure. MS1 It was provided as a white solid. Yield: 12.8 g (75.3%). 1 H 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).

[0189] Synthesis of Monomer MS2

[0190]

[0191] 1,1'-carbonyldiimidazole (CDI) (11.0 g, 67.8 mmol) was added in portions to a solution of 4-vinylbenzoic acid (10.0 g, 67.5 mmol) in THF (100 mL). The resulting mixture was stirred at room temperature for 15 minutes. Subsequently, the temperature of the reaction mixture was increased to 60°C, 2-(methylsulfonyl)ethanol-1-ol (8.4 g, 69.13 mmol) was added, the resulting mixture was stirred, and heated at 60°C for 16 hours. Subsequently, the reaction mixture was allowed to cool to room temperature. The solvent was removed under reduced pressure to produce a crude product as an oil residue. The crude product was dissolved in dichloromethane (150 mL), and the solution was washed twice with aqueous ammonium chloride (30 mL, saturated solution) and then twice with deionized water (DI) (30 mL). The organic phase was separated, and the solvent was removed under reduced pressure. MS2 was provided as a white solid. Yield: 15.85 g (92.3%). 1 ¹H NMR (δ, acetone-d6): 8.03 ppm (d, 2H, 3Ar H ), 7.62 ppm (d, 2H, 2Ar H ), 6.84 ppm (m, 1H, C H =CH2), 5.99 ppm (d, 1H, CH=C H 2), 5.44 ppm (d, 1H, CH=C H 2), 4.76 ppm (t, 2H, C H 2O), 3.65 ppm (t, 2H, C H 2SO2), and 3.1 ppm (s, 3h SO2CH3).

[0192] Synthesis of Monomer MS3

[0193]

[0194] 2-propanethiol (12.5 mL, 134.6 mmol) was slowly added to a solution of potassium hydroxide (8.36 g, 149.3 mmol) in methanol (150 mL). 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. Intermediate product MS3-i ...was extracted from water using methyl t-butyl ether and isolated, then washed with a dilute aqueous potassium hydroxide solution and subsequently washed with a brine solution. The resulting intermediate product was dried under vacuum to obtain a clear oil. Yield: 11.71 g (96%).

[0195] Intermediate product MS3-i A solution was prepared by combining (11.1 g, 53.3 mmol) and triethylamine (TEA, 20 mL, 143.5 mmol) with 150 mL of methyl t-butyl ether. To this, methacryloyl chloride (7 mL, 71.7 mmol) was added dropwise at room temperature while constantly stirring, and the reaction mixture was then stirred for an additional 4 hours. The intermediate product was extracted using methyl t-butyl ether and water. MS3-ii ...was isolated. The resulting product was washed twice with a dilute aqueous hydrochloric acid solution, once with a dilute aqueous potassium hydroxide solution, and then once with an aqueous brine solution. The obtained product was dried under reduced pressure to obtain an intermediate product as a transparent oil. MS3-ii was obtained. Yield: 11.60 g (79%).

[0196] 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 in five separate additions, and the resulting reaction mixture was stirred at room temperature for an additional 1 hour. The crude product was isolated by extraction using methyl t-butyl ether and water. The product was crystallized from a minimum volume of heptane and further purified as a wax-type solid MS3 Provided. Yield: 5.37 g (39%). 1 H-NMR (δ, acetone-d6): 6.18 ppm (d, 1H, CH=CH H ), 5.83 ppm (tt, 1H, OC H ), 5.72 ppm (p, 1H, CH=CH H ), 3.73 ppm (qd, 4H, SO2C H 2), 3.32 ppm (p, 2H, SO2C H ), 1.95 ppm (s, 3H, CC H 3), and 1.37 ppm (dd, 12H, CHC H 3).

[0197] Synthesis of Monomer MS4

[0198]

[0199] 1-Hexanethiol (21 mL, 148.8 mmol) was slowly added to a solution of potassium hydroxide (8.42 g, 150.1 mmol) in methanol (200 mL). 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 an additional 15 hours. Intermediate product MS4-i [The substance] was extracted and isolated using methyl t-butyl ether and water, then washed with a dilute aqueous potassium hydroxide solution and subsequently washed with a saline solution. 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.

