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

Abstract

Provided are a polymer including a first repeating unit represented by the following Formula 1 and a second repeating unit represented by the following Formula 2, a resist composition including the same, and a method of forming a pattern using the same. In formulae 1 and 2, L11 to L13, L21 to L24, a11 to a13, a21 to a24, A11, A21, X11, R11, R12, R21 to R23, b12, b22, b23, p11, and p21 are as described in the specification. # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority from Korean Patent Application No. 10-2023-0137032 filed on October 13, 2023 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference. Technical Field

[0003] The present disclosure relates to polymers, resist compositions including the same, and methods of forming patterns using the same. 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 photoresists have been widely used. Chemically amplified resists enable patterning because the base resin of the chemically amplified photoresist reacts with an acid generated via a reaction between light and a photoacid generator (photoacid generator), resulting in a change in the solubility of the base resin in the developer.

[0005] However, in the case of chemically amplified photoresists, the acid generated can diffuse into unexposed areas, leading to problems such as a reduction in pattern uniformity or an increase in surface roughness. In addition, it is difficult to control the diffusion of acid in increasingly sophisticated semiconductor processes, and therefore new resist methods need to be developed.

[0006] Recently, in order to overcome the limitations of chemically amplified photoresists, attempts have been made to develop materials whose physical properties are changed by exposure. However, the dose required for exposure is still high.

[0007] Therefore, there is a need to develop materials whose physical properties change under low doses of light via rapid reactions. Summary of the invention

[0008] Therefore, provided are a polymer whose physical properties, particularly solubility, are changed by exposure even to low doses of light, a resist composition comprising the same, and a method of forming a pattern using the same.

[0009] 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.

[0010] According to an embodiment of the present disclosure, the polymer may include a first repeating unit represented by Formula 1 below and a second repeating unit represented by Formula 2 below.

[0011] <Formula 1>

[0012]

[0013] <Formula 2>

[0014]

[0015] In equations 1 and 2,

[0016] L 11 To L 13 and L 21 To L 24 Each independently may be a single bond, O, S, C(=O), C(=O)O, OC(=O), C(=O)NH, NHC(=O), S(=O), S(=O) 2 O,OS(=O) 2 , or optionally including heteroatoms, linear, branched, or cyclic C 1 -C 30 Divalent hydrocarbon groups,

[0017] a11 to a13 and a21 to a24 can each independently be an integer of 1 to 4,

[0018] A 11 and A 21 Each independently can be C 6 -C 30 Aryl or C 1 -C 30 Heteroaryl,

[0019] X 11 It may be a photodegradable group,

[0020] R 11 It may be a halogen atom, or a linear, branched, or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0021] R 21 It may be a halogen atom, or a linear, branched, or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0022] R 12 and R 22 Each independently may be hydrogen, deuterium, a halogen atom, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a thiol group, a carbonyl moiety, an ester moiety, a sulfonate moiety, a carbonate moiety, a lactone moiety, a sultone moiety, a carboxylic anhydride moiety, or a linear, branched, or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0023] R 23It may be hydrogen, deuterium, a halogen atom, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a thiol group, a carbonyl moiety, an ester moiety, a sulfonate moiety, a carbonate moiety, a lactone moiety, a sultone moiety, a carboxylic anhydride moiety, a linear, branched, or cyclic C 1 -C 30 A monovalent hydrocarbon group, or a photodegradable group,

[0024] b12, b22, and b23 may each independently be an integer from 1 to 10,

[0025] p11 can be an integer from 1 to 3,

[0026] p21 may be an integer from 0 to 4, and

[0027] *Can be a binding site with adjacent atoms.

[0028] According to an embodiment of the present disclosure, the resist composition may include the above-mentioned polymer and an organic solvent.

[0029] According to an embodiment of the present disclosure, a method for forming a pattern may include: forming a resist film by applying the above-mentioned resist composition on a substrate, exposing a portion of the resist film to high-energy rays to provide an exposed resist film, and developing the exposed resist film using a developer. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The above and other aspects, features, and advantages of some embodiments will become more apparent from the following description considered in conjunction with the accompanying drawings, in which:

[0031] Figure 1 is a flow chart showing a method of forming a pattern according to an embodiment;

[0032] Figures 2A to 2C is a side cross-sectional view showing a method of forming a pattern according to an embodiment;

[0033] Figures 3A to 3E is a side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment; and

[0034] Figures 4A to 4E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment. DETAILED DESCRIPTION

[0035] Embodiments will now be described in detail, examples of which are illustrated 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, embodiments are described below 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. Expressions such as "at least one (kind) of", if 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 (e.g., "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.

[0036] When the term "about" or "substantially" is used in conjunction with a numerical value in this specification, it is intended that the associated 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, the intention is not to require the accuracy of the geometric shape, but rather 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. When a range is specified, the range includes all values ​​therebetween, such as increments of 0.1%.

[0037] Because the following disclosure allows for multiple changes and many embodiments, specific embodiments will be shown in the drawings and described in detail in the written description. However, this is not intended to limit the present disclosure 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 present disclosure. In the following description of the present disclosure, when the detailed description of the known functions and configurations introduced herein may obscure the subject matter of the present disclosure, its detailed description will be omitted.

[0038] Although the terms “first,” “second,” “third,” etc. may be used herein to describe various elements, these terms are only used to distinguish one element from another, and the order, type, etc. of the elements are not limited thereby.

[0039] Throughout the specification, it will be understood that when an element such as a layer, film, region, or panel is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween.

[0040] Expressions used in the singular encompass expressions in the plural, unless they have clearly different meanings in the context. In this specification, it will be understood that terms such as "including" or "having" are intended to indicate the presence of features, numbers, processes, operations, elements, parts, components (parts), materials, or combinations thereof disclosed in this specification, and are not intended to exclude the possibility that one or more other features, numbers, processes, operations, elements, parts, components (parts), materials, or combinations thereof may exist or may be added, unless otherwise specified.

[0041] Whenever a range of values ​​is recited, the range includes all values ​​corresponding to the range, as if explicitly recited, and also includes the boundaries of the range. Thus, the range "X to Y" includes all numbers between X and Y, and also includes X and Y.

[0042] As used herein, the term “C x -C y " means that the number of carbon atoms constituting the substituent is from x to y. For example, the term "C 1 -C 6 " means that the number of carbon atoms constituting the substituent is 1 to 6, and the term "C 6 -C 20 " means that the number of carbon atoms constituting the substituent is 6 to 20.

[0043] As used herein, the term "monovalent hydrocarbon group" refers to a monovalent moiety derived from an organic compound including carbon and hydrogen or a derivative thereof, and examples thereof may include a linear 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 (cycloalkyl group, for example, 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, for example, allyl); a monovalent unsaturated alicyclic hydrocarbon group (cycloalkenyl, for example, 3-cyclohexenyl); an aryl group (for example, phenyl, 1-naphthyl, and 2-naphthyl); an arylalkyl group (for example, benzyl and diphenylmethyl); a monovalent hydrocarbon group containing a heteroatom (for example, 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, or nitrogen, or a halogen atom, or some carbon atoms may be replaced by a moiety including a heteroatom such as oxygen, sulfur, or nitrogen, and thus, these groups may include a hydroxyl group, a cyano group, a carboxyl group, an ether bond, a carbonyl moiety, an ester moiety, a sulfonate moiety, a carbonate moiety, a lactone moiety, a sultone moiety, a carboxylic anhydride moiety, or a halogenated alkyl moiety.

[0044] As used herein, the term "divalent hydrocarbon group" refers to a divalent moiety in which at least one hydrogen atom of a monovalent hydrocarbon group is replaced by a binding site to an adjacent atom. The divalent hydrocarbon group may include, for example, a linear or branched alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a cycloalkenylene group, an arylene group, and a group in which some carbon atoms are replaced by heteroatoms.

[0045] As used herein, the term "alkyl" refers to a linear or branched monovalent saturated aliphatic hydrocarbon group, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. As used herein, the term "alkylene" refers to a linear or branched divalent saturated aliphatic hydrocarbon group, and examples thereof include methylene, ethylene, propylene, butylene, and isobutylene.

[0046] As used herein, the term "haloalkyl" refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom, and examples thereof include CF 3 .

[0047] As used herein, the term "alkoxy" refers to a group consisting of the formula -OA 101 A is a monovalent group represented by 101 is an alkyl group. Examples thereof include methoxy, ethoxy, and isopropoxy.

[0048] 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.

[0049] As used herein, the term "haloalkoxy" refers to an alkoxy group in which at least one hydrogen atom is replaced by a halogen atom, and examples thereof include -OCF 3 .

[0050] As used herein, the term "haloalkylthio" refers to an alkylthio group in which at least one hydrogen atom is replaced by a halogen atom, and examples thereof include -SCF 3 .

[0051] As used herein, the term "cycloalkyl" refers to a monovalent saturated hydrocarbon cyclic group, and examples thereof include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, and fused polycyclic groups such as norbornyl and adamantyl. As used herein, the term "cycloalkylene" refers to a divalent saturated hydrocarbon cyclic group, and examples thereof include cyclopentylene, cyclohexylene, adamantylene, adamantylene methyl, norbornylene, norbornylene methyl, tricyclodecylene, tetracyclododecylene, tetracyclododecylene methyl, and dicyclohexylene methyl.

