Polymer, resist composition including the same, and method for forming pattern by using resist composition

Abstract

Provided are a polymer including a first repeating unit represented by Formula 1 wherein the description of L11 to L14, a11 to a13, A11, X11, R11, R12, b12 and p in Formula 1 is provided in the specification, a resist composition including the polymer, and a method of forming a pattern using the resist composition. Formula 1 # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority of Korean Patent Application No. 10-2023-0084525 filed on June 29, 2023, and Korean Patent Application No. 10-2023-0159280 filed on November 16, 2023, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein in their entirety by reference. Technical Field

[0003] The present disclosure relates to a polymer, a resist composition including the same, and a method of forming a pattern by using the resist composition Background Art

[0004] In semiconductor manufacturing, resists whose physical properties change in response to light are used to form fine patterns. Among these resists, chemically amplified resists have been widely used. Chemically amplified resists enable patterning by changing the solubility of the base resin in the developer by reacting the acid formed by the reaction between light and a photoacid generator (photoacid generator) with the base resin again.

[0005] In particular, when high-energy rays such as EUV rays having relatively very high energy are used, the number of photons may be very small even when light having the same energy is irradiated. Therefore, there may be a need for a resist composition that can effectively function even when used in a small amount and that can provide improved sensitivity and / or resolution. Summary of the invention

[0006] Provided are a polymer capable of providing improved sensitivity and / or improved resolution, a resist composition including the polymer, and a method of forming a pattern by using the resist composition.

[0007] Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0008] According to an embodiment of the present disclosure, the polymer may include a first repeating unit represented by Formula 1:

[0009] Formula 1

[0010]

[0011] Among them, in formula 1,

[0012] L 11 To L 13Each independently may be a single bond, O, S, C(=O), C(=O)O, OC(=O), C(=O)NH, NHC(=O), or a linear, branched or cyclic C optionally including a heteroatom. 1 -C 30 Divalent hydrocarbon groups,

[0013] L 14 It may be a linear, branched or cyclic C 1 -C 30 Divalent hydrocarbon groups,

[0014] a11 to a13 may each independently be an integer from 1 to 4,

[0015] A 11 Can be C 6 -C 30 Aromatic group or C 1 -C 30 Heteroaromatic groups,

[0016] R 11 and R 12 Each of them may be independently hydrogen, deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, or a linear, branched or cyclic C optionally including heteroatoms. 1 -C 30 Monovalent hydrocarbon groups,

[0017] b12 can be an integer from 1 to 10,

[0018] X 11 Can be OH, SH or NH 2 ,

[0019] p may be an integer from 1 to 5, and

[0020] *Indicates the binding site with the adjacent atom.

[0021] According to an embodiment of the present disclosure, a resist composition may include the polymer, a photoacid generator, and an organic solvent.

[0022] According to an embodiment of the present disclosure, a method of forming a pattern may include: forming a resist film by applying the photoresist composition, exposing at least a portion of the resist film to high-energy rays to provide an exposed resist film, and developing the exposed resist film by using a developer. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The above and other aspects, features and advantages of some embodiments of the present disclosure will become more apparent from the following description considered in conjunction with the accompanying drawings, in which:

[0024] Figure 1 is a flow chart showing a pattern forming method according to an embodiment;

[0025] Figures 2A to 2C Each is a side cross-sectional view illustrating a pattern forming method according to an embodiment;

[0026] Figures 3A to 3J graphs each showing the normalized residual film thickness according to the exposure level evaluated in Evaluation Example 1;

[0027] Figures 4A to 4E A side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment; and

[0028] Figures 5A to 5E A side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment. DETAILED DESCRIPTION

[0029] Embodiment will now be introduced in detail, and its example is shown in the accompanying drawings, wherein the same reference numerals always refer to the same elements. In this regard, the present embodiment may have different forms and should not be construed as being limited to the description set forth herein. Therefore, the following only describes the embodiment with reference to the accompanying drawings to illustrate aspects. As used herein, the term "and / or" includes any and all combinations of one or more of the related enumerated items. Statements such as "at least one (kind) of" when before or after the list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, "at least one (kind) of A, B and C" and similar language (for example, "selected from at least one (kind) of A, B and C") can be interpreted as only A, only B, only C, or any combination of two or more of A, B and C such as ABC, AB, BC and AC.

[0030] When the term "about" or "substantially" is used in conjunction with a numerical value in this specification, it is intended that the relevant numerical value includes a manufacturing or operating tolerance (e.g., ±10%) around the stated numerical value. In addition, when the words "substantially" and "substantially" are used in conjunction with a geometric shape, it is intended that the accuracy of the geometric shape is not required, but that the tolerance for the shape is within the scope of the present disclosure. In addition, regardless of whether a numerical value or shape is modified as "about" or "substantially", it will be understood that these values ​​and shapes should be interpreted as including a manufacturing or operating tolerance (e.g., ±10%) around the stated numerical value or shape.

[0031] Since the embodiments allow for a variety of changes and many embodiments, the exemplary embodiments will be shown in the drawings and described in detail in the written description. However, this is not intended to limit the embodiments to a specific mode of practice, and it will be understood that all changes, equivalents, and substitutes that do not depart from the spirit and technical scope of the present disclosure are included in the embodiments. In the description of the embodiments, some detailed descriptions of the related art are omitted when it is considered that they may unnecessarily obscure the essence of the present disclosure.

[0032] Terms such as “first”, “second”, “third”, etc. may be used to describe various components, but are only used to distinguish one component (component) from another component (component) and do not limit the order, type, etc. of the components (components).

[0033] It will be understood that when a component such as a layer, film, region or plate is referred to in this specification as being "on" or "over" another component, the component can be directly in contact with, above, below, to the right or to the left of the other component, as well as above, below, to the left or to the right of the other component in a non-contact manner.

[0034] Expressions used in the singular encompass expressions in the plural unless they have clearly different meanings in the context. It will be understood that terms such as "comprises", "having" and "including" are intended to indicate the presence of features, numbers, steps, actions, parts (components), parts, ingredients, materials or combinations thereof disclosed in this specification, and are not intended to exclude the possibility that one or more other features, numbers, steps, actions, parts (components), parts, ingredients, materials or combinations thereof may be present or may be added.

[0035] Whenever a range of values ​​is recited, that range includes all values ​​within that range, as if clearly and unambiguously recorded, and may further include the boundaries of that range. Thus, the statement "X" to "Y" includes all values ​​between X and Y, including X and Y.

[0036] As used herein, the term "C x -C y " refers to the case where the number of carbon atoms constituting the substituent is x to y. For example, the term "C 1 -C 6 " refers to the case where the number of carbon atoms constituting the substituent is 1 to 6, and the term "C 6 -C 20 ” refers to the case where the number of carbon atoms constituting the substituent is 6 to 20.

[0037] The term "monovalent hydrocarbon group" as used herein refers to a monovalent residue derived from an organic compound including carbon and hydrogen or a derivative of the organic compound, and examples thereof may include: a straight-chain or branched alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); a monovalent saturated alicyclic hydrocarbon group (i.e., a cycloalkyl group) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecyl); , tetracyclododecylmethyl, and dicyclohexylmethyl); a monovalent unsaturated aliphatic hydrocarbon group (alkenyl or alkynyl) (e.g., alkenyl, alkynyl, and allyl); a monovalent unsaturated alicyclic hydrocarbon group (e.g., cycloalkenyl and 3-cyclohexenyl); an aryl group (e.g., phenyl, 1-naphthyl, and 2-naphthyl); an arylalkyl group (e.g., benzyl and diphenylmethyl); a monovalent hydrocarbon group containing a heteroatom (e.g., tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl); or any combination thereof. In addition, in these groups, some hydrogen atoms may be replaced by a moiety including a heteroatom such as oxygen, sulfur, nitrogen, or halogen, or some carbon atoms may be replaced by a moiety including a heteroatom such as oxygen, sulfur, or nitrogen. Thus, these groups may each include a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, an ether linkage (bond), an ester linkage, a sulfonate linkage, a carbonate linkage, a lactone ring, a sultone ring, a carboxylic anhydride moiety, or a haloalkyl moiety.

[0038] The term "divalent hydrocarbon group" as used herein refers to a divalent residue in which one hydrogen of the monovalent hydrocarbon group is replaced by a bonding site with an adjacent atom. Examples of divalent hydrocarbon groups may include linear or branched alkylene, cycloalkylene, alkenylene, alkynylene, cycloalkylene, arylene, or a group in which some carbon atoms are replaced by heteroatoms.

[0039] The term "alkyl" as used herein refers to a linear or branched saturated aliphatic hydrocarbon monovalent group, and examples thereof may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, etc. The term "alkylene" as used herein refers to a linear or branched saturated aliphatic divalent hydrocarbon group, and examples thereof may include methylene, ethylene, propylene, butylene, isobutylene, etc.

[0040] The term "haloalkyl" as used herein refers to a group in which one or more hydrogen atoms of an alkyl group are replaced by a halogen, and examples thereof may include CF 3 wait.

[0041] As used herein, the term "alkoxy" refers to a group consisting of the formula -OA 101 A is a monovalent group represented by 101 Examples thereof may include methoxy, ethoxy, isopropoxy and the like.

