Resist composition and pattern forming method using the same

Abstract

To provide a resist composition and a pattern forming method using the same.SOLUTION: The present invention relates to a resist composition and a pattern forming method using the same, the resist composition containing: a polymer which contains a first repeating unit represented by the following chemical formula 1 and does not contain a crosslinking group; and an additive represented by the following chemical formula 2. In the chemical formulae 1 and 2, explanations regarding L11-L13, a11-a13, R11, X11, A21, L21, a21 and n21 are described in the specification.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Resists whose physical properties change in response to light are used to form fine patterns during semiconductor manufacturing. Among them, chemically amplified resists have been widely used. Chemically amplified resists 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] In particular, when high-energy rays having relatively high energy such as EUV are used, there is a problem that the number of photons is significantly reduced even when irradiated with light of the same energy. As a result, there is a demand for a resist composition that can effectively act even when used in a small amount and can provide improved sensitivity, improved resolution, and / or reduced defects. Summary of the Invention [Problem to be solved by the invention]

[0004] The problem to be solved by the present invention is to provide a resist composition that can provide improved sensitivity, improved resolution, and / or reduced defects, and a pattern formation method using the same. [Means for solving the problem]

[0005] In one aspect, there is provided a resist composition comprising a polymer comprising a first repeating unit represented by the following Chemical Formula 1 and not comprising a crosslinking group, and an additive represented by the following Chemical Formula 2: [ka]

[0006] In the above Chemical Formulas 1 and 2, L 11 ~L 13 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 12 ;NR 12 C(=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 a11 to a13 each independently represent an integer of 1 to 4, R 11 and R 12 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 moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a C1-C group optionally containing a heteroatom. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of X 11 is an acid labile group, A 21 represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted C-C 30 Alkyl groups, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C1-C 30 Heterocycloalkyl groups, substituted or unsubstituted C2-C 30 Alkenyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyl groups, substituted or unsubstituted C1-C 30 Heterocycloalkenyl groups, substituted or unsubstituted C2-C 30 Alkynyl groups, substituted or unsubstituted C6-C 30 Aryl groups, or substituted or unsubstituted C1-C 30 is a heteroaryl group, Said C1-C 30 Heterocycloalkyl groups, such as C1-C30 heterocycloalkenyl groups, and the C1-C 30 Heteroaryl groups do not contain nitrogen (N) or sulfur (S) as ring members, L 21 is a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 21 ;NR 21 C(=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 a21 is an integer from 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; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C1-C group optionally containing heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of n21 is an integer from 1 to 8, * indicates a bonding site with an adjacent atom.

[0007] In 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]

[0008] Embodiments of the present invention can provide resist compositions with improved sensitivity, improved resolution, and / or reduced defectivity. [Brief explanation of the drawings]

[0009] [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

[0010] 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.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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 moieties containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, or some carbon atoms are replaced by moieties containing heteroatoms such as oxygen, sulfur, or nitrogen, so that these groups can also contain hydroxy groups, cyano groups, carbonyl groups, carboxyl groups, ether bonds, ester bonds, sulfonate ester bonds, carbonates, lactone rings, sultone rings, carboxylic anhydride moieties, or haloalkyl moieties.

[0017] As used herein, the term "divalent hydrocarbon group" refers to a divalent residue in which any one hydrogen atom of the monovalent hydrocarbon group is replaced by a bonding site with 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.

[0018] As used herein, "alkyl group" refers to a linear or branched saturated aliphatic hydrocarbon monovalent group, and specific examples 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, "alkylene group" refers to a linear or branched saturated aliphatic hydrocarbon divalent group, and specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, etc.

[0019] 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.

[0020] 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.

[0021] As used herein, an "alkylthio group" is defined as -SA 101 where A 101 is an alkyl group.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] As used herein, a "cycloalkylthio group" refers to a group represented by -SA 102 where A 102 is a cycloalkyl group.

[0027] As used herein, a "heterocycloalkyl group" refers to a cycloalkyl group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen, and the heterocycloalkyl group specifically includes an ether bond, an ester bond, a sulfonate ester bond, a carbonate, a lactone ring, a sultone ring, or a carboxylic acid anhydride moiety. As used herein, a "heterocycloalkylene group" refers to a cycloalkylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0028] As used herein, a "heterocycloalkoxy group" is defined as -OA. 103 where A 103 is a heterocycloalkyl group.

[0029] 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.

[0030] As used herein, an "alkenyloxy group" is defined as -OA 104 where A 104 is an alkenyl group.