[0052] 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 include cyclopropyloxy and cyclobutyloxy.

[0053] As used herein, the term "cycloalkylthio" refers to a cycloalkylthio group of the formula -SA 102 A is a monovalent group represented by 102 It is a cycloalkyl group.

[0054] As used herein, the term "heterocycloalkyl" refers to a cycloalkyl in which some of the carbon atoms are replaced by a portion including heteroatoms such as oxygen, sulphur or nitrogen, and the heterocycloalkyl can specifically include ether bonds, ester bonds, sulfonate bonds, carbonates, lactone rings, sultone rings or carboxylic anhydride moieties. As used herein, the term "heterocycloalkylene" refers to a cycloalkylene in which some of the carbon atoms are replaced by a portion including heteroatoms such as oxygen, sulphur or nitrogen.

[0055] As used herein, the term "heterocycloalkoxy" refers to a103 A is a monovalent group represented by 103 It is a heterocycloalkyl group.

[0056] As used herein, the term "alkenyl" refers to a linear or branched monovalent unsaturated aliphatic hydrocarbon group including at least one carbon-carbon double bond. As used herein, the term "alkenylene" refers to a linear or branched divalent unsaturated aliphatic hydrocarbon group including at least one carbon-carbon double bond.

[0057] As used herein, the term "alkenyloxy" refers to a 104 A is a monovalent group represented by 104 It is an alkenyl group.

[0058] As used herein, the term "cycloalkenyl" refers to a monovalent unsaturated hydrocarbon cyclic group including at least one carbon-carbon double bond. As used herein, the term "cycloalkenylene" refers to a divalent unsaturated hydrocarbon cyclic group including at least one carbon-carbon double bond.

[0059] As used herein, the term "cycloalkenyloxy" refers to a 105 A is a monovalent group represented by 105 It is a cycloalkenyl group.

[0060] As used herein, the term "heterocycloalkenyl" refers to a cycloalkenylene group in which some of the carbon atoms are replaced by a moiety that includes a heteroatom such as oxygen, sulfur, or nitrogen. As used herein, the term "heterocycloalkenylene group" refers to a cycloalkenylene group in which some of the carbon atoms are replaced by a moiety that includes a heteroatom such as oxygen, sulfur, or nitrogen.

[0061] As used herein, the term "heterocycloalkenyloxy" refers to a 106 A is a monovalent group represented by 106 It is a heterocycloalkenyl group.

[0062] As used herein, the term "alkynyl" refers to a straight-chain or branched monovalent unsaturated aliphatic hydrocarbon group including at least one carbon-carbon triple bond.

[0063] As used herein, the term "alkynyloxy" refers to a radical of the formula -OA 107 A is a monovalent group represented by 107 It is an alkynyl group.

[0064] As used herein, the term "aryl" refers to a monovalent group including a carbocyclic aromatic system, and examples thereof include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, and base.

[0065] As used herein, the term "aryloxy" refers to a radical of the formula -OA 108 A is a monovalent group represented by108 It is an aromatic group.

[0066] As used herein, the term "heteroaryl" refers to a monovalent group including a heterocyclic aromatic system, and examples thereof include pyridyl, pyrimidyl, and pyrazinyl. As used herein, the term "heteroarylene" refers to a divalent group including a heterocyclic aromatic system.

[0067] As used herein, the term "heteroaryloxy" refers to a 109 A is a monovalent group represented by 109 It is a heteroaryl group.

[0068] As used herein, the term "substituent" includes deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, an amino group, an ether moiety, a carbonyl moiety, an ester moiety, a sulfonate moiety, a carbonate moiety, a carbamate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic acid anhydride moiety, a 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; and

[0069] C is unsubstituted or substituted as follows 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C20 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, and any combination thereof: deuterium, halogen atom, hydroxyl, cyano, nitro, carboxyl, amino, ether moiety, carbonyl moiety, ester moiety, sulfonate moiety, carbonate moiety, carbamate 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.

[0070] Hereinafter, the embodiments will be described in detail with reference to the accompanying drawings. In the accompanying drawings, the same reference numerals represent the same elements or components having substantially the same functions, and repeated descriptions will be omitted. In the accompanying drawings, the thickness of each layer and region is magnified for clarity. In the accompanying drawings, for ease of description, the thickness of some layers and regions is exaggerated for clarity. At the same time, it should be understood that the embodiments described below are for illustrative purposes only, and various changes in form may be made to the embodiments.

[0071] [polymer]

[0072] The polymer according to an embodiment includes a first repeating unit represented by Formula 1 below and a second repeating unit represented by Formula 2 below.

[0073] <Formula 1>

[0074]

[0075] <Formula 2>

[0076]

[0077] In equations 1 and 2,

[0078] L 11 To L 13 and L 21 To L 24 Each is independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O) 2 O; OS(=O) 2 ; or a linear, branched, or cyclic C optionally including heteroatoms 1 -C 30 Divalent hydrocarbon groups,

[0079] a11 to a13 and a21 to a24 are each independently an integer of 1 to 4,

[0080] A 11 and A 21 Each independently is C 6 -C 30 Aryl or C 1 -C 30 Heteroaryl,

[0081] X 11 is a photodegradable group,

[0082] R 11 is a halogen atom, or a linear, branched, or cyclic C 1 -C30 Monovalent hydrocarbon groups,

[0083] R 21 is a halogen atom, or a linear, branched, or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0084] R 12 and R 22 Each independently is: hydrogen; deuterium; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a thiol group; a carbonyl moiety; an ester moiety; a sulfonate moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a linear, branched, or cyclic C optionally including a heteroatom 1 -C 30 Monovalent hydrocarbon groups,

[0085] R 23 is hydrogen; deuterium; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a thiol group; a carbonyl moiety; an ester moiety; a sulfonate moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; a linear, branched, or cyclic C optionally including a heteroatom 1 -C 30 a monovalent hydrocarbon group; or a photodegradable group,

[0086] b12, b22, and b23 are each independently an integer from 1 to 10,

[0087] p11 is an integer from 1 to 3,

[0088] p21 is an integer from 0 to 4, and

[0089] * is the binding site with the adjacent atom.

[0090] For example, in Equations 1 and 2, L 11 To L 13 and L 21 To L 24 Each independently may be: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O) 2 O; OS(=O) 2 ; 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 30Alkenylene; 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 Arylene.

[0091] As another example, in Formulas 1 and 2, L 11 To L 13 and L 21 To L 24 Each of the following may be independently selected from: a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O) 2 O; OS(=O) 2 ; and C which is unsubstituted or substituted as follows 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 group: deuterium, halogen atom, cyano group, hydroxyl group, amino group, carboxyl group, thiol group, carbonyl moiety, ester moiety, sulfonate moiety, carbonate moiety, carbamate 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.

[0092] As another example, in Formulas 1 and 2, L 11 To L 13 and L21 To L 24 Each of the following may be independently selected from: a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O) 2 O; OS(=O) 2 ; and C which is unsubstituted or substituted as follows 1 -C 20 Alkylene, C 3 -C 20 Cycloalkylene, C 3 -C 20 Heterocycloalkylene, phenylene, and naphthylene: deuterium, halogen atoms, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 alkoxy, phenyl, naphthyl, or any combination thereof.

[0093] In Formulae 1 and 2, a11 to a13 and a21 to a24 each independently refer to L 11 To L 13 and L 21 To L 24 The number of repetitions.

[0094] For example, in Formulae 1 and 2, a11 to a13 and a21 to a24 may each independently be an integer of 1 to 3.

[0095] As another example, in Formulae 1 and 2, a11 to a13 and a21 to a24 may each independently be 1.

[0096] For example, in Formulas 1 and 2, A 11 and A 21 can be independently selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, benzo[9,10]phenanthrenyl, pyrenyl, yl, pyrrolyl, thienyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl, isoquinolyl, benzoquinolyl, quinoxalinyl, quinazolyl, and cinnolinyl.

[0097] In particular, in Formulas 1 and 2, A 11 and A 21 Each may be independently selected from a phenyl group, a biphenyl group, a terphenyl group, and a naphthyl group.

[0098] For example, in Formula 1, X 11 A tertiary non-cyclic alkyl carbon-containing group, a tertiary alicyclic carbon-containing group, an acetal group, or an ON bond-containing group may be included.

[0099] In particular, in Formula 1, X 11 It may be an ester group containing a tertiary non-cyclic alkyl carbon, an ester group containing a tertiary alicyclic carbon, a carbonate group containing a tertiary non-cyclic alkyl carbon, a carbonate group containing a tertiary alicyclic carbon, a carbamate group containing a tertiary non-cyclic alkyl carbon, a carbamate group containing a tertiary alicyclic carbon, an acetal group, a sulfonate group containing a tertiary non-cyclic alkyl carbon, a sulfonate group containing a tertiary alicyclic carbon, or a group containing an ON bond.

[0100] In an embodiment, in Formula 1, X 11 It can be represented by one of the following formulas 6-1 to 6-14.

