Polymer, resist composition containing the same, and pattern forming method using the same

Abstract

To provide a polymer, a resist composition containing the polymer, and a pattern forming method using the resist composition.SOLUTION: There are provided: a polymer which contains 20 mol% or more of a first repeating unit represented by the following chemical formula 1 and does not contain a repeating unit A containing at least one selected from a hydroxy group-substituted aryl group and a hydroxy group-substituted heteroaryl group; a resist composition containing the polymer; and a pattern forming method using the resist composition. In the chemical formula 1, explanations regarding L11-L13, a11-a13, X11, and R11-R13 are described in the specification.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a polymer, a resist composition containing the polymer, and a pattern forming method using the polymer. [Background technology]

[0002] Photoresists whose physical properties change in response to light are used to form fine patterns in semiconductor manufacturing. Among these, chemically amplified photoresists have been widely used. Chemically amplified photoresists enable patterning by forming an acid from a photoacid generator in response to light. The acid reacts with the base resin, changing the solubility of the base resin in a developer.

[0003] However, in the case of chemically amplified photoresists, the formed acid diffuses into unexposed areas, causing problems such as reduced pattern uniformity and increased surface roughness. Furthermore, as semiconductor processes become increasingly miniaturized, it is no longer easy to control acid diffusion, necessitating the development of new resist types.

[0004] In recent years, attempts have been made to overcome the limitations of chemically amplified photoresists by developing materials whose physical properties change upon exposure, but the problem remains that the required dose is still high.

[0005] This has led to a demand for materials whose physical properties can be changed through fast reactions at low doses. Summary of the Invention [Problem to be solved by the invention]

[0006] The problem to be solved by the present invention is to provide a polymer whose physical properties, particularly solubility, change even with low-dose exposure, a resist composition containing the same, and a pattern formation method using the same. [Means for solving the problem]

[0007] In one aspect, there is provided a polymer comprising 20 mol % or more of a first repeating unit represented by the following Chemical Formula 1, and no repeating unit A comprising at least one selected from an aryl group substituted with a hydroxy group and a heteroaryl group substituted with a hydroxy group: [ka] In the above Chemical Formula 1, L 11 ~L 13 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O)2; S(=O)2O; OS(=O)2; or C1-C optionally containing heteroatoms. 30 is a linear, branched, or cyclic divalent hydrocarbon radical of a11 to a13 each independently represent an integer of 1 to 4, R 11 ~R 13 are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl group; an amide group; an ester group; a sulfonate group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic anhydride group; or a C1-C10 group which may optionally contain a heteroatom. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of R 12 and R 13 can optionally be joined together to form a ring; * indicates the bonding site with the adjacent atom.

[0008] In another aspect, there is provided a resist composition comprising the aforementioned polymer and an organic solvent.

[0009] In yet another aspect, there is provided a pattern formation method including the steps of applying the resist composition described above to form a resist film, exposing at least a portion of the resist film to high-energy rays, and developing the exposed resist film using a developer. [Effects of the Invention]

[0010] Advantageous Effects of Invention Embodiments of the present invention can provide a polymer whose physical properties change even at a low dose, a resist composition containing the same, and a pattern formation method using the same. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a flowchart illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2A] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2B] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 2C] 1A to 1C are side cross-sectional views illustrating a pattern formation method according to one embodiment of the present invention. [Figure 3A] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 3B] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 3C] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 3D] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 3E] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4A] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 4B] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 4C] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 4D] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. [Figure 4E] 1A to 1C are side cross-sectional views illustrating a method of forming a semiconductor device according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention can be modified in various ways and can have various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to the specific embodiments, and it should be understood that the present invention includes all modifications, equivalents, and alternatives included within the spirit and technical scope of the present invention. When a detailed description of known technology related to the description of the present invention is considered to obscure the gist of the present invention, the detailed description will be omitted.

[0013] Terms such as "first," "second," and "third" are used to describe various components, but are used only to distinguish one component from another, and do not limit the order, type, etc. of the components.

[0014] In this specification, when a layer, film, region, plate, or other part is described as being "on top" or "above" another part, it includes not only parts that are in contact with each other and are immediately above, below, to the left, or right, but also parts that are not in contact with each other and are immediately above, below, to the left, or right.

[0015] The singular includes the plural unless the context clearly dictates otherwise. Terms such as "comprise" or "have" should be understood to indicate the presence of a feature, number, step, operation, component, part, ingredient, material, or combination thereof stated in the specification, unless specifically stated to the contrary, and not to preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, ingredients, materials, or combinations thereof.

[0016] Whenever a range of values ​​is recited, the range includes all values ​​that fall within the range as expressly recorded, and further includes the boundaries of the range. Thus, a range "from X to Y" includes all values ​​between X and Y, and also includes X and Y.

[0017] As used herein, "C x -C y " means that the number of carbon atoms constituting the substituent is x to y. For example, "C1-C6" means that the number of carbon atoms constituting the substituent is 1 to 6, and "C6-C 20 " means that the number of carbon atoms constituting the substituent is 6 to 20.

[0018] In this specification, the term "monovalent hydrocarbon group" refers to a monovalent residue derived from an organic compound containing carbon and hydrogen or a derivative thereof, and specific examples include linear or branched alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); monovalent saturated cyclic aliphatic hydrocarbon groups (cycloalkyl groups) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl, and the like). monovalent unsaturated aliphatic hydrocarbon groups (alkenyl groups, alkynyl groups) (e.g., allyl groups); monovalent unsaturated cyclic aliphatic hydrocarbon groups (cycloalkenyl groups) (e.g., 3-cyclohexenyl groups); aryl groups (e.g., phenyl groups, 1-naphthyl groups, and 2-naphthyl groups); arylalkyl groups (e.g., benzyl groups and diphenylmethyl groups); heteroatom-containing monovalent hydrocarbon groups (e.g., tetrahydrofuranyl groups, methoxymethyl groups, ethoxymethyl groups, methylthiomethyl groups, acetamidomethyl groups, trifluoroethyl groups, (2-methoxyethoxy)methyl groups, acetoxymethyl groups, 2-carboxy-1-cyclohexyl groups, 2-oxopropyl groups, 4-oxo-1-adamantyl groups, and 3-oxocyclohexyl groups), or any combination thereof. In addition, in these groups, some hydrogen atoms are replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, or some carbon atoms are replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen, so that these groups can also contain a hydroxy group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an amide bond, an ester bond, a sulfonate ester bond, a carbonate, a carbamate, a lactone ring, a sultone ring, a carboxylic anhydride group, or a haloalkyl group.

[0019] As used herein, the term "divalent hydrocarbon group" refers to a divalent residue in which one hydrogen atom of the monovalent hydrocarbon group is replaced by a bonding site to an adjacent atom. Examples of divalent hydrocarbon groups include linear or branched alkylene groups, cycloalkylene groups, alkenylene groups, alkynylene groups, cycloalkylene groups, arylene groups, and groups in which some carbon atoms are replaced by heteroatoms.

[0020] As used herein, the term "alkyl group" refers to a linear or branched saturated aliphatic hydrocarbon monovalent group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an iso-amyl group, a hexyl group, etc. As used herein, the term "alkylene group" refers to a linear or branched saturated aliphatic hydrocarbon divalent group, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, etc.

[0021] As used herein, the term "halogenated alkyl group" refers to an alkyl group in which one or more hydrogen atoms have been substituted with halogen, and specific examples include CF3.

[0022] As used herein, an "alkoxy group" is defined as -OA. 101 where A 101 is an alkyl group. Specific examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group.

[0023] As used herein, an "alkylthio group" is defined as -SA 101 where A 101 is an alkyl group.

[0024] As used herein, the term "halogenated alkoxy group" refers to an alkoxy group in which one or more hydrogen atoms have been substituted with halogen, and specific examples include -OCF3.