[0200] Intermediate product MS4-i A solution was prepared by combining (9.61 g, 32.8 mmol) and TEA (12 mL, 86.1 mmol) with methyl t-butyl ether (120 mL). To this, methacryloyl chloride (5 mL, 51.2 mmol) was added dropwise at room temperature while stirring constantly. The reaction mixture was allowed to be stirred continuously at room temperature for an additional 4 hours. The intermediate product was obtained by extraction using methyl t-butyl ether and water. MS4-ii ...was isolated. The resulting product was washed twice with a dilute aqueous hydrochloric acid solution, once with a dilute aqueous potassium hydroxide solution, and then once with an aqueous brine solution. The obtained product was dried under reduced pressure to obtain an intermediate product as a transparent oil. MS4-ii was obtained. Yield: 12.07 g, with residual hexyl disulfide and methacrylic anhydride. The impurities were transferred and did not affect the next step.

[0201] 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 in a total of five installments, and the resulting reaction mixture was stirred at room temperature for an additional 1 hour. The crude product was isolated by extraction using methyl t-butyl ether and water. The product was crystallized from a minimum volume of heptane and further purified as a wax-type solid MS4 provided. Yield: 4.29 g (62%). 1 H-NMR (δ, chloroform-d1): 6.24 ppm (s, 1H, CH=CHH ), 5.72 ppm (m, 2H, CH=CH H and OC H ), 3.59 ppm (qd, 4H, SO2C H 2CH), 3.08 ppm (m, 4H, SO2C H 2 CH2), 1.99 ppm (s, 3H, CC H 3), 1.87 ppm (m, 4H, SO2CH2C H 2), 1.46 ppm (p, 4H, SO2CH2CH2C H 2), 1.34 ppm (m, 4H, CH3CH2C H 2), 1.34 ppm (m, 4H, CH3CH2C H 2 and CH3C H 2), and 0.92 ppm (t, 6H, CH2C H 3).

[0202] Polymer synthesis

[0203] Polymers P1 to P6 and comparative polymers CP1 to CP4 were prepared using the following monomers.

[0204]

[0206] Synthesis of polymer P1

[0207] Polymer P1 was prepared from monomers MA1, MB2, and MS1 in a molar feed ratio of 45:45:10. A feed 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 prepared separately by dissolving 2.32 g of azo-initiator dimethyl 2,2'-azobis(2-methylpropionate) (obtained as V-601 from Wako Pure Chemical Industries, Ltd.) in 6.43 g of a 1:1 (w / w / ) mixture of PGMEA / tetrahydrofuran.

[0208] Polymerization was carried out in a three-necked round-bottom flask equipped with a thermometer and a water condenser to monitor the reaction within the flask. 10.0 g of PGMEA was charged into the reactor and heated to 75°C. Using a syringe pump, the feed solution and the initiator solution were supplied to the reactor separately over a period of 4 hours. After addition, the contents were stirred for an additional 2 hours. Subsequently, the contents were cooled to room temperature and diluted with 20 g of PGMEA to produce a crude polymer solution. Next, the acetal groups within 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 resulting crude polymer was dissolved in acetone (25 g). The acetone polymer solution was slowly added to an excess amount of deionized water to precipitate the polymer. The generated polymer precipitate was isolated by filtration and washed with deionized water. Subsequently, the polymer product was dried at 35°C under reduced pressure.

[0209] Synthesis of polymers P2 to P5 and comparative polymers CP1 to CP4

[0210] Each of the polymers in Table 1 was prepared using a procedure similar to that described for the preparation of polymer P1, except that monomers and molar feed ratios (mol%, based on a total of 100 mol%) as specified in Table 1 were used.

[0211] [Table 1]

[0212]

[0213] Lithography evaluation

[0214] Formulation Information

[0215] A photoresist composition was prepared by dissolving solid components in a solvent using the materials and amounts indicated in Tables 2 and 3, wherein the amounts are expressed in weight% units based on 100 wt% of the total weight of the solids. The total solid content of the photoresist composition was 2.5 wt%. The solvent system contained PGMEA (50 wt%) and methyl-2-hydroxyisobutyrate (50 wt%). Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disc filter having a pore size of 0.2 microns.