[0101]

[0102] In equations 6-1 to 6-14,

[0103] X 61 is an ester moiety, a carbonate moiety, a carbamate moiety, or a sulfonate moiety;

[0104] a61 is an integer from 0 to 6;

[0105] R 61 and R 68 are each independently a linear, branched, or cyclic C 1 -C 20 a monovalent hydrocarbon group;

[0106] R 62 To R 67 Each independently is: hydrogen; deuterium; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a thiol group; a carbonyl moiety; an ester moiety; a sulfonate moiety; a carbonate moiety; a carbamate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a linear, branched, or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0107] In R 61 To R 68 , two neighbors are optionally bound to each other to form a ring,

[0108] b64 is an integer from 1 to 10, and

[0109] * is the binding site with the adjacent atom.

[0110] For example, in Formula 1, R 11 It can be a halogen atom, a substituted or unsubstituted C 1 -C 20 Alkyl, or substituted or unsubstituted C 1 -C20 Halogenated alkyl.

[0111] In particular, in Formula 1, R 11 Can be F, CH 3 , CH 2 CH 3 , CH 2 F. CHF 2 CF 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 .

[0112] For example, in Formula 2, R 21 It may be a halogen atom, or a substituted or unsubstituted C 1 -C 20 Halogenated alkyl.

[0113] In particular, in Formula 2, R 21 Can be F, CH 2 F. CHF 2 CF 3 , CHFCH 3 , CHFCH 2 F. CHFCHF 2 , CHFCF 3 CF 2 CH 3 CF 2 CH 2 F. CF 2 CHF 2 CF 2 CF 3 , Cl, CH 2 Cl, CHCl 2 , CCl 3 , CHClCH 3 , CHClCH 2 Cl, CHClCHCl 2 , CHClCCl 3 , CCl 2 CH 3 , CCl 2 CH 2 Cl, CCl 2CHCl 2 , or CCl 2 CCl 3 .

[0114] For example, in Formulas 1 and 2, R 12 and R 22 may be independently selected from: hydrogen; deuterium; halogen atoms; cyano groups; hydroxyl groups; amino groups; carboxyl groups; thiol groups; and C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, and C 6 -C 20 Aryl group: deuterium, halogen atom, cyano group, hydroxyl group, amino group, carboxyl group, thiol group, carbonyl moiety, 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.

[0115] In particular, in Formulas 1 and 2, R 12 and R 22 can be independently: hydrogen; deuterium; halogen atom; cyano group; hydroxyl group; amino group; carboxyl group; thiol group; C 1 -C 20 Alkyl; C 1 -C 20 Haloalkyl; C 3 -C 20 Cycloalkyl; or C 6 -C 20 Aryl.

[0116] For example, in Formula 2, R 23 can be selected from: photodegradable groups; hydrogen; deuterium; halogen atoms; cyano groups; hydroxyl groups; amino groups; carboxyl groups; thiol groups; and C each being unsubstituted or substituted as follows 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, and C 6 -C 20Aryl group: deuterium, halogen atom, cyano group, hydroxyl group, amino group, carboxyl group, thiol group, carbonyl moiety, 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.

[0117] In particular, in Formula 2, R 23 It can be: photodegradable group; hydrogen; deuterium; halogen atom; cyano group; hydroxyl group; amino group; carboxyl group; thiol group; C 1 -C 20 Alkyl; C 1 -C 20 Haloalkyl; C 3 -C 20 Cycloalkyl; or C 6 -C 20 Aryl.

[0118] For example, in Formula 1, p11 may be 1.

[0119] For example, in Formula 2, p21 may be 0 or 1.

[0120] In an embodiment, the first repeating unit may be represented by the following Formula 1-1.

[0121] <Formula 1-1>

[0122]

[0123] In formula 1-1,

[0124] L 11 To L 13 、a11 to a13、X 11 , R 11 , R 12 , and p11 are as described above, c12 is an integer from 1 to 4, and

[0125] * is the binding site with the adjacent atom.

[0126] In particular, the first repeating unit may be selected from the repeating units of Group I below.

[0127] <Group I>

[0128]

[0129]

[0130] In an embodiment, the second repeating unit may be represented by one of the following Formulae 2-1 and 2-2.

[0131]

[0132] In formulas 2-1 and 2-2,

[0133] L 21 To L 24 、a21 to a24、R 21 To R 23 , and b23 are as defined in Formula 2,

[0134] c22 is an integer from 1 to 4, and

[0135] * is the binding site with the adjacent atom.

[0136] In an embodiment, the second repeating unit may be selected from the repeating units of Group II below.

[0137] <Group II>

[0138]

[0139] In an embodiment, the polymer may include (or consist of) the first repeating unit and the second repeating unit. In particular, the polymer may include about 1 mol % to about 99 mol % of the first repeating unit and about 1 mol % to about 99 mol % of the second repeating unit. More particularly, the polymer may include about 20 mol % to about 90 mol % of the first repeating unit and about 10 mol % to about 80 mol % of the second repeating unit. In particular, the first repeating unit and the second repeating unit may be included in the polymer in a molar ratio of about 5:1 to about 1:5.

[0140] The polymer may further include a third repeating unit represented by Formula 3 below.

[0141] <Formula 3>

[0142]

[0143] In formula 3,

[0144] L 31 To L 33Each independently represents: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O) 2 O; OS(=O) 2 ; or a linear, branched, or cyclic C optionally including heteroatoms 1 -C 30 Divalent hydrocarbon groups,

[0145] a31 to a33 are each independently an integer of 1 to 4,

[0146] R 31 is: hydrogen; deuterium; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a thiol group; a carbonyl moiety; an ester moiety; a sulfonate moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a linear, branched, or cyclic C optionally including a heteroatom 1 -C 30 Monovalent hydrocarbon groups,

[0147] X 31 is a photodegradable group or a non-acid-labile group, and

[0148] * is the binding site with the adjacent atom.

[0149] In formula 3, L 31 To L 33 As mentioned above, L in Formula 1 11 As described in

[0150] In Formula 3, a31 to a33 are as described above in a11 of Formula 1,

[0151] In formula 3, R 31 As mentioned above in Formula 1, R 12 As described in

[0152] In Formula 3, the photodegradable group is as described above in X of Formula 1. 11 As described in

[0153] In Formula 3, the non-acid-labile group may be: hydrogen; a halogen atom; a cyano group; a hydroxyl group; a carboxyl group; a thiol group; an amino group; or optionally a linear, branched, or cyclic C 1 -C 30 Monovalent hydrocarbon groups: halogen atoms, cyano groups, hydroxyl groups, thiol groups, carboxyl groups, O, C=O, C(=O)O, OC(=O), S(=O) 2 O, OS (=O) 2 , a lactone portion, a sultone portion, and a carboxylic anhydride portion.

[0154] In an embodiment, the non-acid-labile group of Formula 3 may be selected from hydrogen, hydroxyl, and

[0155] One of the groups represented by formulae 5-1 to 5-12.

[0156]

[0157] In formulas 5-1 to 5-12,

[0158] a51 can be 1 or 2;

[0159] R 51 To R 56 can be independently: a binding site with an adjacent atom; hydrogen; a hydroxyl group; a carboxyl group; a carbonyl moiety; an ester moiety; a carbonate moiety; a carbamate moiety; a lactone moiety; a carboxylic anhydride moiety; or a linear, branched, or cyclic C 1 -C 20 Monovalent hydrocarbon groups,

[0160] R 51 To R 53 One, R 54 One, and R 55 and R 56 One of them may be a binding site with a neighboring atom,

[0161] b51 can be an integer from 1 to 4,

[0162] b52 can be an integer from 1 to 10,

[0163] b53 can be an integer from 1 to 8,

[0164] b54 can be an integer from 1 to 5,

[0165] b55 can be an integer from 1 to 7,

[0166] b56 can be an integer from 1 to 11,

[0167] b57 can be an integer from 1 to 13,

[0168] b58 can be an integer from 1 to 15,

[0169] b59 can be an integer from 1 to 2, and

[0170] m51 can be an integer from 1 to 4.

[0171] In particular, the non-acid-labile group of Formula 3 may be selected from hydroxyl groups, and groups represented by Formulas 5-1, 5-6, and 5-10.

[0172] In an embodiment, the third repeating unit may be selected from the repeating units of Group III below.

[0173] <Group III>

[0174]

[0175]

[0176] In an embodiment, the polymer may include (or consist of) the first repeating unit, the second repeating unit, and the third repeating unit. The polymer may include about 1 mol % to about 98 mol % of the first repeating unit, about 1 mol % to about 98 mol % of the second repeating unit, and about 1 mol % to about 98 mol % of the third repeating unit. In particular, the first repeating unit and the third repeating unit may be included in the polymer in a molar ratio of about 10:1 to about 1:10.

[0177] The polymer may have a weight average molecular weight Mw of about 1,000 to about 500,000, specifically about 3,000 to about 200,000, more specifically about 5,000 to about 50,000, as measured by gel permeation chromatography using a tetrahydrofuran solvent and polystyrene as a standard material.

[0178] The polymer may have a polydispersity index (PDI: Mw / Mn) of about 1.0 to about 3.0. In the case where the above range is met, the dispersibility and / or compatibility of the polymer can be easily controlled, the possibility of foreign (foreign) substances remaining on the pattern can be reduced, or the deterioration of the pattern profile can be minimized. Therefore, the resist composition can become more suitable for forming fine patterns.