[0025] As used herein, the term "halogenated alkylthio group" refers to an alkylthio group in which one or more hydrogen atoms have been substituted with halogen, and specific examples include -SCF3.

[0026] As used herein, the term "cycloalkyl group" refers to a monovalent saturated hydrocarbon ring group, specific examples of which include monocyclic groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and fused polycyclic groups such as a norbornyl group and an adamantyl group. As used herein, the term "cycloalkylene group" refers to a divalent saturated hydrocarbon ring group, specific examples of which include a cyclopentylene group, a cyclohexylene group, an adamantylene group, an adamantylmethylene group, a norbornylene group, a norbornylmethylene group, a tricyclodecanylene group, a tetracyclododecanylene group, a tetracyclododecanylmethylene group, and a dicyclohexylmethylene group.

[0027] As used herein, a "cycloalkoxy group" is defined as -OA. 102 where A 102 is a cycloalkyl group. Specific examples thereof include a cyclopropoxy group, a cyclobutoxy group, and the like.

[0028] As used herein, a "cycloalkylthio group" refers to a group represented by -SA 102 where A 102 is a cycloalkyl group.

[0029] As used herein, a "heterocycloalkyl group" refers to a cycloalkyl group in which some carbon atoms are replaced by a group containing a heteroatom, such as oxygen, sulfur, or nitrogen. Specific examples of heterocycloalkyl groups include an ether bond, an amide bond, an ester bond, a sulfonate ester bond, a carbonate, a carbamate, a lactone ring, a sultone ring, or a carboxylic acid anhydride group. As used herein, a "heterocycloalkylene group" refers to a cycloalkylene group in which some carbon atoms are replaced by a group containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0030] As used herein, a "heterocycloalkoxy group" is defined as -OA 103 where A 103 is a heterocycloalkyl group.

[0031] As used herein, the term "alkenyl group" refers to a linear or branched, unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon double bonds. As used herein, the term "alkenylene group" refers to a linear or branched, unsaturated aliphatic hydrocarbon divalent group containing one or more carbon-carbon double bonds.

[0032] As used herein, an "alkenyloxy group" is defined as -OA 104 where A 104 is an alkenyl group.

[0033] As used herein, a "cycloalkenyl group" refers to a monovalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds. As used herein, a "cycloalkenylene group" refers to a divalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds.

[0034] As used herein, a "cycloalkenyloxy group" is defined as -OA 105 where A 105 is a cycloalkenyl group.

[0035] As used herein, a "heterocycloalkenyl group" refers to a cycloalkenylene group in which some carbon atoms are replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen. As used herein, a "heterocycloalkenylene group" refers to a cycloalkenylene group in which some carbon atoms are replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen.

[0036] As used herein, a "heterocycloalkenyloxy group" is defined as -OA 106 where A106 is a heterocycloalkenyl group.

[0037] As used herein, the term "alkynyl group" refers to a linear or branched, unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon triple bonds.

[0038] As used herein, an "alkynyloxy group" is defined as -OA 107 where A 107 is an alkynyl group.

[0039] As used herein, "aryl group" means a monovalent group having a carbocyclic aromatic system, and specific examples include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, and the like.

[0040] As used herein, an "aryloxy group" is defined as -OA 108 where A 108 is an aryl group.

[0041] As used herein, the term "heteroaryl group" refers to a monovalent group having a heterocyclic aromatic system, and specific examples include pyridinyl groups, pyrimidinyl groups, pyrazinyl groups, etc. As used herein, the term "heteroarylene group" refers to a divalent group having a heterocyclic aromatic system.

[0042] As used herein, a "heteroaryloxy group" is defined as -OA 109 where A 109 is a heteroaryl group.

[0043] As used herein, a "substituent" includes deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether group, ester group, sulfonate ester group, carbonate group, carbamate group, amide group, lactone group, sultone group, carboxylic acid anhydride group, C1-C 20 Alkyl groups, C1-C 20Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryl groups, C1-C 20 Heteroaryloxy group, or C1-C 20 heteroarylthio groups; Deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether group, ester group, sulfonate ester group, carbonate group, carbamate group, amide group, lactone group, sultone group, carboxylic acid anhydride group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryl groups, C1-C 20 Heteroaryloxy groups, C1-C 20 C-C substituted with heteroarylthio groups, and any combination thereof 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryl groups, C1-C 20 Heteroaryloxy groups, C1-C 20 heteroarylthio groups; and any combination thereof.

[0044] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the description with reference to the drawings, substantially identical or corresponding components are given the same drawing numbers, and redundant description thereof will be omitted. In the drawings, thicknesses of multiple layers and regions are exaggerated to clearly show them. Also, in the drawings, thicknesses of some layers and regions are exaggerated for convenience of explanation. Meanwhile, the embodiments described below are merely examples, and various modifications are possible from such embodiments.

[0045] [polymer] The polymer according to an exemplary embodiment comprises 20 mol % or more of a first repeating unit represented by the following Chemical Formula 1: does not contain a repeating unit A containing at least one selected from an aryl group substituted with a hydroxy group and a heteroaryl group substituted with a hydroxy group: [ka] In the above Chemical Formula 1, L 11 ~L 13 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O)2; S(=O)2O; OS(=O)2; or C1-C optionally containing heteroatoms.30 is a linear, branched, or cyclic divalent hydrocarbon radical of a11 to a13 each independently represent an integer of 1 to 4, R 11 ~R 13 are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl group; an amide group; an ester group; a sulfonate group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic anhydride group; or a C1-C10 group which may optionally contain a heteroatom. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of R 12 and R 13 can optionally be joined together to form a ring; * indicates the bonding site with the adjacent atom.

[0046] For example, in the above Chemical Formula 1, L 11 ~L 13 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O)2; S(=O)2O; OS(=O)2; substituted or unsubstituted C1-C 30 Alkylene group; substituted or unsubstituted C3-C 30 Cycloalkylene group; substituted or unsubstituted C3-C 30 Heterocycloalkylene groups; substituted or unsubstituted C2-C 30 Alkenylene group; substituted or unsubstituted C3-C 30 Cycloalkenylene group; substituted or unsubstituted C3-C 30 Heterocycloalkenylene group; substituted or unsubstituted C6-C 30 arylene groups; or substituted or unsubstituted C1-C 30 It is a heteroarylene group.

[0047] As another example, in the above Chemical Formula 1, L 11 ~L 13are each independently a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); and deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, ester group, sulfonate ester group, carbonate group, carbamate group, lactone group, sultone group, carboxylic acid anhydride group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C6-C 20 C1-C substituted or unsubstituted aryl groups, or any combination thereof 20 Alkylene group, C3-C 20 Cycloalkylene group, C3-C 20 Heterocycloalkylene groups, C2-C 20 Alkenylene group, C3-C 20 Cycloalkenylene group, C3-C 20 Heterocycloalkenylene group, C6-C 20 Arylene groups, and C1-C 20 heteroarylene groups;

[0048] As another example, in the above Chemical Formula 1, L 11 ~L 13 are each independently a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); and deuterium, halogen, ester group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 C1-C substituted or unsubstituted with alkoxy, phenyl, naphthyl, or any combination thereof 20 Alkylene group, C3-C 20 Cycloalkylene group, C3-C 20 heterocycloalkylene groups, phenylene groups, and naphthylene groups.

[0049] In the above chemical formula 1, a11 to a13 are each L11 ~L 13 means the number of iterations.

[0050] For example, in the above Chemical Formula 1, a11 to a13 are each independently an integer of 1 to 3.

[0051] As another example, in the above Chemical Formula 1, a11 to a13 are each independently 1.