[0031] 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.

[0032] As used herein, a "cycloalkenyloxy group" is defined as -OA 105 where A 105 is a cycloalkenyl group.

[0033] As used herein, a "heterocycloalkenyl group" refers to a cycloalkenylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen. As used herein, a "heterocycloalkenylene group" refers to a cycloalkenylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0034] As used herein, a "heterocycloalkenyloxy group" is defined as -OA 106where A 106 is a heterocycloalkenyl group.

[0035] 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.

[0036] As used herein, an "alkynyloxy group" is defined as -OA 107 where A 107 is an alkynyl group.

[0037] 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.

[0038] As used herein, an "aryloxy group" is defined as -OA 108 where A 108 is an aryl group.

[0039] 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.

[0040] As used herein, a "heteroaryloxy group" is defined as -OA 109 where A 109 is a heteroaryl group.

[0041] As used herein, a "substituent" is any of deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether moiety, ester moiety, sulfonic acid ester moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, 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 group, or C1-C 20 heteroarylthio groups; Deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether moiety, ester moiety, sulfonic acid ester moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, 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-C20 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 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, and C1-C 20 heteroarylthio groups; or any combination thereof.

[0042] 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.

[0043] [Resist composition] A resist composition according to an exemplary embodiment includes a polymer including a first repeating unit represented by the following Chemical Formula 1 and not including a crosslinking group, and an additive represented by the following Chemical Formula 2: [ka]

[0044] In the above Chemical Formulas 1 and 2, L 11 ~L 13 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 12 ;NR 12 C(=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 a11 to a13 each independently represent an integer of 1 to 4, R 11 and R 12 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 moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a C1-C group optionally containing a heteroatom. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of X 11 is an acid labile group, A 21 represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted C-C 30 Alkyl groups, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C1-C 30 Heterocycloalkyl groups, substituted or unsubstituted C2-C 30 Alkenyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyl groups, substituted or unsubstituted C1-C 30 Heterocycloalkenyl groups, substituted or unsubstituted C2-C 30 Alkynyl groups, substituted or unsubstituted C6-C 30 Aryl groups, or substituted or unsubstituted C1-C 30 is a heteroaryl group, Said C1-C 30 Heterocycloalkyl groups, such as C1-C 30 heterocycloalkenyl groups, and the C1-C 30 Heteroaryl groups do not contain nitrogen (N) or sulfur (S) as ring members, L 21 is a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 21 ;NR 21 C(=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 a21 is an integer from 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; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C1-C group optionally containing heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of n21 is an integer from 1 to 8, * indicates a bonding site with an adjacent atom.

[0045] <Polymer> 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-C30 Heterocycloalkenylene group; substituted or unsubstituted C6-C 30 arylene groups; or substituted or unsubstituted C-C 30 It is a heteroarylene group.

[0046] 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, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, ester moiety, sulfonate ester moiety, carbonate moiety, carbamate moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, 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;

[0047] 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, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C1-C 20C1-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.

[0048] In the above chemical formula 1, a11 to a13 are each L 11 ~L 13 means the number of iterations.

[0049] For example, in the above Chemical Formula 1, a11 to a13 are each independently an integer of 1 to 3.

[0050] As another example, in the above Chemical Formula 1, a11 to a13 are each independently 1.

[0051] For example, in the above formula 1, R 11 is hydrogen; deuterium; halogen; cyano group; hydroxy group; amino group; carboxylic acid group; thiol group; and deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, ester moiety, sulfonate ester moiety, carbonate moiety, carbamate moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, 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;

[0052] As another example, in Formula 1, R 11is hydrogen; deuterium; halogen; cyano group; and C-C substituted or unsubstituted with deuterium, halogen, cyano group, or any combination thereof. 20 alkyl groups;

[0053] As another example, in Formula 1, R 11 is H, D, F, CH3, CH2F, CHF2, CF3, CH2CH3, CHFCH3, CHFCH2F, CHFCHF2, CHFCF3, CF2CH3, CF2CH2F, CF2CHF2, CF2CF3, Cl, CH2Cl, CHCl2, CCl3, CHClCH3, CHClCH2Cl, CHClCHCl2, CHClCCl3, CCl2CH3, CCl2CH2Cl, CCl2CHCl2, or CCl2CCl3.

[0054] For example, in the above formula 1, R 12 represents hydrogen, deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, C1-C 20 Alkyl groups, C1-C 20 Halogenated alkyl groups, C3-C 20 Cycloalkyl groups, or C6-C 20 It is an aryl group.