[0179] Because the physical properties of the polymer itself can be changed by high-energy rays, the polymer can be used in non-chemically amplified resist compositions. In particular, when the main chain of the polymer is decomposed, the molecular weight of the polymer decreases, resulting in increased solubility in the developer.

[0180] In addition, because the R 11 is not hydrogen, so the stability of the free radicals generated as a result of the decomposition of the main chain can be improved, and thus it is more convenient to include hydrogen as R 11 The rate and / or speed of decomposition of the backbone may be increased compared to the polymer.

[0181] This will be described in more detail. In general, the decomposition mechanism of a copolymer of an α-alkylstyrene and an α-halogenated acrylate having a substituent at the α position by high-energy rays can be represented as Scheme 1. In the polymer decomposition reaction, after the dissociation of the halogen ion occurs, β-fragmentation (cutting) of the free radical obtained thereby occurs. In this case, the decomposition rate (rate) can be increased because R on the carbon in the β position1 Therefore, the decomposition rate of the polymer including alkyl as a substituent can be greater than that of the polymer including hydrogen as R 1 The decomposition rate of the polymer.

[0182] <Scheme 1>

[0183]

[0184] In addition, Gaussian simulation was performed on the polymer represented by Formula A according to density functional theory (DFT) to determine the reaction rate of the main chain of the polymer depending on the type of substituents.

[0185] As shown in Table 1 below, it is confirmed that the content of the present disclosure including methyl or chlorine as R 1 and methyl or chlorine as R 2 The polymer has a ratio including hydrogen or fluorine as R 1 and fluorine as R 2 The polymer has a low bond dissociation energy (BDE). That is, including methyl or chlorine as R 1 and methyl or chlorine as R 2 The polymer can be easily decomposed by high-energy rays.

[0186] <Formula A>

[0187]

[0188] Table 1

[0189]

[0190] In addition, since the polymer includes a photodegradable group on the side chain, the solubility of the polymer in a developer, particularly an alkaline developer that does not include an organic solvent, can be increased due to the decomposition of the side chain by high-energy rays. Therefore, compared with other positive resist compositions using an organic solvent as a developer, environmental pollution can be reduced.

[0191] In addition, since the first repeating unit of the polymer includes the photodegradable group and R 11 (rather than hydrogen), so not only the decomposition reaction of the main chain of the polymer occurs rapidly by the high-energy rays, but also the decomposition reaction for the detachment of the side chain occurs simultaneously. Finally, as the molecular weight of the polymer having a high molecular weight decreases and the amount (or concentration) of polar functional groups soluble in an alkaline developer increases relative to the initial stage of exposure, the solubility in the developer further increases, and thus a fine pattern with increased resolution can be effectively formed even with a lower exposure dose.

[0192] Since the second repeating unit of the polymer comprises R21 , therefore, not only can the decomposition rate of the polymer be increased even at a low dose of high-energy rays, but also a fine pattern with increased resolution can be effectively formed by reducing the molecular weight of the polymer at a low dose.

[0193] Since the polymer has relatively high resistance to oxygen and / or moisture and has physical properties that are changed only by high-energy rays, a resist composition having improved physical properties such as storage stability can be provided.

[0194] Unlike chemically amplified photoresists (which may cause problems such as low pattern uniformity or high surface roughness due to acid generated and diffused to unexposed areas), the solubility of the polymer is not changed by the acid, and thus the problems of low pattern uniformity and / or generation of defects due to diffusion of the acid can be reduced.

[0195] The polymer can be produced by any appropriate method, for example, a method of dissolving a monomer having an unsaturated bond in an organic solvent and performing thermal polymerization in the presence of a radical initiator.

[0196] The structure (composition) of the polymer can be determined by FT-IR analysis, NMR analysis, X-ray fluorescence (XRF) analysis, mass spectrometry, UV analysis, single crystal X-ray diffraction, powder X-ray diffraction (PXRD), liquid chromatography (LC), size exclusion chromatography (SEC), thermal analysis, etc. The detailed description of the determination method is shown in the following examples.

[0197] [Resist composition]

[0198] According to another aspect, a resist composition includes the above-mentioned polymer and an organic solvent. The resist composition may have enhanced properties such as improved developability and / or increased resolution.

[0199] Exposure to high energy rays changes the solubility of the resist composition in a developer. The resist composition may be a positive resist composition that forms a positive resist pattern by dissolving and removing the exposed portion of the resist film.

[0200] In addition, the resist composition according to the embodiment may be a resist composition for an alkaline development process in which an alkaline developer is used for development when forming a resist pattern, or a resist composition for a solvent development process in which an organic solvent-containing developer (hereinafter referred to as an organic developer) is used for development. In particular, the resist composition according to the embodiment may be a resist composition for an alkaline development process.

[0201] Since the physical properties of the polymer are changed by exposure, the resist composition may include (or may substantially exclude) a compound having a molecular weight of 1,000 or more in addition to the polymer.

[0202] Based on 100 parts by weight of the resist composition, the polymer can be used in an amount of about 0.1 parts by weight to about 80 parts by weight. In particular, based on 100 parts by weight of the resist composition, the polymer can be used in an amount of about 0.5 parts by weight to about 5 parts by weight. In the case where the above range is met, the reduction in sensitivity caused by insufficient solubility and / or the formation of particles of foreign substances can be reduced.

[0203] Since the polymer is as described above, hereinafter, the organic solvent and optional components included, if necessary, will be described. In addition, the polymer used may be used alone in the resist composition or at least two thereof may be used in combination.

[0204] <Organic Solvents>

[0205] The organic solvent included in the resist composition is not particularly limited, as long as the polymer and optional components (if necessary) contained therein can be dissolved or dispersed therein. The organic solvent can be used alone, or any combination of two or more different organic solvents can be used. In addition, a mixed solvent of water and an organic solvent can also be used.

[0206] 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, and a hydrocarbon-based solvent.

[0207] More specifically, 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-methylpentanol, tert-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 2-methylpent ... -ethylbutanol, 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 and diacetone alcohol; solvents based on polyols, 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 solvents based on ethers containing polyols, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl The following are the ingredients of the present invention: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene 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 and dipropylene glycol monopropyl ether.

[0208] Examples of the ether-based solvent may include: diethylene glycol dimethyl ether, propylene glycol dimethyl ether; dialkyl ether-based solvents such as diethyl ether, dipropyl ether and dibutyl ether; cyclic ether-based solvents such as tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether-based solvents such as diphenyl ether and anisole.

[0209] 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, and trimethylnonanone; cyclic ketone-based solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; and 2,4-pentanedione, acetonylacetone, and acetophenone.

[0210] Examples of the amide-based solvent may include: cyclic amide-based solvents such as N,N'-dimethylimidazolidinone and N-methyl-2-pyrrolidone; and chain amide-based solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.

[0211] Examples of the ester-based solvent may include: acetate-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-amyl acetate, isoamyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, and n-nonyl acetate; polyol-containing ether carboxylate-based solvents 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 (PGMA) The present invention relates to solvents based on dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate; solvents based on lactate, such as methyl lactate, ethyl lactate, n-butyl lactate and n-amyl lactate; and ethylene glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, dimethyl phthalate and diethyl phthalate.

[0212] Examples of the sulfoxide-based solvent may include dimethyl sulfoxide and diethyl sulfoxide.

[0213] 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, and methylcyclohexane; and aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-pentylnaphthalene.

[0214] In particular, the organic solvent may be selected from the alcohol-based solvent, the amide-based solvent, the ester-based solvent, the sulfoxide-based solvent, and any combination thereof. More particularly, the 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.

[0215] The organic solvent may be included in an amount of about 200 parts to about 5,000 parts by weight, for example about 400 parts to about 3,000 parts by weight, based on 100 parts by weight of the polymer.

[0216] <Optional Components>

[0217] If necessary, the resist composition may further include an acid generator, a quencher, a dissolution enhancer, a dissolution inhibitor, a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof.

[0218] The resist composition may further include an acid generator to improve developability, etc. The acid generator may be an ionic acid generator and a non-ionic acid generator.

[0219] Examples of the acid generator may include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, pyridinium trifluoromethanesulfonate, salicylic acid, 5-sulfosalicylic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, 4-phenolsulfonic acid, methyl 4-phenolsulfonate, benzene disulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-toluenesulfonyloxyphthalimide, N-hydroxynaphthalimide trifluoromethanesulfonate, O-toluenesulfonylacetophenone oxime, N-trifluoromethylsulfonyloxyphthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, )bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluoro-n-butylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(perfluoro-n-octylsulfonyloxy)-1,8-naphthalimide, N-(perfluoro-n-octylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-(3-tetracyclo[4.4.0.1 2,5 .1 7,10 ] dodecyl)-1,1-difluoroethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, or any combination thereof, but are not limited thereto.

[0220]

[0221] Alternatively, the acid generator may be represented by Formula 7 below.

[0222] <Formula 7>

[0223] B 71 + A 71 -

[0224] In formula 7,

[0225] B 71 + It is represented by the following formula 7A, A 71 - is represented by one of the following Formulae 7B to 7D, and

[0226] B 71 + Optionally linked to A via a carbon-carbon covalent bond 71 - .