[0052] For example, in the above formula 1, R 11 are hydrogen, deuterium, halogen, cyano, hydroxy, amino, carboxylic acid, thiol, amide, ester; and deuterium, halogen, cyano, hydroxy, amino, carboxylic acid, thiol, amide, ester, sulfonate, carbonate, carbamate, lactone, sultone, carboxylic anhydride, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C6-C 20 C1-C substituted or unsubstituted aryl groups, or any combination thereof 20 Alkyl groups, C3-C 20 Cycloalkyl groups and C6-C 20 an aryl group;

[0053] As another example, in Formula 1, R 11 is hydrogen; deuterium; halogen; cyano group; amide group; ester group; and C-C substituted or unsubstituted with deuterium, halogen, cyano group, or any combination thereof. 20 Alkyl groups and C6-C 20 an aryl group;

[0054] As another example, in Formula 1, R 11is H, D, F, Cl, C(=O)OCH3, C(=O)N(CH3)2, CH3, CH2F, CHF2, CF3, CH2CH3, CHFCH3, CHFCH2F, CHFCHF2, CHFCF3, CF2CH3, CF2CH2F, CF2CHF2, CF2CF3, CH2Cl, CHCl2, CCl3, CHClCH3, CHClCH2Cl, CHClCHCl2, CHClCCl3, CCl2CH3, CCl2CH2Cl, CCl2CHCl2, CCl2CCl3, or a phenyl group.

[0055] For example, in the above formula 1, R 12 and R 13 are each independently hydrogen; deuterium; -C(=O)R 14 ;-C(R 14 )=NR 15 ;-OR 14 ;-NR 14 R 15 ;-S(=O)R 14 ;-S(=O)2R 14 ;-S(=O)2OR 14 and deuterium, halogen, hydroxyl group, cyano group, nitro group, carboxylic acid group, amino group, ether group, carbonyl group, ester group, sulfonate group, carbonate group, carbamate group, amide group, lactone group, sultone group, carboxylic acid anhydride group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryl groups, C1-C 20 Heteroaryloxy groups, C1-C 20C1-C substituted or unsubstituted heteroarylthio groups, or any combination thereof 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups and C1-C 20 heteroaryl groups; R 14 and R 15 are each independently hydrogen, deuterium, and heavy hydrogen, halogen, hydroxyl group, cyano group, nitro group, carboxylic acid group, amino group, ether group, carbonyl group, ester group, sulfonate group, carbonate group, carbamate group, amide group, lactone group, sultone group, carboxylic acid anhydride group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylthio groups, C1-C 20 Halogenated alkoxy groups, C1-C 20 Halogenated alkylthio groups, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl groups, C6-C 20 Aryloxy group, C6-C 20 Arylthio groups, C1-C 20 Heteroaryl groups, C1-C 20 Heteroaryloxy groups, C1-C 20 C1-C substituted or unsubstituted heteroarylthio groups, or any combination thereof 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups and C1-C 20 heteroaryl groups;

[0056] As another example, in Formula 1, R 12 and R 13are each independently hydrogen; deuterium; -C(=O)R 14 ;-C(R 14 )=NR 15 ;-S(=O)R 14 ;-S(=O)2R 14 ;-S(=O)2OR 14 and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups and C1-C 20 heteroaryl groups; R 14 and R 15 are each independently hydrogen; deuterium; and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups and C1-C 20 heteroaryl groups;

[0057] As another example, R 12 and R 13 are each independently -C(=O)R 14 ;-C(R 14 )=NR 15;-S(=O)2R 14 and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 20 Alkyl groups, C6-C 20 Aryl groups and C1-C 20 heteroaryl groups; R 14 and R 15 are each independently hydrogen; deuterium; and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 20 Alkyl groups, C6-C 20 Aryl groups and C1-C 20 heteroaryl groups;

[0058] In one embodiment, in Formula 1, *-N(R 12 )R 13 is represented by any one of the following chemical formulas 4-1 to 4-7: [ka] In the chemical formulas 4-1 to 4-7, R 12 and R 13 are each independently deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 20 Alkyl groups, C6-C 20 Aryl groups and C1-C 20 heteroaryl groups; R 14 , R 15 , R 14a and R 14b are each independently hydrogen; deuterium; and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl groups, C1-C 20 C-C substituted or unsubstituted heteroaryl groups, or any combination thereof 20 Alkyl groups, C6-C 20 Aryl groups and C1-C 20 heteroaryl groups; R 12 ~R 15 , R 14a and R 14b two adjacent groups in A 41 and A 42 are each independently a C-C group which may optionally contain heteroatoms. 30 Cyclic alkyl groups or C1-C1 optionally containing heteroatoms 30 is an aryl group, R 41 and R 42 are each independently hydrogen, deuterium, halogen, hydroxyl group, cyano group, nitro group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, or C1-C 20 is a heteroaryl group, b41 and b42 each independently represent an integer of 1 to 10, * indicates the bonding site with the adjacent atom.

[0059] In one embodiment, in Formula 1, *-N(R 12 )R 13 is represented by any one of the following chemical formulas 4-11 to 4-40: [ka] [ka] [ka]

[0060] In the chemical formulas 4-11 to 4-40, * indicates the bonding site with the adjacent atom.

[0061] In one embodiment, the first repeat unit is selected from Group I: <Group I> [ka] [ka]

[0062] The polymer may achieve a desired resist film thickness by containing 20 mol % or more of the first repeating unit represented by Chemical Formula 1. Specifically, the polymer may contain 30 mol % or more, particularly 50 mol % or more of the first repeating unit represented by Chemical Formula 1.

[0063] Here, the desired resist film thickness is 10 nm to 300 nm in order to form a fine pattern with improved precision. More specifically, the resist film thickness is 20 nm to 200 nm, 20 nm to 120 nm, 20 nm to 90 nm, and particularly 30 nm to 80 nm.

[0064] The polymer does not contain a repeating unit A containing at least one selected from an aryl group substituted with a hydroxy group and a heteroaryl group substituted with a hydroxy group, and therefore can undergo an appropriate change in solubility in a developer upon exposure.

[0065] Specifically, the repeating unit A is represented by the following formula 10: [ka]

[0066] In the above Chemical Formula 10, L 101 ~L 103 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O)2; S(=O)2O; OS(=O)2; or C1-C optionally containing heteroatoms. 30 is a linear, branched, or cyclic divalent hydrocarbon group of a101 to a103 each independently represent an integer of 1 to 4, R 101 is hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl group; an ester group; a sulfonate group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic anhydride group; or a C1-C group optionally containing heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of A 101 is a substituted or unsubstituted C6-C 30 Aryl groups, or substituted or unsubstituted C1-C 30 is a heteroaryl group, n101 is selected from integers of 1 to 5; * indicates the bonding site with the adjacent atom.

[0067] Specifically, the repeating unit A is represented by the following formula 10-1: [ka]

[0068] In the above Chemical Formula 10-1, L 101 ~L 103 , a101 to a103 and R 101 The explanation regarding is as described above. R 102 is hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl group; an ester group; a sulfonate group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic anhydride group; or a C1-C group optionally containing heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of c101 is selected from integers from 1 to 5; b102 is selected from integers of 0 to 4; * indicates the bonding site with the adjacent atom.

[0069] Furthermore, the polymer does not contain a repeating unit whose structure changes when exposed to an acid.

[0070] Here, the repeating unit whose structure changes in response to an acid refers to a repeating unit containing an acid labile group.

[0071] The acid labile group refers to a group that is released from the polymer by an acid to form a polar group, which serves to make the polymer more easily soluble in a developer, such as an aqueous TMAH solution.

[0072] The acid dissociation constant (pKa) of the acid labile group is 13 or less, specifically 3 to 13, and more specifically 5 to 10 (calculated value).

[0073] For example, acid labile groups refer to tertiary acyclic alkyl carbon-containing groups, tertiary alicyclic carbon-containing groups, or acetals.