[0055] In this specification, the acid labile group means a group that is eliminated from the polymer by an acid to generate a polar group, which serves to make the polymer more easily soluble in a developer, such as an aqueous TMAH solution.

[0056] For example, 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).

[0057] For example, in the above Chemical Formula 1, X 11 includes groups with tertiary acyclic alkyl carbons, groups with tertiary alicyclic carbons, or acetals.

[0058] As another example, in the above-mentioned Chemical Formula 1, X 11is represented by any one of the following chemical formulas 6-1 to 6-12: [ka]

[0059] In the chemical formulas 6-1 to 6-12, X 61 is an ester moiety, a sulfonate ester moiety, a carbonate moiety, or a carbamate moiety; a61 is an integer 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 moiety; a sulfonate ester moiety; a carbonate moiety; a carbamate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; or a C1-C group optionally containing heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of R 61 ~R 68 two adjacent groups among b64 is an integer between 1 and 10, * indicates a bonding site with an adjacent atom.

[0060] Specifically, in the chemical formulas 6-1 to 6-12, X 61 is an ester moiety or a carbonate moiety.

[0061] As another example, in the above Chemical Formula 1, X 11 is represented by any one of the following chemical formulas 6-21 to 6-46: [ka]

[0062] In the chemical formulas 6-21 to 6-46, * indicates a bonding site with an adjacent atom.

[0063] In one embodiment, the first repeat unit is selected from Group I: <Group I> [ka] [ka] [ka] [ka]

[0064] In one embodiment, the polymer may further comprise a second repeating unit represented by Formula 3: [ka]

[0065] In the above Chemical Formula 3, L 31 ~L 33 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 32 ;NR 32 C(=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 a31 to a33 each independently represent an integer of 1 to 4, R 31 and R 32are each independently hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a C1-C group optionally containing a heteroatom. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of X 31 is a non-acid labile group, * indicates a bonding site with an adjacent atom.

[0066] In the above Chemical Formula 3, L 31 ~L 33 The explanation regarding L in Chemical Formula 1 is 11 Please refer to the explanation regarding this.

[0067] In the above Chemical Formula 3, the explanation of a31 to a33 refers to the explanation of a11 in the above Chemical Formula 1.

[0068] In the above formula 3, R 31 The explanation regarding R in Chemical Formula 1 is 11 Please refer to the explanation regarding this.

[0069] In the above formula 3, R 32 The explanation regarding R in Chemical Formula 1 is 12 Please refer to the explanation regarding this.

[0070] For example, in the above Chemical Formula 3, X 31 is a C1-C alkyl group which may optionally contain one or more polar moieties selected from: hydrogen; halogen; cyano; hydroxy; carboxylic acid; thiol; amino; or halogen, cyano, hydroxy, carboxylic acid, thiol, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), lactone moieties, sultone moieties, and carboxylic anhydride moieties. 30 is a linear, branched or cyclic monovalent hydrocarbon group of the formula:

[0071] As another example, in the above-mentioned Chemical Formula 3, X 31 is selected from hydrogen, a hydroxy group, and groups represented by the following chemical formulas 5-1 to 5-16: [ka]

[0072] In the chemical formulas 5-1 to 5-16, a51 is 1 or 2, R 51 ~R 56 are each independently a bonding site to the adjacent atom; hydrogen; deuterium; a halogen; a cyano group; a hydroxy group; an amino group; a carboxylic acid group; a thiol group; a carbonyl moiety; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a carbamate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; 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 a bonding site with an adjacent atom, b51 is an integer from 1 to 4, b52 is an integer from 1 to 10, b53 is an integer from 1 to 8, b54 is an integer from 1 to 5, b55 is an integer from 1 to 7, b56 is an integer from 1 to 11, b57 is an integer from 1 to 13, b58 is an integer from 1 to 15, b59 is an integer between 1 and 2, m51 is an integer from 1 to 4.

[0073] Specifically, in the above-mentioned Chemical Formula 3, X 31is selected from a hydroxy group and formulas 5-11 above.

[0074] In one embodiment, the second repeat unit is selected from Group II: [ka]

[0075] Specifically, the crosslinking group is an epoxy group or an oxetanyl group.

[0076] Because the polymer does not contain crosslinking groups, the polymer does not crosslink under heat, acid and / or high energy radiation.

[0077] In one embodiment, the polymer comprises 1 to 100 mol %, specifically 5 to 100 mol %, and especially 10 to 100 mol % of the first repeat unit.