[0227]

[0228] In Formulas 7A to 7D,

[0229] L 71 To L 73 are each independently a single bond or CRR',

[0230] R and R' are each independently hydrogen, deuterium, a halogen atom, a cyano group, a hydroxyl group, a 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,

[0231] n71 to n73 are each independently 1, 2, or 3,

[0232] x71 to x72 are each independently 0 or 1,

[0233] R 71 and R 73 are each independently a linear, branched, or cyclic C 1 -C 30 a monovalent hydrocarbon group;

[0234] In R 71 To R 73 In the embodiment, two neighbors may optionally be combined with each other to form a fused ring, and

[0235] R 74 To R 76 are each independently hydrogen; a halogen atom; or a linear, branched, or cyclic C optionally including a heteroatom 1 -C 30 A monovalent hydrocarbon group.

[0236] 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, in Formula 7A, R 71 To R 73 Each may independently be a phenyl group.

[0237] Examples of the acid generator may be the compounds shown below.

[0238]

[0239] The acid generator may be included in an amount of about 0.01 to about 30 parts by weight, about 0.05 to about 20 parts by weight, or about 0.1 to about 10 parts by weight, based on 100 parts by weight of the polymer. In the case where the above range is satisfied, appropriate resolution may be obtained, and problems associated with foreign substances after development or during stripping may be reduced.

[0240] The resist composition may further include a quencher to improve developability, etc. The quencher may be a salt that generates an acid having lower acidity than the acid generated from the acid generator.

[0241] The quencher may include an ammonium salt, a sulfonium salt, an iodonium salt, or any combination thereof.

[0242] In an embodiment, the quencher may be represented by Formula 8 below.

[0243] <Formula 8>

[0244] B 81 + A 81 -

[0245] In formula 8,

[0246] B 81 + is represented by one of the following formulas 8A to 8C, and A 81- is represented by one of the following formulae 8D to 8F, and

[0247] B 81 + Optionally linked to A via a carbon-carbon covalent bond 81 - .

[0248]

[0249] In Formulas 8A to 8F,

[0250] L 81 and L 82 are each independently a single bond or CRR',

[0251] R and R' are each independently hydrogen, deuterium, a halogen atom, a cyano group, a hydroxyl group, a C 1 -C 30 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 30 Alkoxy, C 3 -C 30 Cycloalkyl, or C 3 -C 30 Cycloalkoxy,

[0252] n81 and n82 are each independently 1, 2, or 3,

[0253] x81 is 0 or 1,

[0254] R 81 To R 84 Each independently is a linear, branched, or cyclic C 1 -C 30 Monovalent hydrocarbon group, in R 81 To R 84 , two neighbors may optionally bind to each other to form a ring, and

[0255] R 85 and R 86 are each independently hydrogen; a halogen atom; or a linear, branched, or cyclic C optionally including a heteroatom 1 -C 30 A monovalent hydrocarbon group.

[0256] For example, the quencher may be the compound shown below:

[0257]

[0258] The quencher may be included in an amount of 0.01 to 30 parts by weight, 0.05 to 20 parts by weight, or 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. In the case where the above range is satisfied, appropriate resolution may be obtained, and problems associated with foreign substances after development or during stripping may be reduced.

[0259] The quencher may be used alone, or any combination of two or more different quenchers may be used in combination.

[0260] The resist composition may further include a dissolution inhibitor to improve developability, etc. The dissolution inhibitor may include a phenolphthalein derivative, a fluorescein derivative, or any combination thereof. Examples of the dissolution inhibitor include compounds represented by the following formulas I-1 to I-3.

[0261]

[0262] Here, "t-BOC" refers to tert-butoxycarbonyl.

[0263] The resist composition may further include a surfactant to improve coating properties, developability, etc. 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, and polyethylene glycol distearate. Any commercially available product or synthetic product may be used as the surfactant. 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.), Eftop EF301, Eftop EF303, and Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), F171, MEGAFACE F173, R40, R41, and R43 (manufactured by DIC Corporation), FC430, Fluorad FC431 (manufactured by 3M Co., Ltd.), AsahiGuard AG710 (manufactured by AGC Co., Ltd.), and S-382, 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.).

[0264] The surfactant may be included in an amount of about 0 parts by weight to about 20 parts by weight based on 100 parts by weight of the polymer. The surfactant may be used alone, or any mixture of two or more different surfactants may also be used.

[0265] The method for preparing the resist composition is not particularly limited, and any method of mixing the polymer and the optional components added as needed in an organic solvent may also be used. The temperature or time of mixing is not particularly limited. If necessary, filtering may be performed after mixing.

[0266] [Method of forming a pattern]

[0267] In the following, reference will be made to Figure 1 and Figures 2A to 2C A method of forming a pattern according to an embodiment is described in more detail. Figure 1 is a flow chart illustrating a method of forming a pattern according to an embodiment. Figures 2A to 2C is a side cross-sectional view showing a method of forming a pattern according to an embodiment. Hereinafter, a method of forming a pattern using a positive resist composition will be described as an example, but the embodiment is not limited thereto.

[0268] Reference Figure 1 , the method of forming a pattern includes: forming a resist film by applying a resist composition to a substrate 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. If necessary, these processes may be omitted or may be performed in a different order.

[0269] First, a substrate 100 is prepared. The substrate 100 may be a semiconductor substrate such as a silicon substrate and a germanium substrate, or may be formed of glass, quartz, ceramic, copper, etc. In some embodiments, the substrate 100 may include a Group 3-5 compound such as GaP, GaAs, and GaSb.

[0270] The resist film 110 may be formed on the substrate 100 by applying the resist composition to the substrate 100 to a desired thickness using a coating method. If necessary, the resist film 110 may be heated (pre-baking (PB) or post-annealing baking (PAB)) to remove the organic solvent remaining in the resist film 110.

[0271] As coating method, spin coating, dipping, roller coating or other common coating methods can be used. Among them, spin coating can be used in particular. The resist film 110 with a desired thickness can be formed by adjusting the viscosity, concentration and / or rotation speed of the resist composition. In particular, the resist film 110 can have a thickness of 10nm to 300nm. More particularly, the resist film 110 can have a thickness of 30nm to 200nm.

[0272] The lower limit of the pre-baking temperature may be 60° C. or higher, in particular, 80° C. or higher. In addition, the upper limit of the pre-baking temperature may be 150° C. or lower, in particular, 140° C. or lower. The lower limit of the pre-baking time may be 5 seconds or more, in particular, 10 seconds or more. The upper limit of the pre-baking time may be 600 seconds or less, in particular, 300 seconds or less.

[0273] Before the resist composition is applied to the substrate 100, a film to be etched (not shown) may be formed on the substrate 100. The film to be etched may refer to a film to which an image is transferred from a resist pattern to be converted into a 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, and silicon oxynitride. In some embodiments, the film to be etched may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, and a metal silicon nitride. In some embodiments, the film to be etched may be formed to include a semiconductor material such as polysilicon.

[0274] In an embodiment, an anti-reflection film may be further formed on the substrate 100 to maximize the efficiency of the resist. The anti-reflection film may be an organic or inorganic anti-reflection film.

[0275] In an embodiment, a protective film may be further formed on the resist film 110 to reduce the influence of alkaline impurities included during the process. In addition, in the case of performing immersion lithography, a protective film for immersion lithography may be formed on the resist film 110 to avoid direct contact between the immersion medium and the resist film 110.

[0276] Subsequently, at least a portion of the resist film 110 may be exposed to high-energy rays. For example, high-energy rays having passed through the mask 120 may reach at least a portion of the resist film 110. Therefore, the resist film 110 may have an exposed region 111 and an unexposed region 112.

[0277] If necessary, exposure is performed by emitting high-energy rays through a mask having a specific pattern using a liquid such as water as a medium. Examples of high-energy rays may include electromagnetic waves such as ultraviolet rays, deep ultraviolet rays, extreme ultraviolet (EUV) rays (wavelength of 13.5 nm), X-rays, and gamma rays; and charged particle beams such as electron beams and alpha particle beams. Irradiation of these high-energy rays may be collectively referred to as "exposure".

[0278] A variety of light sources can be used for exposure. For example, a light source emitting a laser beam in the UV range, such as a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (wavelength of 193 nm), and a F 2 Excimer laser (wavelength of 157nm), a light source (YAG or semiconductor laser) that emits a harmonic laser beam in the far ultraviolet or vacuum ultraviolet range by converting the wavelength of a laser beam received from a solid laser light source, and a light source that emits an electron beam or EUV. During exposure, a mask corresponding to a desired pattern is generally used. However, in the case of using an electron beam as a light source for exposure, exposure can be performed directly without using a mask.

[0279] When extreme ultraviolet rays are used as high-energy rays, the integrated dose of high-energy rays can be 2000 mJ / cm 2 or less, in particular, 500 mJ / cm 2 Or less. In addition, in the case of using electron beams as high-energy rays, the integrated dose can be 5000 μC / cm 2 or less, in particular, 1000μC / cm 2 or smaller.

[0280] Although not limited to a particular theory, when the main chain of the polymer is decomposed (chain scission) and a portion of the side chain of the polymer (e.g., a photodegradable group) is deprotected in the exposed area 111 by exposure, the molecular weight of the polymer decreases, and thus the solubility and / or dissolution rate (rate) of the polymer in a developer (particularly, an alkaline developer) may increase.