[0216] Lithography Patterning and Data Analysis

[0217] Lithography was performed using a CLEAN TRAC ACT8 (TEL, Tokyo Electron Co.) wafer track. For photolithography testing, a 200 nm wafer was coated with AR™ 3 BARC (DuPont Electronics & Industrial) and soft-baked at 205°C for 60 seconds to provide a 60 nm film. Subsequently, a coating of AR™ 40A BARC (DuPont Electronics & Industrial) was placed on the AR™ 3 layer and soft-baked at 215°C for 60 seconds to form a second BARC layer with a thickness of approximately 80 nm. Subsequently, a photoresist composition was coated on the double BARC stack and soft-baked at 110°C for 60 seconds to provide a photoresist film layer with a thickness of approximately 70 nm.

[0218] CANON FPA-5000 ES4 using a mask with a 1:1 L / S pattern (120 nm line width) The wafer was exposed to 248 nm radiation on a scanner (NA=0.8, external sigma=0.85, internal sigma=0.57). The wafer was exposed at 100°C for 60 seconds, baked, developed with MF™ CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with deionized water, and spin-dried. The critical dimension (CD) linewidth of the formed pattern was measured using a HITACHI S-9380 CD-SEM. Linewidth roughness (LWR) values ​​were determined by top-down SEM at an acceleration voltage of 800 volts (V) and a probe current of 8.0 picoamperes (pA), using 200 Kx magnification at 1.0 digital zoom with a frame rate set to 64. LWR was measured in 40 nm increments over a 2 μm line length and recorded as the average LWR for the measured area. Sizing energy (E 사이즈 The line width roughness (LWR) of the line was determined based on CD measurements.

[0219] The pseudo-Z-factor is recorded below and was determined according to Equation 1:

[0220] [Mathematical Formula 1]

[0221] Pseudo-Z-factor = (E 사이즈 ) x (LWR) 2

[0222] Here, E 사이즈 is millijoules per square centimeter (mJ / cm²) 2 It is recorded in ) units, LWR is recorded in nanometer (nm) units, and the pseudo-Z-factor is mJ x 10 -11It is recorded in units. The pseudo-Z-factor is a variation of the measure of photoresist performance based on the Z-factor, a known parameter representing RLS (resolution, line edge roughness, sensitivity) photoresist performance (see, for example, the literature [Wallow, T. et al Proc. SPIE 6921, 69211F, 2008]). The pseudo-Z-factor is calculated at a constant resolution (CD size).

[0223] Line space (L / S) patterning

[0224] The photoresist compositions of Table 2 were evaluated for L / S patterning under KrF exposure (248 nm) as described above using a bright-field mask pattern. E 사이즈 and the LWR of the space was determined based on CD measurements. E 사이즈 was determined as the irradiation energy dose at which the target 120 nm L / S pattern is resolved. E 사이즈 , LWR and pseudo-Z factor data are shown in Table 2. Amounts are specified in weight% based on total solids.

[0225] [Table 2]

[0226]

[0227] The structures of PAG-A, PAG-B, Q1, and Q2 are shown below.

[0228] .

[0229] As can be seen from Table 2, photoresist compositions PR-1 to PR-6 have a smaller E compared to comparative examples PR-7 to PR-8. 사이즈Improved sensitivity was achieved, as demonstrated by [the result]. The sensitivity improvement of photoresist compositions PR-1 to PR-6 did not impair line / space feature roughness, as demonstrated by the LWR that was comparable or improved compared to comparative compositions PR-7 to PR-9. In each case, the pseudo-Z-factor of the photoresist compositions PR-1 to PR-6 was lower than that of the comparative photoresist compositions PR-7 to PR-9.