[0042] As used herein, the term "alkylthio" refers to a group consisting of the formula -SA 101 A is a monovalent group represented by 101 It is an alkyl group.

[0043] The term "haloalkoxy" as used herein refers to a group in which one or more hydrogen atoms of an alkoxy group are replaced by a halogen, and examples thereof may include -OCF 3 wait.

[0044] The term "haloalkylthio" as used herein refers to a group in which one or more hydrogen atoms of an alkylthio group are replaced by halogen, and examples thereof may include -SCF 3 wait.

[0045] The term "cycloalkyl" as used herein refers to a monovalent saturated hydrocarbon cyclic group, and examples thereof may include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc., and polycyclic condensed groups such as norbornyl and adamantyl. The term "cycloalkylene" as used herein refers to a divalent saturated hydrocarbon cyclic group, and examples thereof may include cyclopentylene, cyclohexylene, adamantylene, adamantylenemethyl, norbornylene, norbornylenemethyl, tricyclodecylene, tetracyclododecylene, tetracyclododecylenemethyl, dicyclohexylenemethyl, etc.

[0046] As used herein, the term "cycloalkoxy" refers to a cycloalkyl group of the formula -OA 102 A is a monovalent group represented by 102 is a cycloalkyl group. Examples thereof may include cyclopropyloxy, cyclobutyloxy, and the like.

[0047] As used herein, the term "cycloalkylthio" refers to a group consisting of the formula -SA 102 A is a monovalent group represented by 102 It is a cycloalkyl group.

[0048] As used herein, term "heterocycloalkyl" refers to a group in which some carbon atoms of cycloalkyl are replaced by a portion including heteroatoms such as oxygen, sulphur or nitrogen, and the example of heterocycloalkyl includes ether connection, ester connection, sulfonate connection, carbonate connection, lactone ring, sultone ring or carboxylic anhydride moiety. As used herein, term "heterocycloalkylene" refers to a group in which some carbon atoms of cycloalkylene are replaced by a portion including heteroatoms such as oxygen, sulphur or nitrogen.

[0049] As used herein, the term "heterocycloalkoxy" refers to a 103 A is a monovalent group represented by 103 It is a heterocycloalkyl group.

[0050] As used herein, the term "alkenyl" refers to a linear or branched unsaturated aliphatic monovalent hydrocarbon group including one or more carbon-carbon double bonds. As used herein, the term "alkenylene" refers to a linear or branched unsaturated aliphatic divalent hydrocarbon group including one or more carbon-carbon double bonds.

[0051] As used herein, the term "alkenyloxy" refers to a 104 A is a monovalent group represented by 104 It is an alkenyl group.

[0052] The term "cycloalkenyl" as used herein refers to a monovalent unsaturated cyclic hydrocarbon group including one or more carbon-carbon double bonds. The term "cycloalkenylene" as used herein refers to a divalent unsaturated cyclic hydrocarbon group including one or more carbon-carbon double bonds.

[0053] As used herein, the term "cycloalkenyloxy" refers to a cycloalkenyloxy group of the formula -OA 105 A is a monovalent group represented by 105 It is a cycloalkenyl group.

[0054] As used herein, the term "heterocycloalkenyl" refers to a group in which some of the carbon atoms of a cycloalkenylene group are replaced by a moiety that includes a heteroatom such as oxygen, sulfur, or nitrogen. As used herein, the term "heterocycloalkenyl" refers to a group in which some of the carbon atoms of a cycloalkenylene group are replaced by a moiety that includes a heteroatom such as oxygen, sulfur, or nitrogen.

[0055] As used herein, the term "heterocycloalkenyloxy" refers to a heterocycloalkyleneoxy group of the formula -OA 106 A is a monovalent group represented by 106 It is a heterocycloalkenyl group.

[0056] The term "alkynyl" as used herein refers to a straight-chain or branched unsaturated aliphatic monovalent hydrocarbon group including one or more carbon-carbon triple bonds.

[0057] As used herein, the term "alkynyloxy" refers to a 107 A is a monovalent group represented by 107 It is an alkynyl group.

[0058] The term "aryl" as used herein refers to a monovalent group having a carbocyclic aromatic system, and examples thereof may include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, Ji et al.

[0059] As used herein, the term "aryloxy" refers to a 108 A is a monovalent group represented by 108 It is an aromatic group.

[0060] The term "heteroaryl" as used herein refers to a monovalent group having a heterocyclic aromatic system, and examples thereof may include pyridyl, pyrimidyl, pyrazinyl, etc. The term "heteroarylene" as used herein refers to a divalent group having a heterocyclic aromatic system.

[0061] As used herein, the term "heteroaryloxy" refers to a 109 A is a monovalent group represented by 109 It is a heteroaryl group.

[0062] The term "substituent" as used herein may include: deuterium, halogen, hydroxyl, cyano, nitro, carbonyl, carboxylic acid group, amino, ether moiety, ester moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, or C 1 -C 20 heteroarylthio;

[0063] Each of C is substituted by 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, or C 1 -C 20 Heteroarylthio: deuterium, halogen, hydroxyl, cyano, nitro, carbonyl, carboxylic acid group, amino, ether moiety, ester moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or any combination thereof; and

[0064] Any combination thereof.

[0065] Hereinafter, the present disclosure will be described in detail by illustrating the embodiments with reference to the accompanying drawings, and substantially the same or corresponding parts are given the same reference numerals in the drawings, and their description will be omitted accordingly. With respect to the drawings, the thickness is enlarged to clearly indicate the various layers and regions. In addition, in the drawings, the thickness of some layers and regions is exaggerated for ease of description. Meanwhile, the embodiments described below are illustrative examples of the embodiments, and various changes may be made in form and detail.

[0066] [polymer]

[0067] The polymer according to an embodiment may include a first repeating unit represented by Formula 1:

[0068] Formula 1

[0069]

[0070] Among them, in formula 1,

[0071] L 11 To L 13 may be independently: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C optionally including a heteroatom 1 -C 30 Divalent hydrocarbon groups,

[0072] L 14 It may be a linear, branched or cyclic C 1 -C 30 Divalent hydrocarbon groups,

[0073] a11 to a13 may each independently be an integer from 1 to 4,

[0074] A 11 Can be C 6 -C 30 Aromatic group or C 1 -C 30 Heteroaromatic groups,

[0075] R 11 and R 12 Each of them may be independently: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms. 1 -C 30 Monovalent hydrocarbon groups,

[0076] b12 can be an integer from 1 to 10,

[0077] X 11 Can be OH, SH or NH 2 ,

[0078] p may be an integer from 1 to 5, and

[0079] *Indicates the binding site with the adjacent atom.

[0080] In an embodiment, L in Formula 1 11 To L 13 may be independently: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); substituted or unsubstituted C 1 -C 30 Alkylene; substituted or unsubstituted C 3 -C 30 Cycloalkylene; substituted or unsubstituted C 3 -C 30 Heterocycloalkylene; substituted or unsubstituted C 2 -C 30 Alkenylene; substituted or unsubstituted C 3 -C 30 Cycloalkenylene; substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene; substituted or unsubstituted C 6 -C 30 Arylene; or substituted or unsubstituted C 1 -C 30 Heteroarylene.

[0081] In an embodiment, L in Formula 1 11 To L 13 may be each independently: a single bond; O; C(=O); C(=O)O; OC(=O); and C(=O) each being unsubstituted or substituted with 1 -C 20 Alkylene, C 3 -C 20 Cycloalkylene, C 3 -C 20 Heterocycloalkylene, C 2 -C 20 Alkenylene, C 3 -C 20 Cycloalkenylene, C 3 -C 20 Heterocycloalkenylene, C 6 -C 20 Arylene, and C 1 -C 20Heteroarylene: deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 6 -C 20 aryl, or any combination thereof.

[0082] In an embodiment, L in Formula 1 11 To L 13 may be each independently: a single bond; O; C(=O); C(=O)O; OC(=O); and C(=O) each being unsubstituted or substituted with 1 -C 20 Alkylene, C 3 -C 20 Cycloalkylene, C 3 -C 20 Heterocycloalkylene, phenylene, and naphthylene: deuterium, halogen, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 alkoxy, phenyl, naphthyl, or any combination thereof.

[0083] In an embodiment, L in Formula 1 14 Can be: substituted or unsubstituted C 1 -C 30 Alkylene; substituted or unsubstituted C 3 -C 30 Cycloalkylene; substituted or unsubstituted C 3 -C 30 Heterocycloalkylene; substituted or unsubstituted C 2 -C 30 Alkenylene; substituted or unsubstituted C 3 -C 30 Cycloalkenylene; substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene; substituted or unsubstituted C 6 -C 30 Arylene; or substituted or unsubstituted C 1 -C 30 Heteroarylene.

[0084] In an embodiment, L in Formula 1 14 can be selected from C which is unsubstituted or substituted by 1 -C 20 Alkylene, C 3 -C 20 Cycloalkylene, C 3 -C 20 Heterocycloalkylene, C 2 -C 20 Alkenylene, C 3 -C 20 Cycloalkenylene, C 3 -C 20 Heterocycloalkenylene, C 6 -C 20 Arylene, and C 1 -C 20 Heteroarylene: deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 6 -C 20 aryl, or any combination thereof.