[0281] In addition, a post-exposure bake (PEB) may be performed after exposure. The lower limit of the PEB temperature may be 50° C. or higher, in particular, 80° C. or higher. The upper limit of the PEB temperature may be 180° C. or lower, in particular, 130° C. or lower. The lower limit of the PEB time may be 5 seconds or more, in particular, 10 seconds or more. The upper limit of the PEB time may be 600 seconds or less, in particular, 300 seconds or less.

[0282] The exposed resist film 110 may be developed using a developer. The exposed region 111 may be washed away by the developer, and the unexposed region 112 may remain without being washed away by the developer.

[0283] As the developer, an alkaline developer, a developer including an organic solvent (hereinafter, referred to as "organic developer"), etc. may be used. The developing method may be dipping, puddling, spraying, a dynamic method, etc. The developing temperature may be, for example, 5° C. to 60° C., and the developing time may be, for example, 5 seconds to 300 seconds.

[0284] Examples of the alkaline developer may include an alkaline aqueous solution including at least one alkaline compound dissolved therein, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, 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), and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN). The alkaline developer may further include a surfactant.

[0285] The lower limit of the amount of the alkaline compound contained in the alkaline developer may be 0.1% by mass or more, particularly 0.5% by mass or more, more particularly 1% by mass or more. In addition, the upper limit of the amount of the alkaline compound contained in the alkaline developer may be 20% by mass or less, particularly 10% by mass or less, more particularly 5% by mass or less.

[0286] After the development, the resist pattern may be cleaned with ultrapure water, and then, the water remaining on the substrate and the pattern may be removed.

[0287] For example, the organic solvent contained in the organic developer may be the same as those described above in <Organic Solvent> of [Resist Composition].

[0288] In the organic developer, the lower limit of the amount of the organic solvent may be 80 wt % or more, specifically 90 wt % or more, more specifically 95 wt % or more, specifically 99 wt % or more.

[0289] The organic developer may include a surfactant. In addition, the organic developer may include trace amounts of moisture. In addition, during development, development may be stopped by replacing the organic developer with a different type of solvent.

[0290] The resist pattern may be further washed after development. Ultrapure water, a cleaning solution, etc. may be used as a cleaning solution. The cleaning solution is not particularly limited as long as the resist pattern is not dissolved therein, and any solution including a common organic solvent may be used. For example, the cleaning solution may be an alcohol-based solvent or an ester-based solvent. After washing, the cleaning solution remaining on the substrate and the pattern may be removed. In addition, when ultrapure water is used, water remaining on the substrate and the pattern may be removed.

[0291] Furthermore, the developer may be used alone, or any combination of two or more different developers may be used.

[0292] After forming the resist pattern as described above, a patterned wiring substrate can be obtained by etching. Any etching method well known in the art can be used, such as dry etching using plasma gas, and wet etching using an alkaline solution, a copper (II) chloride solution, or a ferric chloride solution.

[0293] After the resist pattern is formed, plating may be performed. Although the plating method is not particularly limited, for example, copper plating, solder plating, nickel plating, and gold plating may be used.

[0294] The resist pattern remaining after etching can be stripped using an organic solvent. Examples of the organic solvent may be, but are not limited to, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and ethyl lactate (EL). Although the stripping method is not particularly limited, for example, immersion and spraying can be used. In addition, the wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate, or may have a small diameter through hole.

[0295] In an embodiment, the wiring substrate may be formed by a method including forming a resist pattern, depositing a metal thereon in a vacuum, and melting the resist pattern using a solution, for example, a lift-off method.

[0296] Figures 3A to 3E is a side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment.

[0297] Reference Figure 3A 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), 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.

[0298] Reference Figure 3B , the resist film 110 may be subjected to a pre-exposure baking process and 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 .

[0299] Reference Figure 3C , the exposed resist film 110 may be developed using a developer (eg, a developing solution). The exposed region 111 may be washed away by the developer, while the unexposed region 112 may remain without being washed away by the developer.

[0300] Reference Figure 3D , 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 .

[0301] Reference Figure 3E , the resist pattern 110 may be removed.

[0302] Figures 4A to 4E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment.

[0303] Reference Figure 4A , a gate dielectric 505 (e.g., silicon oxide) may be formed on the substrate 500. The substrate 500 may be a semiconductor substrate, such as a silicon substrate, but is not limited thereto. 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.

[0304] Reference Figure 4B , 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.

[0305] Reference Figure 4C , 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 pattern 515a, and a gate dielectric pattern 505a. The resist pattern 540b and the hard mask pattern 520a may be removed after the gate pattern 515a and the gate dielectric pattern 505a are formed. Alternatively, after the gate pattern 515a and the gate dielectric pattern 505a are formed, the resist pattern 540b may be removed, and the hard mask pattern 520a may remain.

[0306] Reference Figure 4D, a spacer layer may be formed on the gate 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 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.

[0307] Reference Figure 4E , an interlayer insulating layer 560 (e.g., oxide) may be formed on the substrate 500 to cover the gate 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 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 4A to 4E An example of forming a transistor is shown, but the inventive concept is not limited thereto. The resist composition according to one or more embodiments may be used in a patterning process to form other types of semiconductor devices.

[0308] Hereinafter, the present disclosure will be described in more detail according to the following examples and comparative examples. However, the following examples are merely presented to convey the inventive concept of the present disclosure, and the scope of the present disclosure is not limited thereto.

[0309] Example

[0310] Synthesis Example 1: Synthesis of Monomer A-1

[0311]

[0312] (1) Synthesis of Compound A-1_P-1

[0313] In a nitrogen atmosphere, 4-hydroxyacetophenone (10 g, 73.5 mmol) was mixed with tetrahydrofuran (THF, 150 ml), triethylamine (TEA) (15.4 ml, 110 mmol) and 4-dimethylaminopyridine (DMAP) (1.8 g, 14.7 mmol), and the reaction solution was cooled to 0°C. Di-tert-butyl dicarbonate (DTBDC) (18.4 g, 84.5 mmol) dissolved in tetrahydrofuran (THF) (20 ml) was slowly added to the solution, followed by stirring for 16 hours at room temperature (RT). Subsequently, the organic layer obtained by extraction with 300 ml of water and 400 ml of ethyl acetate (EA) was washed with a saturated NaCl aqueous solution and washed with MgSO 4The filtrate thus obtained was decompressed, and the residue thus obtained was separated and purified by silica gel column chromatography (ethyl acetate:n-hexane=10:90 (volume ratio)) to obtain 16.81 g of compound A-1_P-1 (yield: 65%). 1 H-NMR data.

[0314] 1 H-NMR (500 MHz, CDCl 3 -d 1 ) δ 8.95 (d, 2H), 7.23 (d, 2H), 2.54 (s, 3H), 1.52 (s, 9H).

[0315] (2) Synthesis of Monomer A-1

[0316] The solution of methyltriphenylphosphonium bromide (MTPPBr) (24.9g, 69.8mmol) dissolved in tetrahydrofuran (THF, 100ml) was cooled to 0°C in a nitrogen atmosphere. Potassium tert-butoxide (t-BuOK) solution (1M in THF) (70mL, 69.8mmol) was slowly added to the solution. The solution was further stirred at 0°C for 4 hours, and a solution of the synthetic compound A-1_P-1 (15g, 63.5mmol) dissolved in tetrahydrofuran (THF) (50ml) was slowly added thereto. The reaction mixture was further stirred at room temperature for 12 hours. The mixed solution was filtered and concentrated using diatomaceous earth, and then extracted with 100ml of water and 300ml of ethyl acetate (EA). The organic layer thus obtained was washed with a saturated NaCl aqueous solution and MgSO 4 The filtrate thus obtained was decompressed, and the residue thus obtained was separated and purified by silica gel column chromatography (ethyl acetate:n-hexane=5:95 (volume ratio)) to obtain 10.8 g of monomer A-1 (yield: 73%). 1 H-NMR data.

[0317] 1 H-NMR (500 MHz, CDCl 3 -d 1 )δ7.48 (d, 2H), 7.15 (d, 2H), 5.35 (s, 1H), 5.09 (s, 1H), 2.15 (s, 3H), 1.58 (s, 9H).

[0318] Synthesis Example 2: Synthesis of Monomer A-2

[0319]

[0320] (1) Synthesis of Compound A-2_P-1

[0321] In a nitrogen atmosphere, 2-chloroacrylic acid (3.46 g, 32.4 mmol), 4-(tetrahydropyran-2-yloxy)phenol (A-2-P-2) (6 g, 30.9 mmol) and 4-dimethylaminopyridine (DMAP) (0.14 g, 1.1 mmol) were mixed with dichloromethane (DCM) (45 ml), and the mixture was cooled to 0°C. N,N'-dicyclohexylcarbodiimide (DCC) (7.7 g, 37.1 mmol) dissolved in dichloromethane (DCM) (45 ml) was slowly added to the solution, and the reaction mixture was stirred for another 12 hours at room temperature. After the reaction was complete, the precipitate formed was filtered, and the organic layer was washed with 50 ml of water and saturated NaCl aqueous solution and MgSO 4 The filtrate thus obtained was decompressed, and the residue thus obtained was separated and purified by silica gel column chromatography (ethyl acetate:n-hexane=10:90 (volume ratio)) to obtain 6.6 g of compound A-2_P-1 (yield: 75%). 1 H-NMR data.