[0074] More specifically, the acid labile group means a tertiary acyclic alkyl carbon-containing ester group, a tertiary alicyclic carbon-containing ester group, a tertiary acyclic alkyl carbon-containing carbonate group, a tertiary alicyclic carbon-containing carbonate group, a tertiary acyclic alkyl carbon-containing carbamate group, a tertiary alicyclic carbon-containing carbamate group, or an acetal, and is represented, for example, by any one of the following chemical formulas 6-1 to 6-11: [ka]

[0075] In the chemical formulas 6-1 to 6-11, X 61 is an ester group, a sulfonate group, a carbonate group, or a carbamate group, a61 is selected from integers from 0 to 6, R 61 and R 68 are each independently a C-C group which may optionally contain heteroatoms. 20 is a linear, branched, or cyclic monovalent hydrocarbon radical of R 62 ~R 67 are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester group; a sulfonate ester group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic acid anhydride group; or a C1-C10 alkyl group which may optionally contain heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of R 61 ~R 68 two adjacent groups in b64 is selected from the integers 1 to 10, * indicates the bonding site with the adjacent atom.

[0076] In one embodiment, the polymer may further comprise a second repeating unit represented by Formula 2: [ka]

[0077] In the above Chemical Formula 2, L 21 ~L 23 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O)O; OS(=O); or C-C optionally containing heteroatoms. 30 is a linear, branched, or cyclic divalent hydrocarbon radical of a21 to a23 each independently represent an integer of 1 to 4, R 21 is hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl group; an ester group; a sulfonate group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic anhydride group; or a C1-C group optionally containing heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of X 21 is a non-acid labile group, * indicates the bonding site with the adjacent atom.

[0078] Specifically, in the above-mentioned Chemical Formula 2, L 21 ~L 23 are each independently, L 11 Please refer to the explanation regarding this.

[0079] Specifically, in the above Chemical Formula 2, a21 to a23 each independently refer to the explanation for a11.

[0080] Specifically, in the above-mentioned Chemical Formula 2, R 21 is R 11 Please refer to the explanation regarding this.

[0081] Specifically, in the above-mentioned Chemical Formula 2, X 21is not a hydroxy-substituted aryl group or a hydroxy-substituted heteroaryl group.

[0082] More specifically, in the above Chemical Formula 2, X 21 is a C1-C group which may optionally contain one or more polar groups selected from hydrogen, halogen, cyano, hydroxy, carboxylic acid, thiol, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), lactone, sultone, and carboxylic anhydride groups; 30 is a linear, branched or cyclic monovalent hydrocarbon radical of the formula:

[0083] In one embodiment, in Formula 2, X 21 is hydrogen, hydroxyl group, C1-C 10 The alkyl group is selected from the group consisting of alkyl groups and groups represented by the following chemical formulas 5-1 to 5-15: [ka]

[0084] In the chemical formulas 5-1 to 5-15, a51 is 1 or 2, R 51 ~R 56 each independently represents a bonding site to the adjacent atom; hydrogen; deuterium; halogen; cyano group; hydroxy group; amino group; carboxylic acid group; thiol group; carbonyl group; ester group; sulfonate group; carbonate group; carbamate group; lactone group; sultone group; carboxylic anhydride group; or a C1-C group optionally containing a heteroatom. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of R 51 ~R 53 One of them, R 54 One of these and R 55 and R 56 One of these is the bonding site with the adjacent atom, b51 is selected from integers of 1 to 4; b52 is selected from integers from 1 to 10; b53 is selected from integers from 1 to 8; b54 is selected from integers from 1 to 5; b55 is selected from integers from 1 to 7; b56 is selected from integers from 1 to 11; b57 is selected from integers from 1 to 13; b58 is selected from integers from 1 to 15; b59 is selected from integers of 1 to 2; m51 is selected from integers of 1 to 4.

[0085] In particular, in the above-mentioned Chemical Formula 2, X 21 is a hydroxy group and is selected from the group consisting of formulas 5-1, 5-3 and 5-10.

[0086] In one embodiment, the second repeating unit is represented by any one of the following formulas 2-1 to 2-3: [ka]

[0087] In the above chemical formulas 2-1 to 2-3, L 22 ~L 23 , a22~a23, R 21 and X 21 is as explained in Chemical Formula 2, L 24 is a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O)2O; OS(=O)2; or C1-C optionally containing heteroatoms. 30 is a linear, branched, or cyclic divalent hydrocarbon radical of a24 is an integer from 1 to 3, * indicates the bonding site with the adjacent atom.

[0088] In particular, in the chemical formula 2-1, in the chemical formula 2, X 21is hydrogen, hydroxyl group, C1-C 10 The alkyl group is selected from the group consisting of the alkyl groups and the groups of the formulae 5-1, 5-3, and 5-10 to 5-15.

[0089] In one embodiment, the second repeat unit is represented by any one selected from Group II below: <Group II> [ka] [ka]

[0090] In one embodiment, the polymer may consist of the first repeat unit.

[0091] In one embodiment, the polymer contains 1 to 99 mol% of the first repeating unit and 1 to 99 mol% of the second repeating unit. Specifically, the polymer contains 1 to 90 mol% of the first repeating unit and 10 to 99 mol% of the second repeating unit. More specifically, the polymer contains 10 to 80 mol% of the first repeating unit and 20 to 90 mol% of the second repeating unit. In particular, the polymer contains the second repeating unit to the first repeating unit in a molar ratio of 5:1 to 1:5.

[0092] In other embodiments, the polymer may consist of the first repeat unit and the second repeat unit.

[0093] The polymer has a weight average molecular weight (Mw) of 1,000 to 500,000, specifically 3,000 to 200,000, as measured by gel permeation chromatography using tetrahydrofuran solvent and polystyrene as a standard.

[0094] The polydispersity index (PDI: Mw / Mn) of the polymer is 1.0 to 3.0. By satisfying this range, it is easy to control the dispersibility and / or compatibility of the polymer, reducing the possibility of foreign matter remaining on the pattern and minimizing deterioration of the pattern profile. As a result, the resist composition is more suitable for forming fine patterns.

[0095] The polymer itself changes its physical properties when exposed to high-energy radiation, and is therefore used in non-chemically amplified resist compositions.

[0096] The polymer has relatively high resistance to oxygen and / or moisture, and its physical properties change only when exposed to high-energy rays, so that a resist composition with improved storage stability can be provided.

[0097] The polymer induces changes in the physical properties of the polymer through structural changes in the side chains, and therefore, compared to systems that induce changes in physical properties by decomposing the polymer backbone, it is possible to provide a resist composition that enables patterning with improved resolution, improved line edge roughness (LER), and / or improved line width roughness (LWR) even with a low dose of high-energy radiation.

[0098] In particular, unlike chemically amplified photoresists, which have problems such as reduced pattern uniformity and increased surface roughness as the formed acid diffuses into unexposed areas, the acid does not cause a change in the solubility of the polymer, thereby reducing the problem of reduced pattern uniformity and / or defect generation due to acid diffusion.

[0099] The polymer can be produced by any suitable method, for example, by dissolving an unsaturated bond-containing monomer in an organic solvent and then thermally polymerizing the resulting polymer in the presence of a radical initiator.

[0100] The structure (composition) of the polymer can be confirmed by FT-IR analysis, NMR analysis, X-ray fluorescence (XRF) analysis, mass spectrometry, UV analysis, single crystal X-ray structure analysis, powder X-ray diffraction (PXRD) analysis, liquid chromatography (LC) analysis, size exclusion chromatography (SEC) analysis, thermal analysis, etc. Detailed confirmation methods are as described in the Examples.

[0101] [Resist composition] In another aspect, there is provided a resist composition comprising the aforementioned polymer and an organic solvent, which may have properties such as improved developability and / or improved resolution.