[0085] In an embodiment, L in Formula 1 14 can be selected from C which is unsubstituted or substituted by 1 -C 20 Alkylene, C 3 -C 20 Cycloalkylene, C 3 -C 20 Heterocycloalkylene, phenylene, and naphthylene: deuterium, halogen, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 alkoxy, phenyl, naphthyl, or any combination thereof.

[0086] In formula 1, a11 to a13 represent the quantity L 11 To L 13 .

[0087] In an embodiment, a11 to a13 in Formula 1 may each independently be an integer of 1 to 3.

[0088] In an embodiment, a11 to a13 in Formula 1 may each be 1.

[0089] In an embodiment, A in Formula 1 11 It can be a benzene group, a naphthalene group, a phenanthrene group, an anthracene group, group, a pyrene group, a benzo[9,10]phenanthrene group, a fluorene group, a pyrrole group, a pyridine group, a pyrimidine group, a pyrazine group, a triazine group, a quinoline group, an isoquinoline group, a carbazole group, a furan group, a benzofuran group, a dibenzofuran group, a thiophene group, a benzothiophene group, or a dibenzothiophene group.

[0090] In an embodiment, A in Formula 1 11 It can be a benzene group, a naphthalene group, a phenanthrene group, an anthracene group, group, a pyrene group, a benzo[9,10]phenanthrene group, or a fluorene group.

[0091] In an embodiment, A in Formula 1 11 It may be a benzene group or a naphthyl group.

[0092] In an embodiment, R in Formula 1 11 and R 12 may be independently selected from: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; and C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, and C 6 -C 20 Aryl: deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 6 -C 20 aryl, or any combination thereof.

[0093] In an embodiment, R in Formula 1 11 Can be hydrogen, deuterium, halogen, CH 3 , CH 2F. CHF 2 CF 3 , CH 2 CH 3 , CHFCH 3 , CHFCH 2 F. CHFCHF 2 , CHFCF 3 CF 2 CH 3 CF 2 CH 2 F. CF 2 CHF 2 , or CF 2 CF 3 .

[0094] In an embodiment, R in Formula 1 12 It can be: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; C 1 -C 20 Alkyl; C 1 -C 20 Haloalkyl; C 3 -C 20 Cycloalkyl; or C 6 -C 20 Aryl.

[0095] In an embodiment, X in Formula 1 11 It may be OH.

[0096] In an embodiment, the first repeating unit may be represented by Formula 1-1:

[0097] Formula 1-1

[0098]

[0099] Among them, in formula 1-1,

[0100] L 11 To L 14 、a11 to a13、X 11 , R 11 and p may each be defined as in Formula 1,

[0101] R 13 It can be hydrogen, deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, or C 6 -C 20 Aryl,

[0102] b13 may be an integer from 1 to 5, and

[0103] *Indicates the binding site with the adjacent atom.

[0104] In Formula 1-1, p may be an integer of 1-4, and b13 may be an integer of 1-4.

[0105] In an embodiment, the first repeating unit may be selected from Group I:

[0106] Group I

[0107]

[0108] In one or more embodiments, the polymer may further include at least one of a second repeating unit represented by Formula 2 and a third repeating unit represented by Formula 3:

[0109]

[0110] Wherein, in equations 2 and 3,

[0111] L 21 To L 23 and L 31 To L 33 may be independently: a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C optionally including a heteroatom 1 -C 30 Divalent hydrocarbon groups,

[0112] a21 to a23 and a31 to a33 may each independently be an integer of 1 to 4,

[0113] R 21 and R 31 Each of them may be independently: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms 1 -C 30 Monovalent hydrocarbon groups,

[0114] X 21 may be an acid-labile group,

[0115] X31 may be a non-acid labile group, and

[0116] *Indicates the binding site with the adjacent atom.

[0117] In an embodiment, L in Formulas 2 and 3 21 To L 23 and L 31 To L 33 Can be independently 11 As defined in .

[0118] In an embodiment, a21 to a23 and a31 to a33 in Formulae 2 and 3 may each independently be as defined in a11.

[0119] In an embodiment, R in Formulas 2 and 3 21 and R 31 Can be independently as R 11 As defined in .

[0120] In an embodiment, the polymer may include a second repeating unit represented by Formula 2, and X in Formula 2 21 It can be expressed by formula 4-1 or 4-2:

[0121]

[0122] Among them, in formulas 4-1 and 4-2,

[0123] X 41 It can be a carbon atom or a silicon atom,

[0124] R 41 To R 45 Each of them may be independently: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms 1 -C 30 Monovalent hydrocarbon groups,

[0125] R 46 It may be a linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon group, R 41 To R 46 Adjacent two of may optionally be bonded to each other to form a ring, and

[0126] *Indicates the binding site with the adjacent atom.

[0127] In an embodiment, R in Formula 4-1 and 4-2 41 To R 43may not be simultaneously selected from hydrogen, deuterium, halogen, cyano, and amino.

[0128] In an embodiment, the polymer may include a second repeating unit represented by Formula 2, and X in Formula 2 21 The groups represented by free formulas 5-1 to 5-11 may be selected:

[0129]

[0130]

[0131] Among them, in formulas 5-1 to 5-11,

[0132] a51 can be an integer from 0 to 6,

[0133] R 51 and R 58 may be each independently a linear, branched or cyclic C 1 -C 20 Monovalent hydrocarbon groups,

[0134] R 52 To R 57 Each of them may be independently: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms 1 -C 20 Monovalent hydrocarbon groups,

[0135] R 51 To R 58 Adjacent two of may optionally be bonded to each other to form a ring,

[0136] b54 can be an integer from 1 to 10, and

[0137] *Indicates the binding site with the adjacent atom.

[0138] When a51 in Formula 5-3 is 0, (CR 55 R 56 ) a51 Can be a single bond.

[0139] In an embodiment, X in Formula 2 21 The groups represented by free formulae 5-1 and 5-3 may be selected.

[0140] In an embodiment, the polymer may include a second repeating unit represented by Formula 2, and the second repeating unit may be represented by one or two or more selected from Group II:

[0141] Group II

[0142]

[0143] In an embodiment, the polymer may include a third repeating unit represented by Formula 3, and X in Formula 3 31 can be: hydrogen; halogen; cyano; hydroxyl; carboxylic acid group; thiol group; amino group; or a linear, branched or cyclic C optionally including one or more polar moieties selected from the following 1 -C 30 Monovalent hydrocarbon groups: halogen, cyano, hydroxyl, thiol group, carboxylic acid group, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), lactone moiety, sultone moiety, and carboxylic anhydride moiety.

[0144] In an embodiment, X in Formula 3 31 It can be: hydrogen; hydroxyl; or a linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon groups: hydroxyl, O, C=O, C(=O)O, OC(=O), lactone moieties, and carboxylic acid anhydride moieties.

[0145] In an embodiment, the polymer may include a third repeating unit represented by Formula 3, and X in Formula 3 31 It may be: hydrogen; hydroxyl; or a group represented by one of formulae 6-1 to 6-10:

[0146]

[0147] Among them, in formulas 6-1 to 6-10,

[0148] a61 can be 1 or 2,

[0149] R 61 To R 66 can be independently: a binding site with an adjacent atom; hydrogen; a hydroxyl group; a carboxylic acid group; an ester moiety; a carbonate moiety; a lactone moiety; a carboxylic anhydride moiety; or a linear, branched or cyclic C 1 -C 20 Monovalent hydrocarbon groups,

[0150] R 61 To R 63 One, R 64 One, and R 65 and R 66 One of them can each be a binding site with an adjacent atom,

[0151] b61 can be an integer from 1 to 4,

[0152] b62 can be an integer from 1 to 10,

[0153] b63 can be an integer from 1 to 8,

[0154] b64 can be an integer from 1 to 5.

[0155] b65 can be an integer from 1 to 7,

[0156] b66 can be an integer from 1 to 11,

[0157] b67 can be an integer from 1 to 13,

[0158] b68 can be an integer from 1 to 15, and

[0159] m61 can be an integer from 1 to 4.

[0160] In an embodiment, the polymer may include a third repeating unit represented by Formula 3, and X in Formula 3 31 It may be selected from a hydroxyl group and a group represented by Formula 6-6.

[0161] In an embodiment, the polymer may include a third repeating unit represented by Formula 3, and the third repeating unit may be represented by one or two or more selected from Group III:

[0162] Group III

[0163]

[0164] In an embodiment, the polymer may include the first repeating unit in an amount ranging from about 1 mol % to about 100 mol %, from about 5 mol % to about 100 mol %, and from about 10 mol % to about 100 mol %, for example, from about 40 mol % to about 80 mol %, or from about 10 mol % to about 40 mol %.

[0165] In one or more embodiments, the polymer may consist of the first repeating unit.

[0166] In one or more embodiments, the polymer may include the second repeating unit in an amount ranging from about 0 mol % to about 99 mol %, from about 1 mol % to about 99 mol %, and from about 10 mol % to about 90 mol %, for example, from about 20 mol % to about 60 mol %.

[0167] In one or more embodiments, the polymer may include the third repeating unit in an amount ranging from about 0 mol % to about 99 mol %, from about 1 mol % to about 99 mol %, and from about 10 mol % to about 90 mol %, for example, from about 10 mol % to about 40 mol %.