[0230] Line space (L / S) patterning

[0231] The photoresist compositions of Table 3 were prepared in a manner similar to the previous example and evaluated for line / space patterning under KrF exposure. A 200 mm silicon wafer overcoated with a 60 nm thick BARC stack of AR3 anti-reflective agent on an 80 nm thick AR40A anti-reflective agent (DuPont Electronics & Industrial) was spin-coated with each photoresist composition on a TEL Clean Track ACT8 wafer track and soft-baked at 110°C for 60 seconds to provide a photoresist layer with a thickness of approximately 120 nm. The wafers were each exposed to 248 nm radiation on a CANNON FPA-5000 ES4 scanner (NA=0.8, external sigma=0.85, internal sigma=0.57) using a mask having a 120 nm line / space (l / s) pattern. The wafer was exposed at 100°C for 60 seconds, baked, developed with MF-CD26 TMAH developer (DuPont Electronics & Imaging) for 60 seconds, rinsed with deionized water, and spin-dried. The critical dimension (CD) of the formed l / s pattern was measured using a Hitachi S-9380 CD SEM. The linewidth roughness (LWR) in the target 120 nm space was determined based on the CD measurement. The results are shown in Table 3, where the amounts are specified in weight% based on the total solids.

[0232] [Table 3]

[0233]

[0234] As can be seen in Table 3, photoresist compositions PR-10 and PR-11 achieved improved LWR compared to comparative photoresist composition PR-12.

[0235] Although the present disclosure has been described in relation to exemplary embodiments currently available for practice, the invention is not limited to the disclosed embodiments but should be understood to include various modifications and equivalent configurations that fall within the spirit and scope of the appended claims.

Claims

Claim 1 As a polymer, chemical formula -C(R a )(R b A first repeating unit comprising a sulfone group directly bonded to the )- group; and a second repeating unit comprising an acid-unstable group, a base-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, wherein R a and R b Each is 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 R a and R b A polymer in which at least one of the elements is hydrogen, and the first repeating unit is derived from a first monomer represented by Chemical Formula 1: [Chemical Formula 1] (In Chemical Formula 1, X a is a polymerizable group containing an ethylene-based unsaturated carbon-carbon double bond; L 1 is a single bond or linker; each L 2 is independently a single bond, substituted, or unsubstituted C 1-30 Alkylene, or substituted or unsubstituted C 3-30 Becomes cycloalkylene; however, L 1 or L 2 At least one of them is not a single bond; each R 1 C that is independently substituted or unsubstituted 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 becomes an alkylheteroaryl; provided that at least one L 2 or at least one R 1 The chemical formula -C(R) that is directly bonded to -S(=O)2- a )(R b Includes the group of )-; n is an integer from 1 to 5). Claim 2 In paragraph 1, at least one L 2 The chemical formula -C(R that is directly bonded to -S(=O)2- a )(R b A polymer containing )- groups. Claim 3 In paragraph 1, at least one R 1 The chemical formula -C(R that is directly bonded to this -S(=O)2- a )(R b A polymer containing )- groups. Claim 4 The polymer of claim 1, wherein the first repeating unit is derived from a first monomer represented by Chemical Formula 2 or 3: [Chemical Formula 2] [Chemical Formula 3] (In chemical formulas 2 and 3, X b and X c are each independently polymerizable groups comprising an ethylene-based unsaturated carbon-carbon double bond; L 3 and L 4 are each independently a single linkage or a divalent linkage; R 2 , R 3 and R 4 C, each independently substituted or unsubstituted 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 alkylheteroaryl). Claim 5 A polymer according to claim 1, wherein the first monomer comprises a (meth)acryloyl group or a vinyl aromatic group. Claim 6 A polymer according to claim 1, wherein the second repeating unit comprises an acid-unstable group. Claim 7 A photoresist composition comprising the polymer of claim 1; and a solvent. Claim 8 A photoresist composition according to claim 7, wherein the second repeating unit of the polymer comprises an acid-unstable group. Claim 9 A photoresist composition according to claim 7, further comprising a photogenerator. Claim 10 A photoresist composition according to claim 7, further comprising a second polymer structurally different from the polymer. Claim 11 A method for forming a pattern, comprising: a step of applying a layer of the photoresist composition of claim 7 onto a substrate to form a photoresist composition layer; a step of exposing the photoresist composition layer in a patterned manner using active radiation to form an exposed photoresist composition layer; and a step of developing the exposed photoresist composition layer. Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete

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