[0078] For example, the polymer may consist of the first repeat unit.

[0079] In another example, the polymer contains 0 to 99 mol %, specifically 1 to 99 mol %, and more specifically 10 to 90 mol % of the second repeat unit.

[0080] In one embodiment, the polymer may be composed of the first repeating unit and the second repeating unit, for example, the polymer may contain 1 to 99 mol %, specifically 10 to 90 mol %, of the first repeating unit and 1 to 99 mol %, specifically 10 to 90 mol %, of the second repeating unit.

[0081] The polymer has a weight average molecular weight (Mw) of 1,000 to 500,000, specifically 3,000 to 100,000, and more specifically 5,000 to 50,000, as measured by gel permeation chromatography using tetrahydrofuran solvent and polystyrene as the standard.

[0082] The polydispersity index (PDI: Mw / Mn) of the polymer is 1.0 to 3.0, specifically 1.0 to 2.5. By satisfying this range, the possibility of foreign matter remaining on the pattern can be reduced and deterioration of the pattern profile can be minimized. This makes the resist composition more suitable for forming fine patterns.

[0083] As the polymer, one type may be used, or two or more different types may be used in combination.

[0084] <Additives> For example, in the above Chemical Formula 2, A 21 represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted C-C 30 Alkyl groups, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C1-C 30 Heterocycloalkyl groups, substituted or unsubstituted C2-C 30 Alkenyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyl groups, substituted or unsubstituted C1-C 30 Heterocycloalkenyl groups, substituted or unsubstituted C2-C 30 Alkynyl groups, substituted or unsubstituted C6-C 30 Aryl groups, or substituted or unsubstituted C1-C 30 is a heteroaryl group, Said C1-C 30 Heterocycloalkyl groups, such as C1-C 30 heterocycloalkenyl groups, and the C1-C 30 The heteroaryl group may contain oxygen (O), selenium (Se) or phosphorus (P) as a heteroatom constituting the ring.

[0085] As another example, in the above-mentioned Chemical Formula 2, A 21 represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted C-C 30 Alkyl groups, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C2-C30 Alkenyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyl groups, substituted or unsubstituted C2-C 30 Alkynyl group, or substituted or unsubstituted C6-C 30 It is an aryl group.

[0086] As another example, in the above-mentioned Chemical Formula 2, A 21 is a substituted or unsubstituted C1-C 20 Alkyl group or substituted or unsubstituted C3-C 20 It is a cycloalkyl group.

[0087] Specifically, in the above-mentioned chemical formula 2, A 21 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, cyclopentyl, cyclohexyl, phenyl, or any combination thereof, unsubstituted or substituted with deuterium, halogen, cyano, hydroxy, amino, carboxylic acid, thiol, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, sec-pentyl, tert-pentyl, neo-pentyl, 3-pentyl, 3-methyl-2-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, and naphthyl.

[0088] For example, in the above Chemical Formula 2, L 21 is a single bond; O; C(=O); C(=O)O; OC(=O); substituted or unsubstituted C1-C 30 Alkylene group; substituted or unsubstituted C3-C 30 Cycloalkylene group; substituted or unsubstituted C2-C 30 Alkenylene group; substituted or unsubstituted C3-C 30 cycloalkenylene group; or substituted or unsubstituted C6-C 30 It is an arylene group.

[0089] As another example, in the above-mentioned Chemical Formula 2, L 21 is selected from a single bond; O; C(═O); C(═O)O; OC(═O); and methylene, ethylene, n-propylene, n-butylene, isobutylene, cyclopentylene, and cyclohexylene groups unsubstituted or substituted with deuterium, halogen, cyano, hydroxy, amino, carboxylic acid, thiol, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, cyclopentyl, cyclohexyl, phenyl, or any combination thereof.

[0090] For example, in the above Chemical Formula 2, n21 is an integer of 1 to 6.

[0091] As another example, in the above Chemical Formula 2, n21 is an integer of 2 to 4.

[0092] In one embodiment, the additive is selected from Group III: [ka]

[0093] The additive is included in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the polymer. Specifically, the additive is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polymer. If the amount satisfies the above range, acid is generated at an appropriate level, while any performance loss, such as a decrease in sensitivity and / or formation of foreign particles due to insufficient solubility, can be reduced.

[0094] When the resist composition contains a photoacid generator, the additive is contained in an amount of 0.01 to 70 parts by weight relative to 100 parts by weight of the photoacid generator. Specifically, the additive is contained in an amount of 5 to 60 parts by weight relative to 100 parts by weight of the photoacid generator. If the above range is satisfied, the uniformity of the pattern can be improved while the formation of foreign particles due to insufficient solubility can be reduced.