[0168] In one or more embodiments, the polymer may consist of the first repeating unit and the second repeating unit. In one or more embodiments, the polymer may include the first repeating unit in an amount ranging from about 1 mol % to about 99 mol % or from about 10 mol % to about 90 mol %, for example, from about 40 mol % to about 80 mol %, and include the second repeating unit in an amount ranging from about 1 mol % to about 99 mol % or from about 10 mol % to about 90 mol %, for example, from about 20 mol % to about 60 mol %.

[0169] In one or more embodiments, the polymer may consist of the first repeating unit and the third repeating unit. In one or more embodiments, the polymer may include the first repeating unit in an amount ranging from about 1 mol % to about 99 mol % or from about 10 mol % to about 90 mol %, for example, from about 40 mol % to about 80 mol %, and include the third repeating unit in an amount ranging from about 1 mol % to about 99 mol % or from about 10 mol % to about 90 mol %.

[0170] In one or more embodiments, the polymer may be composed of the first repeating unit, the second repeating unit and the third repeating unit. In one or more embodiments, the polymer may include the first repeating unit in an amount ranging from about 1 mol % to about 98 mol % or about 5 mol % to about 90 mol %, for example, about 10 mol % to about 40 mol %, include the second repeating unit in an amount ranging from about 1 mol % to about 98 mol % or about 5 mol % to about 90 mol %, for example, about 20 mol % to about 60 mol %, for example, about 50 mol %, and include the third repeating unit in an amount ranging from about 1 mol % to about 98 mol % or about 5 mol % to about 90 mol %, for example, about 10 mol % to about 40 mol %.

[0171] The polymer may have a weight average molecular weight (Mw) ranging from about 1,000 to 500,000, for example, from about 3,000 to about 100,000, or from about 5,000 to about 50,000, wherein the weight average molecular weight is measured by gel permeation chromatography using tetrahydrofuran solvent and polystyrene as a standard material.

[0172] The polymer may have a polydispersity index (PDI: Mw / Mn) in the range of about 1.0 to about 3.0, for example, about 1.0 to about 2.5. When the PDI of the polymer is satisfied within the above range, there is less possibility of residual foreign substances on the pattern, or degradation of the pattern profile may be minimized. Therefore, the resist composition including the polymer may be more suitable for forming fine patterns.

[0173] The structure (composition) of the polymer can be confirmed by performing FT-IR analysis, NMR analysis, X-ray fluorescence (XRF) analysis, mass spectrometry, UV analysis, single crystal X-ray structure analysis, powder X-ray diffraction (PXRD) analysis, liquid chromatography (LC) analysis, size exclusion chromatography (SEC) analysis, thermal analysis, etc. The detailed confirmation method is described in the following examples.

[0174] Typically, since EUV (13.5nm) has a smaller number of photons than ArF (193nm) immersion light sources at the same exposure dose, the lower the exposure dose, the noise at the boundary area between the area exposed by the EUV light source and the unexposed unexposed area increases significantly. In the case of a photolithography process using an EUV light source, in order to compensate for this, a larger amount of photoacid generator can be used compared to a photolithography process using another light source with the same amount of light. However, when the resist composition includes a high content of photoacid generator, the glass transition temperature (Tg) of the base resin can be changed and its thermal stability can be degraded. In addition, due to the residual photoacid generator during the photolithography process using the EUV light source, the resolution of the formed resist pattern can be degraded.

[0175] The polymer including the first repeating unit represented by Formula 1 can be crosslinked under an acid catalyst, and in particular, can be crosslinked by heat via a condensation reaction. In other words, when an acid formed by a photoacid generator by high-energy rays is used as a catalyst, the polymer including the first repeating unit represented by Formula 1 can be crosslinked by an etherification reaction, for example, when X 11 Therefore, even if a relatively small amount of the photoacid generator is used, the physical properties of the polymer can be changed, and thus the resolution of a resist pattern obtained therefrom can be improved.

[0176] In addition, when the polymer including the first repeating unit represented by Formula 1 is cross-linked, its solubility in a developer may be reduced compared to that of a polymer that is not cross-linked, and thus the resolution of a resist pattern obtained may be improved.

[0177] In addition, since the polymer including the first repeating unit represented by Formula 1 is cross-linked, the elastic modulus of the resist film formed therefrom may be improved, so that defects caused by pattern collapse during a pattern preparation process may be reduced.

[0178] In addition, since the polymer including the first repeating unit represented by Formula 1 is cross-linked, etching resistance may be improved, etching speed may be reduced, and the thickness of the resist film remaining after development may be relatively thick, and thus the residual rate of the resist film may be improved.

[0179] [Resist composition]

[0180] Another aspect provides a resist composition comprising the polymer, a photoacid generator and an organic solvent. The resist composition may have, for example, improved developability and / or improved resolution.

[0181] The solubility of the resist composition in the developer is changed by exposure to high-energy rays. The resist composition may be a positive resist composition corresponding to a case where the exposed portion of the resist film is dissolved and removed to form a positive resist pattern, or a negative resist composition corresponding to a case where the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern. In particular, the resist composition may be a negative resist composition.

[0182] Furthermore, the resist composition according to the embodiment may be used in an alkali development process using an alkali developer for the development process in forming a resist pattern, or in a solvent development process using a developer containing an organic solvent (hereinafter referred to as an organic developer) for the development process.

[0183] As the polymer including the repeating unit represented by Formula 1 used in the resist composition, one type of polymer or a combination of two or more different types of polymers may be used.

[0184] The polymer may be included in an amount of about 0.1 to about 10 parts by weight based on 100 parts by weight of the resist composition. In particular, the polymer may be included in an amount of about 0.5 to about 5 parts by weight based on 100 parts by weight of the resist composition. When the amount of the polymer is met within the above range, any performance loss, such as a deterioration in sensitivity due to lack of solubility and / or a reduction in the formation of foreign particles, may be reduced.

[0185] The photoacid generator, the organic solvent, and optional components contained as required such as a quencher will be described below.

[0186] <Photoacid generator>

[0187] The photoacid generator may be any compound capable of generating an acid when exposed to high-energy rays such as UV rays, DUV rays, EB, EUV rays, X rays, α rays, and γ rays.

[0188] The photoacid generator may include a sulfonium salt, an iodonium salt, or a combination thereof.

[0189] In an embodiment, the photoacid generator may be represented by Formula 7:

[0190] Formula 7

[0191] B 71 + A 71-

[0192] Among them, in formula 7,

[0193] B 71 + It can be expressed by formula 7A, and A 71 - can be represented by one of Formulas 7B to 7D, and

[0194] B 71 + and A 71 - Optionally linked via a carbon-carbon covalent bond:

[0195]

[0196] In Formulas 7A to 7D,

[0197] L 71 To L 73 can be independently a single bond or CRR',

[0198] R and R' can each independently be hydrogen, deuterium, halogen, cyano, hydroxyl, C 1 -C 30 Alkyl, C 1 -C 30 Haloalkyl, C 1 -C 30 Alkoxy, C 3 -C 30 Cycloalkyl, or C 3 -C 30 Cycloalkoxy,

[0199] n71 to n73 may each independently be 1, 2 or 3,

[0200] x71 and x72 can be 0 or 1 independently.

[0201] R 71 To R 73 may be each independently a linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0202] R 71 To R 73 Adjacent two of may optionally be bonded to each other to form a fused ring, and

[0203] R 74 To R 76 may be independently: hydrogen; halogen; or a linear, branched or cyclic C optionally including heteroatoms 1 -C 30A monovalent hydrocarbon group.

[0204] For example, in Equation 7, B 71 + It can be expressed by formula 7A, and A 71 - It can be represented by Formula 7B. In particular, R in Formula 7A 71 To R 73 Each may be a phenyl group.

[0205] The photoacid generator may be included in an amount ranging from about 0.01 parts by weight to about 40 parts by weight, from about 0.1 parts by weight to about 40 parts by weight, or from about 0.1 parts by weight to about 20 parts by weight, based on 100 parts by weight of the polymer. When the amount of the photoacid generator is satisfied within the above range, appropriate resolution may be achieved, and problems associated with foreign particles during stripping or after development may be reduced.

[0206] One type of photoacid generator may be used, or a combination of two or more different types of photoacid generators may be used.

[0207] <Organic Solvents>

[0208] The organic solvent included in the resist composition may not be particularly limited as long as it can dissolve or disperse the polymer, the photoacid generator, and an optional component such as a quencher included as needed.

[0209] One type of organic solvent may be used, or a combination of two or more different types of organic solvents may be used. In addition, a mixed solvent in which water and an organic solvent are mixed may be used.

[0210] Examples of the organic solvent may include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, an ester-based solvent, a sulfoxide-based solvent, a hydrocarbon-based solvent, and the like.

[0211] Examples of the alcohol-based solvent may include monohydric alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylpentanol, butanol, 4-methyl-2-pentanol (MIBC), sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc.; polyol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-Butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol; and ether solvents containing polyols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ... Glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

[0212] Examples of the ether-based solvent may include: dialkyl ether-based solvents, such as diethyl ether, dipropyl ether, dibutyl ether, etc.; cyclic ether-based solvents, such as tetrahydrofuran, tetrahydropyran, etc.; aromatic ring-containing ether-based solvents, such as diphenyl ether, anisole, etc.; diethylene glycol dimethyl ether, propylene glycol dimethyl ether; etc.