[0102] The resist composition exhibits a change in solubility in a developer upon exposure to high-energy rays. The resist composition may be a positive resist composition in which exposed areas of the resist film are dissolved and removed to form a positive resist pattern, or a negative resist composition in which unexposed areas of the resist film are dissolved and removed to form a negative resist pattern. Furthermore, the resist composition according to one embodiment may be for use in an alkaline development process in which an alkaline developer is used for the development treatment during resist pattern formation, or may be for use in a solvent development process in which a developer containing an organic solvent (hereinafter also referred to as an organic developer) is used for the development treatment.

[0103] The resist composition is a non-chemically amplified type and therefore does not substantially contain a photoacid generator.

[0104] The resist composition does not substantially contain any compound having a molecular weight of 1,000 or more other than the polymer, because the physical properties of the polymer change upon exposure to light.

[0105] The polymer can be used in an amount of 0.1 to 80 parts by weight per 100 parts by weight of the resist composition. Specifically, the polymer is used in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the resist composition. If the amount satisfies the above range, any performance loss, such as a decrease in sensitivity and / or the formation of foreign particles due to insufficient solubility, can be reduced.

[0106] The polymer is as described above, and the organic solvent and optional components contained as necessary will be described below. The polymer used in the resist composition may be one type, or two or more different types may be used in combination.

[0107] <Organic solvents> The organic solvent contained in the resist composition is not particularly limited as long as it can dissolve or disperse the polymer and optional components contained as needed. One type of organic solvent may be used, or two or more different types may be used in combination. A mixed solvent of water and an organic solvent may also be used.

[0108] In one embodiment, the organic solvent may include a polar aprotic organic solvent.

[0109] In other embodiments, the organic solvent is also a mixture of a polar aprotic organic solvent and a polar protic organic solvent.

[0110] Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, and hydrocarbon-based solvents.

[0111] More specifically, examples of alcohol-based solvents include 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-ethylbutanol, 4-methyl-2-pentanol (MIBC), sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, and 2,6-dimethyl-4-heptanol. Monoalcohol solvents such as ethanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyalcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 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;Examples of the polyhydric alcohol-containing ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl 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.

[0112] Examples of ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, and dibutyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole.

[0113] Examples of ketone solvents include chain ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; and 2,4-pentanedione, acetonylacetone, and acetophenone.

[0114] Examples of amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methyl-2-pyrrolidone; and chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.

[0115] Examples of ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, n-pentyl acetate, isopentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, and cyclohexyl acetate. Acetate ester solvents such as acetate, methylcyclohexyl acetate, and n-nonyl acetate; 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 (PGMEA), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether acetate (PGMEA). Examples of suitable solvents include polyhydric alcohol-containing ether carboxylate solvents such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone and δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; lactate ester solvents such as methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate; glycol diacetate, methoxytriglyceride 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.

[0116] Examples of sulfoxide solvents include dimethyl sulfoxide and diethyl sulfoxide.

[0117] Examples of hydrocarbon solvents include aliphatic hydrocarbon 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 solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-amylnaphthalene.

[0118] Specifically, the organic solvent is selected from ether solvents, ester solvents, ketone solvents, and any combination thereof. More specifically, the organic solvent is selected from tetrahydrofuran, tetrahydropyran, γ-butyrolactone, δ-valerolactone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-pentyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, and any combination thereof.

[0119] The organic solvent is used in an amount of 200 to 100,000 parts by weight, specifically 400 to 10,000 parts by weight, based on 100 parts by weight of the polymer.

[0120] <Optional ingredients> The resist composition may further contain, as necessary, a dissolution enhancer, a dissolution inhibitor, a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof.

[0121] Specifically, the resist composition may further contain a dissolution inhibitor to improve developability, etc. The dissolution inhibitor includes a phenolphthalein derivative, a fluorescein derivative, or any combination thereof. Specific examples of the dissolution inhibitor include the following I-1 to I-3. [ka]

[0122] The resist composition may further contain a surfactant to improve coating properties, developability, etc. Specific examples of the surfactant 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. The surfactant may be a commercially available product or a synthetic product. Examples of commercially available surfactants include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75 and POLYFLOW No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP EF301, FTOP EF303 and FTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE (registered trademark) F171, MEGAFACE F173, R40, R41 and R43 (manufactured by DIC Corporation), Fluorad (registered trademark) FC430 and Fluorad FC431 (manufactured by 3M), AsahiGuard AG710 (manufactured by AGC Corporation), Surflon (registered trademark) 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.) and the like.

[0123] The surfactant is contained in an amount of 0 to 20 parts by weight based on 100 parts by weight of the polymer. One type of surfactant may be used, or two or more different types may be mixed and used.

[0124] The method for producing the resist composition is not particularly limited, and for example, a method of mixing the polymer and optional components added as needed in an organic solvent can be used. The temperature and time during mixing are not particularly limited. If necessary, filtration can be performed after mixing.

[0125] [Pattern formation method] Hereinafter, a pattern formation method according to an exemplary embodiment will be described in more detail with reference to Figures 1 and 2A to 2C. Figure 1 is a flowchart illustrating a pattern formation method according to an exemplary embodiment, and Figures 2A to 2C are side cross-sectional views illustrating a pattern formation method according to an exemplary embodiment. Hereinafter, a pattern formation method using a positive resist composition will be specifically described as an example, but is not limited thereto.

[0126] 1, the pattern forming method includes the steps of applying a resist composition to form a resist film (S101), exposing at least a portion of the resist film to high-energy radiation (S102), and developing the exposed resist film using a developer (S103). These steps may be omitted or performed in a different order, if necessary.

[0127] First, a substrate 100 is prepared. The substrate 100 can be, for example, a semiconductor substrate such as a silicon substrate or a germanium substrate, glass, quartz, ceramic, copper, etc. In some embodiments, the substrate 100 can also include a III-V compound such as GaP, GaAs, or GaSb.

[0128] A resist composition may be applied to a substrate 100 to a desired thickness, specifically by a coating method, to form a resist film 110. If necessary, the resist film 110 may be heated (referred to as pre-baking (PB) or post-annealing baking (PAB)) to remove any organic solvent remaining therein.

[0129] The coating method can be spin coating, dipping, roller coating, or other common coating methods. Among these, spin coating can be used in particular, and the viscosity, concentration, and / or spin speed of the resist composition can be adjusted to form a resist film 110 of a desired thickness. Specifically, the thickness of the resist film 110 is 10 nm to 300 nm. More specifically, the thickness of the resist film 110 is 20 nm to 200 nm.

[0130] The lower limit of the pre-baking temperature is 60°C or higher, specifically 80°C or higher. The upper limit of the pre-baking temperature is 150°C or lower, specifically 140°C or lower. The lower limit of the pre-baking time is 5 seconds or higher, specifically 10 seconds or higher. The upper limit of the pre-baking time is 600 seconds or lower, specifically 300 seconds or lower.

[0131] Before applying the resist composition to the substrate 100, a layer to be etched (not shown) may be formed on the substrate 100. The layer to be etched refers to a layer onto which an image from a resist pattern is transferred and converted into a predetermined pattern. In one embodiment, the layer to be etched may be formed to include an insulating material such as silicon oxide, silicon nitride, or silicon oxynitride. In some embodiments, the layer to be etched may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, or a metal silicide nitride. In some embodiments, the layer to be etched may be formed to include a semiconductor material such as polysilicon.

[0132] In one embodiment, to maximize the efficiency of the resist, an anti-reflective coating may be further formed on the substrate 100. The anti-reflective coating may be an organic or inorganic anti-reflective coating.

[0133] In one embodiment, in order to reduce the influence of alkaline impurities and the like contained in the process, a protective film can be further provided on the resist film 100. Furthermore, when performing immersion exposure, for example, an immersion protective film can be provided on the resist film 100 to prevent direct contact between the immersion medium and the resist film 100.

[0134] Next, at least a portion of the resist film 110 can be exposed to high-energy rays. For example, high-energy rays that have passed through a mask 120 are irradiated onto at least a portion of the resist film 110. This allows the resist film 110 to have an exposed portion 111 and a non-exposed portion 112.