[0095] Typically, EUV (13.5 nm) has a lower photon count than ArF immersion light sources. Therefore, the lower the exposure dose, the more noticeable the noise at the boundary between the EUV-exposed and unexposed regions. To compensate for this, a higher content of photoacid generator is required for EUV lithography compared to lithography using other light sources with the same light intensity. However, if a resist composition contains a high content of photoacid generator, the glass transition temperature (Tg) of the base resin may change, reducing thermal stability. Furthermore, residual photoacid generator remaining during EUV lithography may reduce the resolution of the resist pattern formed.

[0096] The resist composition may have properties such as improved developability and / or improved resolution.

[0097] 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 an exposed portion of the resist film is dissolved and removed to form a positive resist pattern, or a negative resist composition in which an unexposed portion of the resist film is dissolved and removed to form a negative resist pattern. Specifically, the resist composition is a positive resist composition.

[0098] Furthermore, the resist composition according to one embodiment may be for an alkaline development process in which an alkaline developer is used in the development treatment during resist pattern formation, or may be for a solvent development process in which a developer containing an organic solvent (hereinafter also referred to as an organic developer) is used in the development treatment.

[0099] The photoacid generator, organic solvent, and optional components such as a quencher that may be contained as needed will be described below.

[0100] <Photoacid generator> The photoacid generator is any compound that generates an acid when exposed to high-energy rays, such as UV, DUV, EB, EUV, X-rays, α-rays, γ-rays, or the like.

[0101] The photoacid generator includes sulfonium salts, iodonium salts, and combinations thereof.

[0102] In one embodiment, the photoacid generator is represented by Formula 7: [ka]

[0103] In the above Chemical Formula 7, B 71 + is represented by the following chemical formula 7A, and A 71 - is represented by any one of the following chemical formulas 7B to 7D, B 71 + and A 71 - are optionally linked by a carbon-carbon covalent bond; [ka] In the above Chemical Formulae 7A to 7D, L 71 ~L 73 are each independently a single bond or CRR′, R and R' are each independently hydrogen, deuterium, halogen, cyano, hydroxy, C1-C 30 Alkyl groups, C1-C 30 Halogenated alkyl groups, C1-C 30 Alkoxy groups, C3-C 30 Cycloalkyl groups, or C3-C 30 is a cycloalkoxy group, n71 to n73 each independently represent 1, 2, or 3; x71 and x72 each independently represent 0 or 1; R 71 ~R 73are each independently a C-C group which may optionally contain heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of R 71 ~R 73 adjacent two of the groups may optionally be bonded to each other to form a fused ring; R 74 ~R 76 are each independently hydrogen; halogen; or C-C optionally containing heteroatoms. 30 is a linear, branched or cyclic monovalent hydrocarbon group of the formula:

[0104] For example, in the above-mentioned Chemical Formula 7, B 71 + is represented by the above chemical formula 7A, and A 71 - is represented by the above-mentioned Chemical Formula 7B. Specifically, in the above-mentioned Chemical Formula 7A, R 71 ~R 73 are each phenyl groups.

[0105] The photoacid generator is included in an amount of 0.01 to 40 parts by weight, 0.1 to 40 parts by weight, or 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer. If the amount is within the above range, appropriate resolution can be achieved and problems associated with foreign particles after development or during stripping can be reduced.

[0106] The photoacid generator may be used alone or in combination of two or more different types.

[0107] <Organic solvents> The organic solvent contained in the resist composition is not particularly limited as long as it can dissolve or disperse optional components such as an amine compound, a polymer, a photoacid generator, and optional components such as a quencher, which are 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 containing water and an organic solvent may also be used.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] Examples of sulfoxide solvents include dimethyl sulfoxide and diethyl sulfoxide.

[0115] 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.

[0116] Specifically, the organic solvent is selected from alcohol solvents, amide solvents, ester solvents, sulfoxide solvents, and any combination thereof. More specifically, the solvent is 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.

[0117] On the other hand, when an acid labile group in the form of an acetal is used, the organic solvent may further contain a high-boiling alcohol, such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, or 1,3-butanediol, to accelerate the deprotection reaction of the acetal.

[0118] The organic solvent is used in an amount of 200 to 20,000 parts by weight, specifically 2,000 to 10,000 parts by weight, based on 100 parts by weight of the polymer.