[0322] 1 H-NMR (500 MHz, CDCl 3 -d 1 )δ7.07 (m, 4H), 6.73 (s, 1H), 6.17 (s, 1H), 5.39 (t, 1H), 3.91 (s, 1H), 3.62 (s, 1H), 1.86 (m, 1H), 1.68 (m, 1H), 1.67 (m, 4H).

[0323] (2) Synthesis of Monomer A-2

[0324] In a nitrogen atmosphere, the synthesized compound A-2_P-1 (6.6 g, 6323.3 mmol) and p-toluenesulfonic acid (p-TsOH) (0.2 g, 1.0 mmol) were dissolved in 100 ml of methanol (MeOH) and stirred at room temperature for 16 hours. After the reaction was completed, the mixture was added to 100 ml of water and extracted with 300 ml of ethyl acetate (EA). The obtained organic layer was washed with water and a saturated NaCl aqueous solution and MgSO 4 The filtrate thus obtained was decompressed, and the residue thus obtained was separated and purified by silica gel column chromatography (ethyl acetate:n-hexane=1:5 (volume ratio)) to obtain 4.5 g of monomer A-2 (yield: 97%). 1 H-NMR data.

[0325] 1H-NMR (500 MHz, DMSO-d 6 )δ9.54(s, 1H), 7.01(t, 2H), 6.77(t, 2H), 6.77(d, 1H), 6.42(d, 1H).

[0326] Synthesis Example 3: Synthesis of Monomer A-3

[0327]

[0328] 2-Hydroxy-2-trifluoromethylacetophenone (10 g, 49 mmol) was mixed with dichloromethane (DCM) (200 ml) and triethylamine (TEA) (7.5 ml, 53.9 mmol), and 4-vinylbenzenesulfonyl chloride (7.53 g, 37.2 mmol) was added thereto, followed by stirring at room temperature for 18 hours. Subsequently, the organic layer obtained by extraction with 200 ml of water and 200 ml of DCM was washed with saturated NH 4 Cl aqueous solution and saturated NaCl aqueous solution, and MgSO 4 The obtained solid was dissolved in ethyl acetate (EA) (5 ml) and n-hexane (n-Hex) (15 ml) and placed in a refrigerator, and then the recrystallized product was filtered to obtain monomer A-3. The generated compound was determined. 1 H-NMR data.

[0329] 1 H-NMR (500 MHz, DMSO-d 6 ) δ 8.14 (d, 2H), 7.94 (d, 2H), 7.75 (t, 3H), 7.59 (t, 2H), 7.10 (q, 1H), 6.84 (dd, 1H), 6.08 (d, 1H), 5.52 (d, 1H).

[0330] Synthesis Example 4: Synthesis of Monomer A-4

[0331]

[0332] In a nitrogen atmosphere, 4-(prop-1-en-2-yl)benzoic acid (5 g, 31 mmol) was dissolved in acetonitrile (ACN) (100 ml), and the solution was cooled to 0°C. 1,1'-Carbonyldiimidazole (CDI) (9.0 g, 55.5 mmol) was slowly added to the solution, and the reaction mixture was stirred at 0°C for 1 hour and further stirred at room temperature for 3 hours. 1-Ethylcyclopentanol (8.8 g, 77 mmol) was added to the reaction mixture, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (11.5 ml, 77 mmol) was slowly added thereto. The mixture was further reacted at 50°C for 16 hours. The reaction was stopped by adding 50 ml of water thereto, and the organic layer was then washed with a saturated aqueous NaCl solution and washed with MgSO 4 The filtrate thus obtained was decompressed, and the residue thus obtained was separated and purified by silica gel column chromatography (ethyl acetate:n-hexane=1:10 (volume ratio)) to obtain 7.3 g of monomer A-4 (yield: 91%). 1 The produced compound was identified by H-NMR.

[0333] 1 H-NMR (500 MHz, CDCl 3 -d 1 )δ7.98 (d, 2H), 7.50 (d, 2H), 5.45 (s, 1H), 5.17 (s, 1H), 2.30 (m, 2H), 2.16 (s, 3H), 2.12 (m, 2H), 1.78 (m, 4H), 1.67 (s, 2H), 0.94 (t, 3H).

[0334] Synthesis Example 5: Synthesis of Polymer P-1

[0335] Monomer A-1 (1.50 g, 6.4 mmol), monomer A-2 (1.27 g, 6.4 mmol), and initiator V601 (0.19 g, 0.64 mmol) were dissolved in cyclopentanone solvent (2.8 g). After stirring the solution at 60° C. for 6 hours, the white solid powder obtained by precipitation in n-hexane was filtered to obtain polymer P-1 (1.53 g, yield: 55%).

[0336] Synthesis Example 6: Synthesis of Polymer P-2

[0337] Polymer P-2 (0.75 g, yield: 43%) was obtained in the same manner as in Synthesis Example 5, except that monomer A-1 (0.94 g, 4.0 mmol), monomer A-2 (0.80 g, 4.0 mmol), initiator V601 (0.12 g, 0.4 mmol), and cyclopentanone (7.0 g) were used.

[0338] Synthesis Example 7: Synthesis of Polymer P-3

[0339] Polymer P-3 (1.52 g, yield: 64%) was obtained in the same manner as in Synthesis Example 5, except that monomer A-1 (1.51 g, 6.5 mmol), monomer A-2 (0.86 g, 4.3 mmol), initiator V601 (0.12 g, 0.54 mmol), and cyclopentanone (5.5 g) were used.

[0340] Synthesis Example 8: Synthesis of Polymer P-4

[0341] Polymer P-4 (1.84 g, yield: 61%) was obtained in the same manner as in Synthesis Example 5, except for the following: monomer A-1 (1.50 g, 6.4 mmol), monomer A-2 (1.02 g, 5.1 mmol), monomer A-3 (0.47 g, 1.3 mmol), initiator V601 (0.15 g, 0.64 mmol), and cyclopentanone (7.0 g) were used.

[0342] Synthesis Example 9: Synthesis of Polymer P-5

[0343] Polymer P-5 (1.84 g, yield: 61%) was obtained in the same manner as in Synthesis Example 5, except for the following: monomer A-1 (1.50 g, 6.4 mmol), monomer A-2 (1.00 g, 5.1 mmol), monomer A-3 (0.22 g, 0.60 mmol), initiator V601 (0.14 g, 0.60 mmol), and cyclopentanone (6.4 g) were used.

[0344] Synthesis Example 10: Synthesis of Polymer P-6

[0345] Polymer P-6 (1.12 g, yield: 49%) was obtained in the same manner as in Synthesis Example 5, except that monomer A-4 (1.53 g, 5.9 mmol), monomer A-2 (0.78 g, 3.9 mmol), initiator V601 (0.11 g, 0.49 mmol), and cyclopentanone (5.4 g) were used.

[0346] Synthesis Example 11: Synthesis of Polymer P-7

[0347] Polymer P-7 (1.35 g, yield: 72%) was obtained in the same manner as in Synthesis Example 5, except that monomer A-1 (1.02 g, 4.4 mmol), monomer A-2 (0.86 g, 4.4 mmol), initiator V601 (0.10 g, 0.44 mmol), and cyclopentanone (4.4 g) were used.

[0348] Synthesis Example 12: Synthesis of polymer PX

[0349] Polymer PX (2.57 g, yield: 77%) was obtained in the same manner as in Synthesis Example 5, except that monomer B-1 (1.0 g, 8.5 mmol), monomer B-2 (2.53 g, 8.5 mmol), initiator V601 (0.19 g, 0.85 mmol), and cyclopentanone (7.8 g) were used.

[0350] Synthesis Example 13: Synthesis of polymer PY

[0351] A polymer PY precursor (2.26 g, yield: 70%) was obtained in the same manner as in Synthesis Example 5, except for the following: monomer B-4 (0.5 g, 4.8 mmol), monomer B-5 (1.48 g, 6.7 mmol), monomer B-6 (1.25 g, 7.7 mmol), initiator V601 (0.22 g, 0.96 mmol), and cyclopentanone (7.5 g) were used.

[0352] The obtained precursor was dissolved in a tetrahydrofuran / methanol (1 / 1, v / v) solution, and then an acetyl group present at the position of monomer B-6 was deprotected using an aqueous ammonia solution. The reaction solution was reprecipitated in n-hexane to obtain polymer PY. 1 As a result of H-NMR analysis, it was confirmed that all acetyl groups were deprotected.

[0353] Synthesis Example 14: Synthesis of Polymer PZ

[0354] The polymer PZ precursor (2.18 g, yield: 65%) was obtained in the same manner as in Synthesis Example 5, except that monomer B-7 (2.0 g, 11.4 mmol), monomer B-3 (1.37 g, 11.4 mmol), initiator V601 (0.26 g, 1.14 mmol), and cyclopentanone (7.9 g) were used.

[0355] The obtained precursor was dissolved in a tetrahydrofuran / methanol (1 / 1, v / v) solution, and then an aqueous ammonia solution was used to perform a deprotection reaction of the acetyl group present at the monomer B-7 site. The reaction solution was reprecipitated in n-hexane to obtain a polymer PZ. 1 As a result of H-NMR analysis, it was confirmed that all acetyl groups were deprotected.