[0135] Without being limited to a particular theory, exposure decomposes the polymer side chains in the exposed areas 111, generating acidic sulfonic acids in the polymer side chains, thereby increasing the solubility of the polymer in a developer, particularly an alkaline developer. Specifically, the reaction proceeds as shown in the following schematic diagram. [ka]

[0136] In some cases, the exposure is carried out by irradiating a high-energy beam through a mask having a predetermined pattern using a liquid such as water as a medium. Examples of the high-energy beam include ultraviolet, far ultraviolet, extreme ultraviolet (EUV, wavelength 13.5 nm), electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as electron beams (EB) and alpha rays. Irradiation with these high-energy beams is collectively referred to as "exposure."

[0137] A variety of exposure light sources can be used, including those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F2 excimer laser (wavelength 157 nm), those that convert the wavelength of laser light from a solid-state laser light source (such as a YAG or semiconductor laser) to emit harmonic laser light in the far ultraviolet or vacuum ultraviolet region, and those that irradiate with electron beams or extreme ultraviolet (EUV). During exposure, exposure is usually performed through a mask corresponding to the desired pattern, but if the exposure light source is an electron beam, exposure can also be performed by direct writing without using a mask.

[0138] The cumulative dose of high-energy rays, for example, when extreme ultraviolet rays are used as high-energy rays, is 2000 mJ / cm 2 Specifically, 500mJ / cm 2 When using electron beams as high-energy rays, the cumulative dose is 5000 μC / cm 2 Specifically, 1000 μC / cm 2 Also the following:

[0139] After exposure, post-exposure baking (PEB) can be performed. The lower limit of the PEB temperature is 50°C or higher, specifically 80°C or higher. The upper limit of the PEB temperature is 180°C or lower, specifically 130°C or lower. The lower limit of the PEB time is 5 seconds or higher, specifically 10 seconds or higher. The upper limit of the PEB time is 600 seconds or lower, specifically 300 seconds or lower.

[0140] Since the resist composition does not substantially contain a photoacid generator, PEB can be omitted.

[0141] The exposed resist film 110 can then be developed using a developer. The exposed portions 111 are washed away by the developer, while the unexposed portions 112 remain without being washed away by the developer. Alternatively, the opposite may occur: the unexposed portions 112 are washed away by the developer, while the exposed portions 111 remain without being washed away by the developer.

[0142] Examples of the developer include an alkaline developer and a developer containing an organic solvent (hereinafter also referred to as an "organic developer"). Examples of the development method include a dipping method, a puddle method, a spray method, and a dynamic administration method. The development temperature is, for example, 5°C or higher and 60°C or lower, and the development time is, for example, 5 seconds or higher and 300 seconds or lower.

[0143] Examples of alkaline developers include alkaline aqueous solutions containing one or more alkaline compounds 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 contain a surfactant.

[0144] The lower limit of the alkaline compound content in the alkaline developer is 0.1% by mass or more, specifically 0.5% by mass or more, and more specifically 1% by mass or more, and the upper limit of the alkaline compound content in the alkaline developer is 20% by mass or less, specifically 10% by mass or less, and more specifically 5% by mass or less.

[0145] After development, the resist pattern can be washed with ultrapure water, and then any water remaining on the substrate and pattern can be removed.

[0146] As the organic solvent contained in the organic developer, for example, the same organic solvents as those exemplified in the <Organic solvent> section of the above [Resist composition] can be used.

[0147] The lower limit of the content of the organic solvent in the organic developer is 80% by weight or more, specifically 90% by weight or more, more specifically 95% by weight or more, and particularly 99% by weight or more.

[0148] The organic developer may contain a surfactant. The organic developer may also contain a trace amount of water. During development, the organic developer may be replaced with a different solvent to stop development.

[0149] The resist pattern after development can be further washed. Ultrapure water, a rinse solution, or the like can be used as the washing solution. The rinse solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. For example, the rinse solution is an alcohol-based solvent or an ester-based solvent. After washing, the rinse solution remaining on the substrate and pattern can be removed. Furthermore, when ultrapure water is used, water remaining on the substrate and pattern can be removed.

[0150] The developer may be used alone or in combination of two or more.

[0151] After forming the resist pattern as described above, etching is performed to obtain a patterned wiring substrate. The etching method is carried out by a known method such as dry etching using plasma gas or wet etching using an alkaline solution, cupric chloride solution, ferric chloride solution, or the like.

[0152] After forming the resist pattern, plating can be carried out. The plating method is not particularly limited, but examples thereof include copper plating, solder plating, nickel plating, and gold plating.

[0153] The remaining resist pattern after etching can be stripped using an organic solvent. Examples of such organic solvents include, but are not limited to, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and ethyl lactate (EL). Stripping methods include, but are not limited to, immersion and spraying. The wiring substrate on which the resist pattern is formed can also be a multilayer wiring substrate and can have small through-holes.

[0154] In one embodiment, the wiring substrate can also be formed by a method in which, after forming a resist pattern, a metal is evaporated in a vacuum, and then the resist pattern is dissolved in a solution, that is, by a lift-off method.

[0155] 3A-3E are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention.

[0156] 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), or a metal (e.g., copper). In some embodiments, the material layer 130 may have a multi-layer structure. The material of the material layer 130 is different from the material of the substrate 100.

[0157] As shown in FIG. 3B, the resist film 110 undergoes a pre-exposure bake process and is then exposed to high-energy rays through a mask 120, after which the resist film 110 includes an exposed region 111 and a non-exposed region 112.

[0158] 3C, the exposed resist film 110 is developed using a developer (e.g., a developer). The exposed portions 111 are washed away by the developer, and the unexposed portions 112 remain without being washed away by the developer.

[0159] As shown in FIG. 3D, the exposed portions 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.

[0160] As shown in FIG. 3E, the resist pattern 110 can be removed.

[0161] 4A-4E are cross-sectional side views illustrating a method of forming a semiconductor device according to one embodiment.

[0162] 4A, a gate dielectric 505 (e.g., silicon dioxide) is formed on a substrate 500. The substrate 500 may be a semiconductor substrate, such as a silicon substrate. A gate layer 515 (e.g., doped polysilicon) is formed on the gate dielectric 505. A hard mask layer 520 is formed on the gate layer 515.

[0163] 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 an embodiment of the present invention. The resist composition may include an organic solvent.

[0164] As shown in FIG. 4C, the gate layer 515 and the gate dielectric 505 may be etched to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a.

[0165] As shown in FIG. 4D, a spacer layer may be formed on the gate electrode pattern 515a and the gate dielectric pattern 505a. The spacer layer may be formed using a deposition process (e.g., CVD). The spacer layer may be etched to form spacers 535a (e.g., silicon nitride) on the sidewalls of the gate electrode pattern 515a and the gate dielectric pattern 505a. After the spacers 535a are formed, ions may be implanted into the substrate 500 to form source / drain impurity regions S / D.

[0166] 4E, an interlayer insulating film 560 (e.g., oxide) may be formed on the substrate 500 to cover the gate electrode pattern 515a, the gate dielectric pattern 505a, and the spacers 535a. Then, electrical contacts 570a, 570b, and 570c connected to the gate electrode 515a and the source / drain regions are formed in the interlayer insulating film 560. The electrical contacts 570a, 570b, and 570c are made of a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewalls of the interlayer insulating film 560 and the electrical contacts 570a, 570b, and 570c.

[0167] 4A-4E illustrate an example of forming a transistor, but the present invention is not limited thereto.

[0168] The resist composition according to an embodiment may be used in patterning processes for forming other types of semiconductor devices.