[0213] Examples of the ketone-based solvent may include: chain ketone-based solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, etc.; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, etc.; 2,4-pentanedione; acetone acetone; acetophenone; etc.

[0214] Examples of the amide-based solvent may include: cyclic amide-based solvents such as N,N'-dimethylimidazolidinone, N-methyl-2-pyrrolidone, etc.; chain amide-based solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, etc.; etc.

[0215] Examples of the ester solvent may include: acetate solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate (n-BA), isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, etc.; ether carboxylate solvents containing polyols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc.; lactone solvents such as γ-butyrolactone and δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; lactate solvents such as methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, etc.; glycol diacetate; methoxytriglycol acetate; ethyl propionate; n-butyl propionate; isoamyl propionate; diethyl oxalate; di-n-butyl oxalate; methyl acetoacetate; ethyl acetoacetate; diethyl malonate; dimethyl phthalate; diethyl phthalate, etc.

[0216] Examples of the sulfoxide-based solvent may include dimethyl sulfoxide, diethyl sulfoxide, and the like.

[0217] Examples of the hydrocarbon-based solvent may include: aliphatic or alicyclic hydrocarbon-based solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane, etc.; and aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, etc.

[0218] In an embodiment, the organic solvent may be selected from an alcohol-based solvent, an amide-based solvent, an ester-based solvent, a sulfoxide-based solvent, and any combination thereof. In one or more embodiments, the organic solvent may be selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, ethyl lactate, dimethyl sulfoxide, and any combination thereof.

[0219] In an embodiment, when an acid-labile group in the form of acetal is used, the organic solvent may further include a high boiling point alcohol, such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, or 1,3-butanediol, to accelerate the deprotection reaction of the acetal.

[0220] The organic solvent may be used in an amount ranging from about 200 parts by weight to about 20,000 parts by weight, for example, from about 2,000 to about 10,000 parts by weight, based on 100 parts by weight of the polymer.

[0221] <Quencher>

[0222] The resist composition may further include a quencher.

[0223] The quencher may be a salt that generates an acid having weaker acidity than an acid generated by the photoacid generator.

[0224] The quencher may include an ammonium salt, a sulfonium salt, an iodonium salt, or a combination thereof.

[0225] In an embodiment, the quencher may be represented by Formula 8:

[0226] Formula 8

[0227] B 81 + A 81 -

[0228] Among them, in formula 8,

[0229] B 81 + can be represented by one of Formulas 8A to 8C, and A 81 - can be represented by one of Formulas 8D to 8F, and

[0230] B 81 + and A 81 - may optionally be linked to each other via carbon-carbon covalent bonds:

[0231]

[0232] Wherein, in Formulas 8A to 8F,

[0233] L 81 and L 82 can be independently a single bond or CRR',

[0234] R and R' can each independently be hydrogen, deuterium, halogen, cyano, hydroxyl, C 1 -C 30 Alkyl, C 1 -C 30 Haloalkyl, C 1 -C 30 Alkoxy, C 3 -C 30 Cycloalkyl, or C 3 -C 30 Cycloalkoxy,

[0235] n81 and n82 can each independently be 1, 2 or 3,

[0236] x81 can be 0 or 1,

[0237] R 81 To R 84 may be each independently a linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0238] R 81 To R 84 Adjacent two of may optionally be bonded to each other to form a fused ring, and

[0239] R 85 and R 86 may be independently: hydrogen; halogen; or a linear, branched or cyclic C optionally including heteroatoms 1 -C 30 A monovalent hydrocarbon group.

[0240] The quencher may be included in an amount ranging from about 0 to about 10 parts by weight, 0.05 to about 5 parts by weight, or about 0.1 to about 3 parts by weight, based on 100 parts by weight of the polymer. When the amount of the quencher is satisfied within the above range, appropriate resolution may be achieved, and problems associated with foreign particles during stripping or after development may be reduced.

[0241] One type of quencher may be used, or two or more different types of quenchers may be used in combination.

[0242] <Base resin>

[0243] The resist composition may further include a base resin. The base resin does not include the first repeating unit represented by Formula 1.

[0244] The base resin may include a repeating unit represented by Formula 2 and including an acid-labile group:

[0245] Formula 2

[0246]

[0247] Among them, in formula 2,

[0248] L 21 To L 23 may be independently: a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C optionally including a heteroatom 1 -C 30 divalent hydrocarbon group, a21 to a23 may each independently be an integer of 1 to 4,

[0249] R 21 It may be: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms. 1 -C 30 Monovalent hydrocarbon groups,

[0250] X 21 may be an acid-labile group, and

[0251] *Indicates the binding site with the adjacent atom.

[0252] The description of Formula 2 can be defined as described above.

[0253] The base resin including the repeating unit represented by Formula 2 may be decomposed by an acid to generate a carboxyl group, thereby being converted to have alkali solubility.

[0254] In addition to the repeating unit represented by Formula 2, the base resin may further include a repeating unit represented by Formula 3:

[0255] Formula 3

[0256]

[0257] Among them, in formula 3,

[0258] L 31 To L 33may be independently: a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a linear, branched or cyclic C optionally including a heteroatom 1 -C 30 divalent hydrocarbon group, a31 to a33 may each independently be an integer of 1 to 4,

[0259] R 31 It may be: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a linear, branched or cyclic C optionally including heteroatoms. 1 -C 30 Monovalent hydrocarbon groups,

[0260] X 31 may be a non-acid labile group, and

[0261] *Indicates the binding site with the adjacent atom.

[0262] The description of Formula 3 can be defined as described above.

[0263] For example, in the ArF photolithography process, X 31 It can include lactone ring as polar part, and in KrF, EB and EUV lithography processes, X 31 It may be phenol.

[0264] In an embodiment, the base resin may further include a portion including anions and / or cations. For example, the base resin may further include a portion in which a photoacid generator and / or a quencher are bonded to a side chain.

[0265] The base resin may have a weight average molecular weight (Mw) ranging from about 1,000 to 500,000, for example, from about 3,000 to about 100,000, wherein the weight average molecular weight (Mw) is measured by gel permeation chromatography using a tetrahydrofuran solvent and polystyrene as a standard material.

[0266] The base resin may have a polydispersity index (PDI: Mw / Mn) in the range of about 1.0 to about 3.0, for example, about 1.0 to about 2.0. When the PDI of the base resin is satisfied within the above range, there is less possibility of residual impurity substances on the pattern, or degradation of the pattern profile may be minimized. Therefore, the resist composition including the base resin may be more suitable for forming a fine pattern.

[0267] The base resin may be prepared by any appropriate method, for example, a method in which an unsaturated bond-containing monomer is dissolved in an organic solvent and thermally polymerized in the presence of a radical initiator.

[0268] In the base resin, the mole fraction (mol %) of each repeating unit derived from each monomer is as follows, but not limited thereto:

[0269] i) including a repeating unit represented by Formula 2 in an amount ranging from about 1 mol% to about 60 mol%, for example, from about 5 mol% to about 50 mol%, and for example, from about 10 mol% to about 50 mol%; and

[0270] ii) including the repeating unit represented by Formula 3 in an amount ranging from about 40 mol % to about 99 mol %, for example, from about 50 mol % to about 95 mol %, and for example, from about 50 mol % to about 90 mol %.

[0271] The base resin may be one type of polymer, or may include a mixture of two or more types of polymers having different compositions, different weight average molecular weights (Mw), and / or different PDIs (Mw / Mn).

[0272] <Optional Components>

[0273] If necessary, the resist composition may further include a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof.

[0274] The resist composition may further include a surfactant to improve coating properties and developing properties. Examples of the surfactant may include: nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, etc.; etc. For use as a surfactant, commercially available products may be used, or synthetic products may be used. Examples of commercially available products may include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75 and POLYFLOW No. 95 (manufactured by Kyoeisha Chemical Co., LTD.), FTOP EF301, FTOP EF303, and FTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE F171 (registered trademark), MEGAFACE F173, R40, R41, and R43 (manufactured by DIC Corporation), Fluorad FC430 (registered trademark) and Fluorad FC431 (manufactured by 3M Company), AsahiGuard AG710 (product of AGC Corporation), Surflon S-382 (registered trademark), Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, and Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.), and the like.

[0275] The surfactant may be included in an amount ranging from about 0 parts by weight to about 20 parts by weight based on 100 parts by weight of the polymer.

[0276] One type of surfactant may be used, or a combination of two or more different types of surfactants may be used.

[0277] The method for preparing the resist composition is not particularly limited, and for example, a method of mixing a polymer, a photoacid generator and an optional component added as required in an organic solvent can be used. The temperature or time during mixing is not particularly limited. If necessary, filtering can be performed after mixing.

[0278] [Pattern Formation Method]

[0279] In the following, reference will be made to Figure 1 and 2A2C describe the pattern forming method according to the embodiment in more detail. Figure 1 is a flow chart showing a pattern forming method according to an embodiment, and Figures 2A to 2C Each is a side cross-sectional view illustrating a pattern forming method according to an embodiment. Hereinafter, an example of a pattern forming method using a negative resist composition will be described in detail, but embodiments of the present disclosure are not limited thereto.