[0356] The weight average molecular weight and PDI of the polymers obtained in Synthesis Examples 5 to 14 are shown in Table 2.

[0357] Table 2

[0358]

[0359]

[0360]

[0361]

[0362] Evaluation Example 1: Evaluation of Thin Film Development

[0363] (1) Terminology

[0364] E 0 refers to the exposure dose at the point where the film is fully developed (thickness of the film no longer decreases), and E 1 It refers to the exposure dose at the point where development of the film is initiated. γ representing the contrast curve is a value calculated by the following Equation 1.

[0365] Equation 1

[0366]

[0367] (2) Evaluation of film development

[0368] The polymer synthesized in Synthesis Examples 5 to 14 was dissolved in a casting solvent of PGME / PGMEA (7 / 3 (w / w)) at 1.5 wt%. In the case of Examples 7 to 10, PAG-1 (23 mmol) as an acid generator and PDQ (20 mmol) as a quencher, or PAG-2 (30 mmol) as an acid generator were added thereto based on 100 parts by weight of each polymer, followed by filtration using a 0.2 μm separation filter. A silicon wafer treated with HMDS (hexamethyldisilazane) was spin-coated with the casting solution at a speed of 1500 rpm and dried at 110° C. for 1 minute (PAB) to form a film. Subsequently, the film was heated to 0 mJ / cm 2 Up to 200mJ / cm 2 The obtained film was immersed in a 2.38 wt % TMAH aqueous solution at 25° C. for 60 seconds, washed with water, and naturally dried, and then measured using a film thickness measuring instrument ( F-20) The thickness of the remaining film was measured and is shown in Table 3 below.

[0369] Table 3

[0370]

[0371]

[0372] Referring to Table 3, it was confirmed that after exposure to EUV, the solubility was changed in all the synthesized polymers. In the case of the polymer PX of Comparative Example 1, during development using an alkaline developer, even at 200 mJ / cm 2 At a dose of , there was no change in thickness at all, and it was therefore determined that no development occurred.

[0373] Referring to Table 3, it is confirmed that the resist compositions including polymers P-1 to P-7 according to the embodiment show smaller E 1 and E 0 Based on this, it was confirmed that the resist compositions including the polymers P-1 to P-7 had increased photosensitivity compared to the resist compositions including the polymers PX to PZ.

[0374] According to an embodiment, a polymer having physical properties that change at a low dose, a resist composition including the same, and a method of forming a pattern using the same may be provided.

[0375] 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. Polymers, including: A first repeating unit represented by the following Formula 1; and A second repeating unit represented by the following Formula 2, <Formula 1> <Formula 2> Wherein, in formula 1 and 2, L 11 To L 13 and L 21 To L 24 Each independently represents: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O)2O; OS(=O)2; or a linear, branched, or cyclic C1-C2-C3-C4-C5-C6-C7-C8-C9-C10-C11-C12-C13-C14-C13-C15-C16-C18-C19-C18 ... 30 Divalent hydrocarbon groups, a11 to a13 and a21 to a24 are each independently an integer of 1 to 4, A 11 and A 21 Each independently is C6-C 30 Aryl or C1-C 30 Heteroaryl, X 11 is a photodegradable group, R 11 is a halogen atom, or a linear, branched, or cyclic C1-C 30 Monovalent hydrocarbon groups, R 21 is a halogen atom, or a linear, branched, or cyclic C1-C 30 Monovalent hydrocarbon groups, R 12 and R 22 Each is independently: hydrogen; deuterium; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a thiol group; a carbonyl moiety; an ester moiety; a sulfonate moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a linear, branched, or cyclic C1-C ... 30 Monovalent hydrocarbon groups, R 23 is: hydrogen; deuterium; halogen atom; cyano group; hydroxyl group; amino group; carboxyl group; thiol group; carbonyl moiety; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; a straight-chain, branched, or cyclic C1-C2-4-nitrogen moiety optionally including heteroatoms; 30 a monovalent hydrocarbon group; or a photodegradable group, b12, b22, and b23 are each independently an integer from 1 to 10, p11 is an integer from 1 to 3, p21 is an integer from 0 to 4, and * is the binding site with the adjacent atom.

2. The polymer according to claim 1, wherein L 11 To L 13 and L 21 To L 24 Each independently represents: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O)2O; OS(=O)2; 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.

3. The polymer according to claim 1, wherein A 11 and A 21 Each is independently selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, benzo[9,10]phenanthrenyl, pyrenyl, yl, pyrrolyl, thienyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl, isoquinolyl, benzoquinolyl, quinoxalinyl, quinazolyl, and cinnolinyl.

4. The polymer according to claim 1, wherein A 11 and A 21 Each is independently selected from phenyl, biphenyl, terphenyl, and naphthyl.

5. The polymer according to claim 1, wherein X 11 It is a group containing a tertiary non-cyclic alkyl carbon, a group containing a tertiary alicyclic carbon, an acetal group, or a group containing an ON bond.

6. The polymer according to claim 1, wherein X 11 It is represented by one of the following formulas 6-1 to 6-14: In formulas 6-1 to 6-14, X 61 is an ester moiety, a carbonate moiety, a carbamate moiety, or a sulfonate moiety; a61 is an integer from 0 to 6; R 61 and R 68 Each is independently a linear, branched, or cyclic C1-C 20 a monovalent hydrocarbon group; R 62 To R 67 each independently: hydrogen; deuterium; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a thiol group; a carbonyl moiety; an ester moiety; a sulfonate moiety; a carbonate moiety; a carbamate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a linear, branched, or cyclic C1-C ... 30 Monovalent hydrocarbon groups, In R 61 To R 68 , two neighbors are optionally bound to each other to form a ring, b64 is an integer from 1 to 10, and * is the binding site with the adjacent atom.

7. The polymer according to claim 1, wherein R 11 is a halogen atom, a substituted or unsubstituted C1-C 20 Alkyl, or substituted or unsubstituted C1-C 20 Halogenated alkyl.

8. The polymer according to claim 1, wherein R 21 is a halogen atom or a substituted or unsubstituted C1-C 20 Halogenated alkyl.

9. The polymer according to claim 1, wherein R 12 and R 22 each independently selected from: hydrogen; deuterium; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a thiol group; and C1-C 20 Alkyl, C3-C 20 Cycloalkyl, and C6-C 20 Aryl: deuterium, halogen atom, cyano group, hydroxyl group, amino group, carboxyl group, thiol group, carbonyl moiety, 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, C6-C 20 aryl, or any combination thereof.

10. The polymer according to claim 1, wherein R 23 selected from: photodegradable groups; hydrogen; deuterium; halogen atoms; cyano groups; hydroxyl groups; amino groups; carboxyl groups; thiol groups; and C1-C2-4-1,4-dihydro-2-nitro-1-nitro ... 20 Alkyl, C3-C 20 Cycloalkyl, and C6-C 20 Aryl: deuterium, halogen atom, cyano group, hydroxyl group, amino group, carboxyl group, thiol group, carbonyl moiety, 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, C6-C 20 aryl, or any combination thereof. The polymer according to claim 1 , wherein p11 is 1.

12. The polymer according to claim 1, wherein p21 is 0 or 1.

13. The polymer according to claim 1, wherein The first repeating unit is represented by the following formula 1-1, and The second repeating unit is represented by one of the following formulae 2-1 and 2-2: Wherein in Formulas 1-1, 2-1, and 2-2, L 11 To L 13 、a11 to a13、X 11 , R 11 , R 12 , and p11 are as defined in Formula 1, c12 is an integer from 1 to 4, L 21 To L 24 、a21 to a24、R 21 To R 23 , and b23 are as defined in Formula 2, c22 is an integer from 1 to 4, and * is the binding site with the adjacent atom.

14. The polymer according to claim 1, wherein The first repeating unit is selected from the repeating units of the following Group I, and the second repeating unit is selected from the repeating units of the following Group II: <Group I> <Group II> 15. The polymer of claim 1, further comprising: A third repeating unit represented by the following Formula 3: <Formula 3> In formula 3, L 31 To L 33 Each independently represents: a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O)2O; OS(=O)2; or a linear, branched, or cyclic C1-C2- 30 Divalent hydrocarbon groups, a31 to a33 are each independently an integer of 1 to 4, R 31 is: hydrogen; deuterium; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a thiol group; a carbonyl moiety; an ester moiety; a sulfonate moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a linear, branched, or cyclic C1-C ... 30 Monovalent hydrocarbon groups, X 31 is a photodegradable group or a non-acid-labile group, and * is the binding site with the adjacent atom.

16. A resist composition comprising: The polymer according to any one of claims 1 to 15; and Organic solvents.

17. The resist composition according to claim 16, further comprising: Acid generator.

18. A method for forming a pattern, the method comprising: forming a resist film by applying the resist composition according to claim 16 or 17 on a substrate; exposing 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 according to claim 18, wherein exposing the at least a portion of the resist film is performed by applying at least one of ultraviolet rays, deep ultraviolet (DUV) rays, extreme ultraviolet (EUV) rays, X-rays, gamma rays, electron beams (EB), and alpha rays.

20. The method of claim 18, wherein The exposed resist film includes an exposed area and an unexposed area, and The exposed region is removed in developing the exposed resist film by using the developer.

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