[0169] The present invention will be described in more detail using the following examples and comparative examples, but the technical scope of the present invention is not limited to the following examples. [Example]

[0170] Synthesis Example 1: Synthesis of P1 (1) Synthesis of Monomer A1 [ka]

[0171] 1) Synthesis of Compound A1-1 N-methylhydroxylamine hydrochloride (4.816 g, 57.66 mmol) and sodium bicarbonate (NaHCO3) (9.7 g, 115 mmol) were placed in a round-bottom flask (RBF) and dissolved in a mixture of 72 mL of tetrahydrofuran (THF) and 7 mL of water (HO). Benzoyl chloride (BzCl) (7.36 mL, 63.4 mmol) was gradually added at 0°C over approximately 5 minutes, followed by stirring at room temperature for 20 hours. The reaction solvent was distilled under reduced pressure to partially remove the THF, and then water was added and the organic matter was extracted with dichloromethane (DCM). The resulting organic layer was washed with brine, dried over Na2SO4, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain compound A1-1 (6.98 g, 80%). The resulting compound was 1 This was confirmed by H-NMR. 1 H-NMR(500MHz,CDCl3)δ8.86(s,1H),7.52(m,2H),7.47(m,1H),7.41(m,2H),3.38(s,3H)

[0172] 2) Synthesis of Compound A1 Compound A1-1 (6.9 g, 45.6 mmol) was placed in an RBF and dissolved by adding 37 mL of pyridine. 4-Vinylbenzenesulfonyl chloride (9.7 g, 47.9 mmol) was added at 0°C, and the mixture was stirred at room temperature for 20 hours. 200 mL of water and 200 mL of ethyl acetate (EA) were added to extract the organic matter, and the organic layer was washed three times with saturated aqueous ammonium chloride (NH4Cl). The resulting organic layer was washed with brine, dried over Na2SO4, and filtered. The filtrate was concentrated, and the resulting residue was purified by silica gel column chromatography to obtain compound A1 (8.8 g, 61%). The compound produced was 1 This was confirmed by H-NMR. 1 H-NMR(500MHz,CD2Cl2)δ7.71-7.69(m,2H),7.47-7.42(m,3H),7.35-7.30(m,4H),6.75(dd,1H),5.93(d,1H),5.51(d,1H),3.48(s,3H)

[0173] (2) Synthesis of polymer P1 [ka]

[0174] Monomer A1 (0.650 g, 2.05 mmol), 2-oxotetrahydrofuran-3-yl methacrylate (B1, 0.349 g, 2.05 mmol), and V601 (0.094 g, 0.410 mmol) were placed in a vial and dissolved in 4.2 mL of 1,4-dioxane. After stirring at 70 °C for 20 h, the mixture was precipitated in a 5:1 (volume ratio) mixture of ethyl acetate and n-hexane. The resulting solid powder was filtered to obtain polymer P1 (0.711 g).

[0175] Synthesis Examples 2-10 Polymers P2 to P10 were synthesized in the same manner as in the synthesis of polymer P1 in Synthesis Example 1, except that the monomers in Table 1 below were used in the molar ratios in Table 1 below instead of monomer A1 and monomer B1.

[0176] [Table 1]

[0177] [ka]

[0178] Evaluation example 1: Thin film development evaluation (1) Terminology E0 is the exposure dose at which the thin film is completely developed (the thickness of the thin film does not become thinner), E1 is the exposure dose at which the thin film begins to develop, and γ is the contrast curve, calculated by the following equation 1.

number

[0179] (2) Thin film development evaluation The polymers synthesized in Synthesis Examples 1 to 10 were dissolved at 2.4 wt % in the casting solvents shown in Table 2 below. The casting solutions were spin-coated on HMDS-treated silicon wafers at 1500 rpm and then dried (PAB) at 110°C for 1 minute to produce films with a thickness of 70 nm shown in Table 2 below. Subsequently, EUV light with a wavelength of 13.5 nm was applied at 0 to 120 mJ / cm. 2 The films obtained after exposure were immersed in the developer shown in Table 2 below at 25°C for 60 seconds, then washed with water and air-dried. The remaining film thickness was measured using a film thickness measuring device (Filmetrics (registered trademark), F-20), and the results are shown in Table 3. Figure 3A is a graph showing data for polymer P1, Figure 3B is for polymer P2, Figure 3C is for polymer P3, Figure 3D is for polymer P4, Figure 3E is for polymer P5, Figure 3F is for polymer P6, Figure 3G is for polymer P8, Figure 3H is for polymer P9, Figure 3I is for polymer P10, and Figure 3J is for polymer P7.

[0180] [Table 2]

[0181] [Table 3]

[0182] Referring to Table 3, it can be seen that the solubility in the developer changed after EUV exposure in all of Examples 1 to 8. In addition, in Examples 1 to 8, the solubility in the developer was almost 30 mJ / cm. 2 It can be seen that even at a low dose below this, the sensitivity to change in solubility in the developer is improved or that the γ is relatively large.

[0183] However, in the case of Comparative Example 1, since no change in contrast occurs after EUV exposure, the E0 value could not be determined, and therefore the E1 and γ values ​​could not be determined either.

[0184] Furthermore, it can be seen that Comparative Example 2 has a relatively small γ, but it is not possible to effectively control the difference in polymer solubility between exposed and unexposed conditions, which means that Comparative Example 2 is not suitable for patterning.

Claims

1. The polymer contains 20 mol % or more of a first repeating unit represented by the following chemical formula 1: A polymer that does not contain a repeating unit A containing at least one selected from an aryl group substituted with a hydroxy group and a heteroaryl group substituted with a hydroxy group: 【Chemistry 1】 In the above Chemical Formula 1, L １１ ~L １３ are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O) ２ ; S(=O) ２ O; OS (= O) ２ or C, which may optionally contain heteroatoms; １ -C ３０ is a linear, branched, or cyclic divalent hydrocarbon radical of a11 to a13 each independently represent an integer of 1 to 4, R １１ ~R １３ are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl group; an amide group; an ester group; a sulfonate group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic anhydride group; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon radical of R １２ and R １３ can optionally be joined together to form a ring; * indicates a bonding site with an adjacent atom.

2. L １１ ~L １３ are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O) ２ ; S(=O) ２ O; OS (= O) ２ ; substituted or unsubstituted C １ -C ３０ Alkylene group; substituted or unsubstituted C ３ -C ３０ Cycloalkylene group; substituted or unsubstituted C ３ -C ３０ Heterocycloalkylene group; substituted or unsubstituted C ２ -C ３０ Alkenylene group; substituted or unsubstituted C ３ -C ３０ Cycloalkenylene group; substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylene group; substituted or unsubstituted C ６ -C ３０ an arylene group; or a substituted or unsubstituted C １ -C ３０ The polymer of claim 1 which is a heteroarylene group.

3. R １１ represents hydrogen; deuterium; halogen; cyano group; hydroxy group; amino group; carboxylic acid group; thiol group; amide group; ester group; and deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, amide group, ester group, sulfonate ester group, carbonate group, carbamate group, lactone group, sultone group, carboxylic anhydride group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C １ -C ２０ Alkoxy group, C ３ -C ２０ Cycloalkyl group, C ３ -C ２０ Cycloalkoxy group, C ６ -C ２０ aryl groups, or any combination thereof, substituted or unsubstituted, １ -C ２０ Alkyl group, C ３ -C ２０ Cycloalkyl groups, and C ６ -C ２０ aryl groups;