[0280] Reference Figure 1 , the pattern forming method may include: forming a resist film by applying a resist composition S101; exposing at least a portion of the resist film to high-energy rays S102; and developing the exposed resist film by using a developer S103. The above steps may be omitted as needed, or may be performed in a different order.

[0281] First, the board 100 may be prepared. The board 100 may be, for example, a semiconductor board such as a silicon board or a germanium board, or may be formed of glass, quartz, ceramic, copper, etc. In an embodiment, the board 100 may include a III-V group compound such as GaP, GaAs, GaSb, etc.

[0282] The resist film 110 may be formed by applying a resist composition to a desired thickness on the board 100 by a coating method. If necessary, the method may include heating (pre-bake (PB) or post-annealing bake (PAB) step) to remove the organic solvent remaining in the resist film 110.

[0283] The coating method may include spin coating, dipping, roller coating or other common coating methods. In an embodiment, spin coating may be used, and the thickness of the resist film 110 may be regulated by controlling the viscosity, concentration and / or rotation speed of the resist composition. In an embodiment, the thickness of the photoresist film 110 may be in the range of about 10nm to about 300nm. In one or more embodiments, the thickness of the resist film 110 may be in the range of about 30nm to about 200nm.

[0284] The lower limit of the temperature of PB may be 60° C. or higher, such as 80° C. or higher. In addition, the upper limit of the temperature of PB may be 150° C. or lower, such as 140° C. or lower. The lower limit of the PB time may be 5 seconds or more, such as 10 seconds or more. The upper limit of the PB time may be 600 seconds or less, such as 300 seconds or less.

[0285] Before the resist composition is applied to the plate 100, an etching target film (not shown) may be further formed on the plate 100. The etching target film may refer to a layer on which an image is transferred from a resist pattern and transformed into a certain pattern. In an embodiment, the film to be etched may be formed to include, for example, an insulating material such as silicon oxide, silicon nitride, or silicon oxynitride. In one or more embodiments, the film to be etched may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, or a metal silicon nitride. In one or more embodiments, the film to be etched may be formed to include a semiconductor material such as polysilicon.

[0286] In an embodiment, an anti-reflection film may be further formed on the board 100 to maximize the efficiency of the resist. The anti-reflection film may be an organic-based anti-reflection layer or an inorganic-based anti-reflection layer.

[0287] In an embodiment, a protective film may be further provided on the resist film 110 to reduce the influence of alkaline impurities etc. included in the process. In addition, in the case of immersion exposure, for example, a protective film for immersion may be provided on the resist film 110 to avoid direct contact between the immersion medium and the resist film 110.

[0288] Next, at least a portion of the resist film 110 may be exposed to high energy rays. For example, high energy rays may be irradiated onto at least a portion of the resist film 110 through the mask 120. Thus, the resist film 110 may have an exposed portion 111 and an unexposed portion 112.

[0289] Exposure can be performed by irradiating high-energy rays through a mask having a predetermined pattern, and in some cases by using a liquid such as water as a medium. Examples of the high-energy rays may include electromagnetic waves such as ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV rays, wavelength of 13.5 nm), X-rays, gamma rays, etc.; charged particle beams such as electron beams (EB), alpha rays, etc.; etc. Such irradiation of high-energy rays may be collectively referred to as "exposure".

[0290] As a light source used for exposure, various types of radiation can be used, including laser beams irradiating in the extreme ultraviolet region, such as KrF excimer laser (wavelength of 248 nm), ArF excimer laser (wavelength of 193 nm), and F 2 Excimer laser (wavelength of 157 nm); irradiation of a harmonic laser beam in the far ultraviolet or vacuum ultraviolet region by a wavelength conversion method using a laser beam from a solid-state laser source (e.g., YAG or semiconductor laser); irradiation of EB rays or EUV rays; etc. At the time of exposure, exposure can be performed through a mask corresponding to a desired pattern. However, when the light source for exposure is EB, exposure can be performed by direct drawing without using a mask.

[0291] In the case of using EUV rays as high-energy rays, the integrated dose of the high-energy rays may be 2,000 mJ / cm 2 or less, e.g. 500mJ / cm 2 In addition, in the case of using EB as the high-energy ray, the integrated dose of the high-energy ray may be 5,000 μC / cm 2 or less, e.g. 1,000μC / cm 2 or smaller.

[0292] In addition, a post-exposure bake (PEB) may be performed after exposure. The lower limit of the temperature of the PEB may be 50° C. or higher, such as 80° C. or higher. The upper limit of the temperature of the PEB may be 180° C. or lower, such as 130° C. or lower. The lower limit of the PEB time may be 5 seconds or more, such as 10 seconds or more. The upper limit of the PEB time may be 600 seconds or less, such as 300 seconds or less.

[0293] While not being limited to a particular theory, a condensation reaction may occur in the PEB, where the acid formed by the exposure acts as a catalyst to form crosslinks in the polymer.

[0294] Next, the exposed resist film 110 may be developed using a developer. The exposed portion 111 may remain unwashed by the developer, while the unexposed portion 112 may be washed away by using the developer.

[0295] For use as a developer, an alkaline developer, a developer containing an organic solvent (hereinafter also referred to as an "organic developer"), etc. can be used. As a developing method, an immersion method, a puddle method, a spraying method, a dynamic administration method, etc. can be used. The developing temperature can be, for example, 5° C. or higher and 60° C. or lower, and the developing time can be, for example, 5 seconds or more and 300 seconds or less.

[0296] The alkaline developer may be, for example, an alkaline aqueous solution that dissolves at least one alkaline compound, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), etc. The alkaline developer may further include a surfactant.

[0297] The lower limit of the amount of the alkaline compound in the alkaline developer may be 0.1% by mass or more, for example, 0.5% by mass or more, and for example, 1% by mass or more. In addition, the upper limit of the amount of the alkaline compound in the alkaline developer may be 20% by mass or less, for example, 10% by mass or less, and for example, 5% by mass or less.

[0298] As the organic solvent included in the organic developer, for example, the same organic solvent as described in <Organic Solvent> of [Resist Composition] can be used.

[0299] The lower limit of the amount of the organic solvent in the organic developer may be 80% by mass or more, for example, 90% by mass or more, and for example, 95% by mass or more, and for example, 99% by mass or more.

[0300] The organic developer may include a surfactant, a trace amount of water, and / or acetic acid (AA). In addition, during development, the solvent may be replaced with a solvent of a different kind from the organic developer to stop development.

[0301] The resist pattern after development can be further cleaned by using a cleaning solution. For use as a cleaning solution, ultrapure water, a cleaning solution, etc. can be used. The cleaning solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a common organic solvent can be used. For example, the cleaning solution can be an alcohol-based solvent or an ester-based solvent. After washing, the cleaning solution remaining on the plate and the pattern can be removed. In addition, when ultrapure water is used, the water remaining on the plate and the pattern can be removed.

[0302] Furthermore, the developers may be used alone or in combination of two or more types.

[0303] After forming the resist pattern as described above, a patterned interconnection board can be obtained. The etching method can be performed by a known method including: dry etching using plasma gas; wet etching using an alkaline solution, a cupric chloride solution, a ferric chloride solution; and the like.

[0304] After forming the resist pattern, plating may be performed. Although not particularly limited, the plating method may include, for example, copper plating, solder plating, nickel plating, gold plating, and the like.

[0305] The resist pattern remaining after etching can be stripped with an organic solvent. Although not particularly limited, examples of organic solvents may include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), etc. Although not particularly limited, examples of stripping methods may be immersion methods, spraying (spraying) methods, etc. In addition, the interconnect board on which the resist pattern is formed may be a multilayer interconnect board or may have a small diameter through hole.

[0306] In an embodiment, the interconnection board may be formed by a lift-off method in which a resist pattern is formed, a metal is then deposited in a vacuum, and the resist pattern is then dissolved by using a solution.

[0307] The present disclosure will be described in more detail with reference to the following Examples and Comparative Examples, but the technical scope of the present disclosure is not limited thereto.

[0308] [Example]

[0309] Synthesis Example 1: Synthesis of Polymer A

[0310]

[0311] 4 g (22.7 mmol) of 4-vinylbenzyl acetate (VBA, monomer 1) and 0.5 g (2.3 mmol) of azo initiator (V601) were dissolved in 35% methyl ethyl ketone (MEK), and then reacted at 70° C. for 4 hours. Next, hexane was added thereto to allow precipitation, and the precipitate was dried to obtain a solid. The solid thus obtained was dispersed in methanol, and NaOCH was added thereto at a molar ratio twice that of the obtained solid. 3 Solution (25 wt %, methanol). Then, it was allowed to react at room temperature for 4 hours to obtain a reaction product. Thereafter, 50 mL of distilled water (DW) and acetic acid (with NaOCH added) were added to the reaction product. 3 The precipitate was dried at 40° C. for 24 hours to obtain a white powdery polymer A.

[0312] Synthesis Examples 2 to 8

[0313] The polymers were obtained in the same manner as in Synthesis Example 1, except that Monomers 1 to 3 of Table 1 were used instead of Monomer 1. For the polymers obtained in Synthesis Examples 1 to 8, the 1 H-NMR, weight average molecular weight and PDI, and the results are shown in Table 2.