4. R １２ and R １３ are each independently hydrogen; deuterium; -C(=O)R １４ ; -C(R １４ ) = NR １５ ;-OR １４ ;-NR １４ R １５ -S(=O)R １４ -S(=O) ２ R １４ -S(=O) ２ OR １４ and deuterium, halogen, hydroxyl group, cyano group, nitro group, carboxylic acid group, amino group, ether group, carbonyl group, ester group, sulfonate group, carbonate group, carbamate group, amide group, lactone group, sultone group, carboxylic acid anhydride group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C １ -C ２０ Alkoxy group, C １ -C ２０ Alkylthio group, C １ -C ２０ Halogenated alkoxy group, C １ -C ２０ Halogenated alkylthio group, C ３ -C ２０ Cycloalkyl group, C ３ -C ２０ Cycloalkoxy group, C ３ -C ２０ Cycloalkylthio group, C ６ -C ２０ Aryl group, C ６ -C ２０ Aryloxy group, C ６ -C ２０ Arylthio group, C １ -C ２０ Heteroaryl group, C １ -C ２０ Heteroaryloxy group, C １ -C ２０ C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ aryl groups, and C １ -C ２０ heteroaryl groups; R １４ and R １５ are each independently hydrogen; deuterium; and deuterium, halogen, hydroxyl group, cyano group, nitro group, carboxylic acid group, amino group, ether group, carbonyl group, ester group, sulfonate group, carbonate group, carbamate group, amide group, lactone group, sultone group, carboxylic anhydride group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C １ -C ２０ Alkoxy group, C １ -C ２０ Alkylthio group, C １ -C ２０ Halogenated alkoxy group, C １ -C ２０ Halogenated alkylthio group, C ３ -C ２０ Cycloalkyl group, C ３ -C ２０ Cycloalkoxy group, C ３ -C ２０ Cycloalkylthio group, C ６ -C ２０ Aryl group, C ６ -C ２０ Aryloxy group, C ６ -C ２０ Arylthio group, C １ -C ２０ Heteroaryl group, C １ -C ２０ Heteroaryloxy group, C １ -C ２０ C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ aryl groups, and C １ -C ２０ 10. The polymer of claim 1, wherein the aryl group is selected from the group consisting of:

5. R １２ and R １３ are each independently hydrogen; deuterium; -C(=O)R １４ ; -C(R １４ ) = NR １５ -S(=O)R １４ -S(=O) ２ R １４ -S(=O) ２ OR １４ and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ aryl groups, and C １ -C ２０ heteroaryl groups; R １４ and R １５ are each independently hydrogen; deuterium; and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ aryl groups, and C １ -C ２０ 10. The polymer of claim 1, wherein the aryl group is selected from the group consisting of:

6. R １２ and R １３ are each independently —C(═O)R １４ ; -C(R １４ ) = NR １５ -S(=O) ２ R １４ and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ２０ Alkyl group, C ６ -C ２０ aryl groups, and C １ -C ２０ heteroaryl groups; R １４ and R １５ are each independently hydrogen; deuterium; and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ２０ Alkyl group, C ６ -C ２０ aryl groups, and C １ -C ２０ 10. The polymer of claim 1, wherein the aryl group is selected from the group consisting of:

7. *-N(R １２ ) R １３ The polymer according to claim 1, wherein the polymer is represented by any one of the following chemical formulas 4-1 to 4-7: 【Chemistry 2】 In the chemical formulas 4-1 to 4-7, R １２ and R １３ are each independently deuterium, halogen, a hydroxyl group, a cyano group, a nitro group, a carbonyl group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ２０ Alkyl group, C ６ -C ２０ aryl groups, and C １ -C ２０ heteroaryl groups; R １４ , R １５ , R １４ａ and R １４ｂ are each independently hydrogen; deuterium; and deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ Aryl group, C １ -C ２０ C, substituted or unsubstituted with heteroaryl groups, or any combination thereof １ -C ２０ Alkyl group, C ６ -C ２０ aryl groups, and C １ -C ２０ heteroaryl groups; R １２ ~R １５ , R １４ａ and R １４ｂ two adjacent groups among A ４１ and A ４２ each independently represents a C which may optionally contain a heteroatom; １ -C ３０ a cyclic alkyl group or a C group optionally containing heteroatoms; １ -C ３０ is an aryl group, R ４１ and R ４２ are each independently hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, C １ -C ２０ Alkyl group, C １ -C ２０ Halogenated alkyl group, C ３ -C ２０ Cycloalkyl group, C ６ -C ２０ an aryl group, or C １ -C ２０ is a heteroaryl group, b41 and b42 each independently represent an integer of 1 to 10; * indicates a bonding site with an adjacent atom.

8. *-N(R １２ ) R １３ The polymer according to claim 1, wherein the polymer is represented by any one of the following chemical formulas 4-11 to 4-40: 【Transformation 3】 【Chemistry 4】 【Transformation 5】 In the chemical formulas 4-11 to 4-40, * indicates a bonding site with an adjacent atom.

9. 2. The polymer of claim 1, wherein the first repeat unit is selected from Group I: <Group I> 【Transformation 6】 【Transformation 7】 。

10. The polymer according to claim 1 , comprising 30 mol % or more of the first repeating unit represented by Chemical Formula 1.

11. The polymer according to claim 1 , comprising at least 50 mol % of the first repeating unit represented by Chemical Formula 1.

12. 10. The polymer of claim 1, further comprising a second repeating unit represented by Formula 2: 【Transformation 8】 In the above Chemical Formula 2, L ２１ ~L ２３ are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O) ２ O; OS (= O) ２ or C, which may optionally contain heteroatoms; １ -C ３０ is a linear, branched, or cyclic divalent hydrocarbon radical of a21 to a23 each independently represent an integer of 1 to 4, R ２１ is hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl group; an ester group; a sulfonate group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic anhydride group; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon radical of X ２１ is a non-acid labile group, * indicates a bonding site with an adjacent atom.

13. X ２１ is hydrogen; a halogen; a cyano group; a hydroxy group; a carboxylic acid group; a thiol group; an amino group; or C optionally containing one or more polar groups selected from a halogen, a cyano group, a hydroxy group, a carboxylic acid group, a thiol group, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), a lactone group, a sultone group, and a carboxylic acid anhydride group. １ -C ３０ 13. The polymer of claim 12, wherein R is a linear, branched, or cyclic monovalent hydrocarbon group of the formula:

14. X ２１ is hydrogen, a hydroxy group, C １ -C １０ The polymer according to claim 12, selected from alkyl groups and groups represented by the following chemical formulas 5-1 to 5-15: 【Chemistry 9】 In the chemical formulas 5-1 to 5-15, a51 is 1 or 2; R ５１ ~R ５６ each independently represents a bonding site to an adjacent atom; hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl group; an ester group; a sulfonate group; a carbonate group; a carbamate group; a lactone group; a sultone group; a carboxylic anhydride group; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon radical of R ５１ ~R ５３ One of them, R ５４ One of these and R ５５ and R ５６ One of these is a bonding site with an adjacent atom, b51 is selected from integers of 1 to 4; b52 is selected from integers from 1 to 10; b53 is selected from integers from 1 to 8; b54 is selected from integers from 1 to 5; b55 is selected from integers from 1 to 7; b56 is selected from integers from 1 to 11; b57 is selected from integers from 1 to 13; b58 is selected from integers from 1 to 15; b59 is selected from integers of 1 to 2; m51 is selected from integers of 1 to 4.

15. 13. The polymer of claim 12, wherein the second repeat unit is selected from Group II: <Group II> 【Chemistry 10】 【Chemistry 11】 。

16. A resist composition comprising the polymer according to claim 1 and an organic solvent.

17. 17. The resist composition according to claim 16, which is substantially free of compounds having a molecular weight of 1,000 or more other than the polymer.

18. Applying the photoresist composition of claim 16 on a substrate to form a photoresist film; exposing at least a portion of the photoresist film to high energy radiation; and developing the exposed photoresist film using a developer.

19. 20. The pattern formation method according to claim 18, wherein the exposing step is performed by irradiating with ultraviolet light, deep ultraviolet (DUV), extreme ultraviolet (EUV), X-rays, gamma rays, electron beams (EB), and / or alpha rays.

20. the exposed resist film includes an exposed portion and a non-exposed portion, The pattern formation method according to claim 18 , wherein the exposed portion is removed in the developing step.

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