[0314] [Table 1]

[0315]

[0316]

[0317] [Table 2]

[0318]

[0319] Evaluation Example 1: Evaluation of thin film phenomenon

[0320] (1) Terminology

[0321] E 0 represents the exposure at the point where the film begins to harden, and E 1 represents the exposure amount at the saturation point where the thickness of the film no longer increases. The residual film ratio refers to the film thickness at the saturation point divided by the initial thickness, expressed as a percentage, and γ refers to the contrast curve value calculated by Equation 1:

[0322] Equation 1

[0323]

[0324] NRT is the abbreviation for normalized residual thickness.

[0325] (2) Evaluation of thin film phenomena

[0326] In a solution containing propylene glycol methyl ether (PGME) / propylene glycol methyl ether acetate (PGMEA) at a ratio of 7:3 (weight / weight), the polymer, PAG A, and PDQ A of Table 3 were dissolved so that the total of these materials was 1.5 wt %. Here, the weight ratios of the polymer, PAG A, and PDQ A are as shown in Table 3. The casting solution was spin-coated at 1,500 rpm on a silicon wafer coated with HMDS as a 3 mm thick lower layer, and then dried at 130° C. for 1 minute to prepare a 50 nm thick film. Next, the resulting film was treated with a DUV having a wavelength of 248 nm at about 0 mJ / cm 2 to about 50mJ / cm 2 The films were exposed to a dose in the range of , and then subjected to PEB at 110° C. for 60 seconds. After immersion in the developer shown in Table 3 at 25° C. for 20 seconds, the thickness of the residual film was measured by using a three-dimensional optical profiler (Bruker, Contour X-100), and the results are shown in Tables 3 and Figures 3A to 3J middle. Figure 3A A graph showing the data of Example 1-1, Figure 3B A graph showing the data for Example 1-2, Figure 3C A graph showing the data for Examples 1-3, Figure 3D A graph showing the data for Examples 1-4, Figure 3E A graph showing the data for Examples 1-5, Figure 3F A graph showing the data for Examples 1-6, Figure 3G A graph showing the data for Examples 1-7, Figure 3H A graph showing the data for Examples 1-8, Fig. 3I A graph showing the data of Comparative Example 1-1, and Figure 3J A graph showing the data of Comparative Example 1-2.

[0327] Table 3

[0328]

[0329]

[0330] Referring to Table 3, it was confirmed that the films of Examples 1-1 to 1-8 had smaller E 1 values ​​and larger γ values, indicating that the films of Examples 1-1 to 1-8 have improved sensitivity compared with the film of Comparative Example 1-2.

[0331] In addition, it was confirmed that the films of Examples 1-2 to 1-5 had larger γ values ​​than the film of Example 1-1, and that the films of Examples 1-6 to 1-8 had smaller E values ​​than the film of Example 1-1. 0 value.

[0332] Evaluation Example 2: Evaluation results of elastic modulus

[0333] The test samples were prepared by cutting the silicon wafer coated with the polymer of Table 4 into a size of 10 mm×10 mm. The elastic modulus of the film was measured in tapping mode using Bruker's Dimension Icon XR and RTESPA-300-30 probe under the conditions of a tip radius of 30 nm and a spring constant of 40 N / m. The results are shown in Table 4.

[0334] Table 4

[0335] polymer Elastic modulus (MPa) Relative value (%) Comparative Example 2-1 D 2,745 100 Example 2-1 A 3,182 116 Example 2-2 B-1 4,307 157 Example 2-3 B-2 3,763 137 Embodiment 2-4 B-3 3,534 129 Embodiment 2-5 B-4 3,243 118 Embodiment 2-6 C-1 3,988 145 Embodiment 2-7 C-2 3,982 145 Embodiment 2-8 C-3 3,666 134

[0336] It can be confirmed that the elastic modulus of the films of Examples 2-1 to 2-8 is improved by about 16% to 57%, particularly up to 57%, compared to the elastic modulus of the film of Comparative Example 2-1. Without being limited to a particular theory, polymers A, B-1 to B-4, and C-1 to C-3 are cross-linked, and therefore the elastic modulus of these polymers is improved compared to the non-cross-linked polymer D.

[0337] Evaluation Example 3: Evaluation of Etching Resistance

[0338] The dry etching apparatus Plasmalab 100RIE (purchased from Oxford Instruments Plasma Technology) was used to etch the CF 4 and O 2 The film was etched for 10 seconds, 20 seconds and 30 seconds at a gas flow rate of 20:5 (sccm) by an etching gas of 1.5 wt % (seem). Then, the etching rate was measured from the thickness change, and the results are shown in Table 5.

[0339] Table 5

[0340]

[0341]

[0342] It was confirmed that the etching rates of the films of Examples 3-1 to 3-8 were reduced by about 9% to 31%, particularly up to 31%, compared to the etching rate of the film of Comparative Example 3-1. Without being limited to a particular theory, polymers A, B-1 to B-4, and C-1 to C-3 are cross-linked, and therefore, compared to polymer D which is not cross-linked, it is expected that the etching rate thereof is slowed down.

[0343] Figures 4A to 4E is a side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment.

[0344] Reference Figure 4A , before forming the resist film 110 on the substrate 100, a material layer 130 may be formed on the substrate 100. The resist film 110 may be formed on top of the material layer 130. The material layer 130 may include an insulating material (e.g., silicon oxide, silicon nitride), a semiconductor material (e.g., silicon), or a metal (e.g., copper). In some embodiments, the material layer 130 may be a multilayer structure. The material of the material layer 130 may be different from the material of the substrate 100. The resist film 110 may include a resist composition according to an example embodiment, and may have a thickness of about 10 nm to about 300 nm or about 30 nm to about 200 nm.

[0345] Reference Figure 4B , the resist film 110 may be exposed to high-energy rays through the mask 120 , after which the resist film 110 may include an exposed region 111 and an unexposed region 112 .

[0346] Reference Figure 4C , the exposed resist film 110 may be developed using a developer (eg, a developing solution). The exposed portion 111 may remain without being washed away by the developing solution, while the unexposed portion 112 may be washed away by the developing solution.

[0347] Reference Figure 4D , the exposed region of the material layer 130 may be etched using the resist pattern 110 as a mask to form a material pattern 135 on the substrate 100 .

[0348] Reference Figure 4E , the resist pattern 110 can be removed.

[0349] Figures 5A to 5E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment.

[0350] Reference Figure 5A , a gate dielectric 505 (e.g., silicon oxide) may be formed on a substrate 500. The substrate 500 may be a semiconductor substrate, such as a silicon substrate. A gate layer 515 (e.g., doped polysilicon) may be formed on the gate dielectric 505. A hard mask layer 520 may be formed on the gate layer 515.

[0351] Reference Figure 5B , a resist pattern 540b may be formed on the hard mask layer 520. The resist pattern 540b may be formed using a resist composition according to example embodiments. The resist pattern 540b may be formed of a resist composition including the polymer, a photoacid generator, an organic solvent, and optionally a quencher and a base resin.

[0352] Reference Figure 5C , the hard mask layer 520, the gate layer 515, and the gate dielectric 505 may be etched to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a.

[0353] Reference Figure 5D , a spacer layer may be formed over the gate electrode pattern 515a and the gate dielectric pattern 505a. The spacer layer may be formed using a deposition process (e.g., CVD). The spacer layer may be etched to form spacers 535a (e.g., silicon nitride) on the sidewalls of the gate electrode pattern 515a and the gate dielectric pattern 505a. After forming the spacers 535a, ions may be implanted into the substrate 500 to form source / drain impurity regions S / D.

[0354] Reference Figure 5E , an interlayer insulating layer 560 (e.g., oxide) may be formed on the substrate 500 to cover the gate electrode pattern 515a, the gate dielectric pattern 505a, and the spacer 535a. Then, electrical contacts 570a, 570b, and 570c may be formed in the interlayer insulating layer 560 to connect to the gate electrode pattern 515a and the S / D region. The electrical contacts may be formed of a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewalls of the interlayer insulating layer 560 and the electrical contacts 570a, 570b, and 570c. Although Figures 5A to 5E An example of forming a transistor is shown, but the inventive concept is not limited thereto.

[0355] The resist composition according to one or more embodiments may be used in a patterning process to form other types of semiconductor devices.

[0356] According to one or more embodiments, examples of the present disclosure may provide a resist composition capable of providing improved sensitivity and / or improved resolution.

[0357] It should be understood that the embodiments described herein should be considered in a descriptive sense only and not for limiting purposes. The description of features or aspects in each embodiment should typically be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and detail may be made therein without departing from the spirit and scope as defined by the appended claims.

Claims

1. A polymer comprising a first repeating unit represented by Formula 1: Formula 1 in, In formula 1, L 11 To L 13 Each is independently: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a straight-chain, branched or cyclic C1-C ... 30 Divalent hydrocarbon groups, L 14 is a linear, branched or cyclic C1-C 30 Divalent hydrocarbon groups, a11 to a13 are each independently an integer of 1 to 4, A 11 C6-C 30 Aromatic groups or C1-C 30 Heteroaromatic groups, R 11 and R 12 Each is independently: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a straight-chain, branched or cyclic C1-C ... 30 Monovalent hydrocarbon groups, b12 is an integer from 1 to 10, X 11 is OH, SH or NH2, p is an integer from 1 to 5, and *Indicates the binding site with the adjacent atom.

2. The polymer according to claim 1, wherein L 11 To L 13 Each is independently: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); a substituted or unsubstituted C1-C 30 Alkylene; substituted or unsubstituted C3-C 30 Cycloalkylene; substituted or unsubstituted C3-C 30 Heterocycloalkylene; substituted or unsubstituted C2-C 30 Alkenylene; substituted or unsubstituted C3-C 30 Cycloalkenylene; substituted or unsubstituted C3-C 30 Heterocycloalkenylene; substituted or unsubstituted C6-C 30 Arylene; or substituted or unsubstituted C1-C 30 Heteroarylene, and L 14 For: substituted or unsubstituted C1-C 30 Alkylene; substituted or unsubstituted C3-C 30 Cycloalkylene; substituted or unsubstituted C3-C 30 Heterocycloalkylene; substituted or unsubstituted C2-C 30 Alkenylene; substituted or unsubstituted C3-C 30 Cycloalkenylene; substituted or unsubstituted C3-C 30 Heterocycloalkenylene; substituted or unsubstituted C6-C 30 Arylene; or substituted or unsubstituted C1-C 30 Heteroarylene.

3. The polymer according to claim 1, wherein A 11 is a phenyl group, a naphthalene group, a phenanthrene group, an anthracene group, group, a pyrene group, a benzo[9,10]phenanthrene group, a fluorene group, a pyrrole group, a pyridine group, a pyrimidine group, a pyrazine group, a triazine group, a quinoline group, an isoquinoline group, a carbazole group, a furan group, a benzofuran group, a dibenzofuran group, a thiophene group, a benzothiophene group, or a dibenzothiophene group.

4. The polymer of claim 1, wherein X 11 For OH.

5. The polymer of claim 1, wherein the first repeating unit is represented by formula 1-1: Formula 1-1 in, In formula 1-1, L 11 To L 14 、a11 to a13、X 11 , R 11 and p are each defined as in Formula 1, R 13 is hydrogen, deuterium, halogen, cyano, hydroxyl, amino, carboxylic acid group, thiol group, ester moiety, sulfonate moiety, carbonate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkoxy, or C6-C 20 Aryl, b13 is an integer from 1 to 5, and *Indicates the binding site with the adjacent atom.

6. The polymer of claim 1, wherein the first repeating unit is selected from Group I: Group I 7. The polymer of claim 1, further comprising: at least one of a second repeating unit represented by Formula 2 and a third repeating unit represented by Formula 3, Among them, in formulas 2 and 3, L 21 To L 23 and L 31 To L 33 Each independently represents: a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a straight-chain, branched or cyclic C1-C ... 30 Divalent hydrocarbon groups, a21 to a23 and a31 to a33 are each independently an integer of 1 to 4, R 21 and R 31 Each is independently: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a straight-chain, branched or cyclic C1-C ... 30 Monovalent hydrocarbon groups, X 21 is an acid-labile group, X 31 is a non-acid-labile group, and *Indicates the binding site with the adjacent atom.

8. The polymer according to claim 7, wherein The polymer includes a second repeating unit represented by Formula 2, and X 21 It is expressed by formula 4-1 or 4-2: in, In equations 4-1 and 4-2, X 41 is a carbon atom or a silicon atom, R 41 To R 45 Each is independently: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a straight-chain, branched or cyclic C1-C ... 30 Monovalent hydrocarbon groups, R 46 is a linear, branched or cyclic C1-C 30 Monovalent hydrocarbon groups, R 41 To R 46 Adjacent two of are optionally bonded to each other to form a ring, and *Indicates the binding site with the adjacent atom.

9. The polymer of claim 7, wherein The polymer includes a second repeating unit represented by Formula 2, and X 21 A group selected from the group represented by formulae 5-1 to 5-11: in, In formulas 5-1 to 5-11, a51 is an integer selected from 0 to 6, R 51 and R 58 Each is independently a linear, branched or cyclic C1-C 20 Monovalent hydrocarbon groups, R 52 To R 57 Each is independently: hydrogen; deuterium; halogen; cyano; hydroxyl; amino; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a straight-chain, branched or cyclic C1-C ... 20 Monovalent hydrocarbon groups, R 51 To R 58 Adjacent two of are optionally bonded to each other to form a ring, b54 is an integer from 1 to 10, and *Indicates the binding site with the adjacent atom.

10. The polymer of claim 7, wherein The polymer includes a second repeating unit represented by Formula 2, and The second repeating unit is one or two or more selected from Group II: Group II 11. The polymer of claim 7, wherein The polymer includes a second repeating unit represented by Formula 3, and X 31 is: hydrogen; halogen; cyano; hydroxyl; carboxylic acid group; thiol group; amino group; or a linear, branched or cyclic C1-C ... 30 Monovalent hydrocarbon groups: halogen, cyano, hydroxyl, thiol group, carboxylic acid group, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), lactone moiety, sultone moiety, and carboxylic anhydride moiety.

12. The polymer of claim 7, wherein The polymer includes a second repeating unit represented by Formula 3, and X 31 is: hydrogen; hydroxyl; or a group represented by one of formulae 6-1 to 6-10: in, In formulas 6-1 to 6-10, a61 is 1 or 2, R 61 To R 66 Each is independently: a binding site to an adjacent atom; a hydrogen; a hydroxyl group; a carboxylic acid group; an ester moiety; a carbonate moiety; a lactone moiety; a carboxylic anhydride moiety; or a linear, branched or cyclic C1-C 20 Monovalent hydrocarbon groups, R 61 To R 63 One, R 64 One, and R 65 and R 66 One of each is a binding site with an adjacent atom, b61 is an integer from 1 to 4, b62 is an integer from 1 to 10, b63 is an integer from 1 to 8, b64 is an integer from 1 to 5, b65 is an integer from 1 to 7, b66 is an integer from 1 to 11, b67 is an integer from 1 to 13, b68 is an integer from 1 to 15, and m61 is an integer from 1 to 4.

13. The polymer of claim 7, wherein The polymer includes a second repeating unit represented by Formula 3, and The third repeating unit is one or two or more selected from Group III: Group III 14. A resist composition comprising: The polymer according to any one of claims 1 to 13; Photoacid generators; and Organic solvents.

15. The resist composition of claim 14, wherein the photoacid generator is represented by Formula 7: Formula 7 B 71 + A 71 - in, In formula 7, B 71 + It is represented by formula 7A, and A 71 - represented by one of Formulas 7B to 7D, and B 71 + and A 71 - Optionally linked to each other via carbon-carbon covalent bonds: Wherein, in Formulas 7A to 7D, L 71 To L 73 are each independently a single bond or CRR', R and R' are each independently hydrogen, deuterium, halogen, cyano, hydroxyl, C1-C 30 Alkyl, C1-C 30 Halogenated alkyl, C1-C 30 Alkoxy, C3-C 30 Cycloalkyl, or C3-C 30 Cycloalkoxy, n71 to n73 are each independently 1, 2 or 3, x71 and x72 are each independently 0 or 1, R 71 To R 73 Each is independently a linear, branched or cyclic C1-C 30 Monovalent hydrocarbon groups, R 71 To R 73 Adjacent two of are optionally bonded to each other to form a fused ring, and R 74 To R 76 are independently: hydrogen; halogen; or a linear, branched or cyclic C1-C 30 A monovalent hydrocarbon group.

16. The resist composition according to claim 14, further comprising: Quencher.

17. The resist composition of claim 16, wherein the quencher is represented by Formula 8: Formula 8 B 81 + A 81 - in, In formula 8, B 81 + Represented by one of Formulas 8A to 8C, A 81 - represented by one of Formulas 8D to 8F, and B 81 + and A 81 - Optionally linked to each other via carbon-carbon covalent bonds: Wherein, in Formulas 8A to 8F, L 81 and L 82 are each independently a single bond or CRR', R and R' are each independently hydrogen, deuterium, halogen, cyano, hydroxyl, C1-C 30 Alkyl, C1-C 30 Halogenated alkyl, C1-C 30 Alkoxy, C3-C 30 Cycloalkyl, or C3-C 30 Cycloalkoxy, n81 and n82 are each independently 1, 2 or 3, x81 is 0 or 1, R 81 To R 84 Each is independently a linear, branched or cyclic C1-C 30 Monovalent hydrocarbon groups, R 81 To R 84 Adjacent two of are optionally connected to each other to form a fused ring, and R 85 and R 86 are independently: hydrogen; halogen; or a linear, branched or cyclic C1-C 30 A monovalent hydrocarbon group.

18. A method for forming a pattern, the method comprising: Forming a resist film by applying the resist composition according to any one of claims 14 to 17 to a substrate; exposing at least a portion of the resist film to high energy radiation to provide an exposed resist film; as well as The exposed resist film is developed using a developer.

19. The method of claim 18, wherein exposing at least a portion of the resist film is performed by irradiating the resist film with at least one of ultraviolet rays, deep ultraviolet (DUV) rays, extreme ultraviolet (EUV) rays, X-rays, gamma rays, electron beams (EB), or alpha rays.

20. The method of claim 18, further comprising: After exposing at least a portion of the resist film to light, heating the exposed resist film, wherein crosslinks are formed in the polymer during heating of the exposed resist film.

Images