[0119] <Quencher> The resist composition may further include a quencher.

[0120] The quencher is a salt that generates an acid that is weaker in acidity than the acid generated from the photoacid generator.

[0121] The quenchers include ammonium salts, sulfonium salts, iodonium salts, and combinations thereof.

[0122] In one embodiment, the quencher is represented by Formula 8: [ka]

[0123] In the above Chemical Formula 8, B 81 + is represented by any one of the following chemical formulas 8A to 8C, and A 81 - is represented by any one of the following chemical formulas 8D to 8F, B 81 + and A 81 - are optionally linked through a carbon-carbon covalent bond; [ka] In the above Chemical Formulas 8A to 8F, L 81 and L 82 are each independently a single bond or CRR′, R and R' are each independently hydrogen, deuterium, halogen, cyano, hydroxy, C1-C 30 Alkyl groups, C1-C 30 Halogenated alkyl groups, C1-C 30 Alkoxy groups, C3-C 30 Cycloalkyl groups, or C3-C 30 is a cycloalkoxy group, n81 and n82 are each independently 1, 2, or 3; x81 is either 0 or 1, R 81 ~R 84 are each independently a C-C group which may optionally contain heteroatoms. 30 is a linear, branched, or cyclic monovalent hydrocarbon radical of R 81 ~R 84 adjacent two of the groups may optionally be bonded to each other to form a fused ring; R 85 and R 86 is hydrogen; halogen; or C-C optionally containing heteroatoms. 30 is a linear, branched or cyclic monovalent hydrocarbon group of the formula:

[0124] The quencher is included in an amount of 0 to 10 parts by weight, 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight, based on 100 parts by weight of the polymer. If the amount is within the above range, appropriate resolution can be achieved and problems associated with foreign particles after development or during stripping can be reduced.

[0125] The quencher may be used alone or in combination of two or more different types.

[0126] <Optional ingredients> The resist composition may further contain, as necessary, a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof.

[0127] 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.

[0128] The surfactant is contained in an amount of 0 to 20 parts by weight based on 100 parts by weight of the polymer.

[0129] The surfactant may be used alone or in combination of two or more different surfactants.

[0130] The method for producing the resist composition is not particularly limited, and for example, a method of mixing an amine compound, a polymer, a photoacid generator, 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.

[0131] [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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] The coating method can be spin coating, dipping, roller coating, or other common coating methods. Among these, spin coating can be particularly used, 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 30 nm to 200 nm.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] During the exposure step, the amine compound is ionized to generate radical positive ions and electrons.

[0142] In some cases, the exposure is carried out by irradiating a high-energy beam through a mask having a predetermined pattern using a liquid medium such as water. Examples of the high-energy beam include ultraviolet light, deep ultraviolet light (DUV), extreme ultraviolet light (EUV, wavelength 13.5 nm), electromagnetic waves such as X-rays and gamma rays, electron beams (EB), and charged particle beams such as alpha rays. Irradiation with these high-energy beams is collectively referred to as "exposure."

[0143] 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.

[0144] The cumulative dose of high-energy rays is, for example, 2000 mJ / cm when extreme ultraviolet rays are used as high-energy rays. 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:

[0145] 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.

[0146] Next, a developer can be used to develop the exposed resist film 110. The exposed portions 111 are washed away by the developer, while the unexposed portions 112 remain without being washed away by the developer.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] After development, the resist pattern can be washed with ultrapure water, and then any water remaining on the substrate and pattern can be removed.

[0151] 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.

[0152] The lower limit of the content of the organic solvent in the organic developer is 80% by mass or more, specifically 90% by mass or more, more specifically 95% by mass or more, and particularly 99% by mass or more.

[0153] 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.

[0154] 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.

[0155] The developer may be used alone or in combination of two or more.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 3A-3E are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] As shown in FIG. 3E, the resist pattern 110 can be removed.

[0166] 4A-4E are cross-sectional side views illustrating a method of forming a semiconductor device according to one embodiment.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 4A-4E illustrate an example of forming a transistor, but the present invention is not limited thereto.

[0173] The resist composition according to an embodiment may be used in patterning processes for forming other types of semiconductor devices.

[0174] 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]

[0175] Synthesis Example 1: Synthesis of polymer HS / EAd [ka] 1.5 g (9.3 mmol) of acetoxystyrene (AHS), 2.3 g (9.3 mmol) of 2-ethyl-2-adamantyl methacrylate (EAd-MA), and 0.2 g (0.9 mmol) of azo initiator (V601) were dissolved in 18 mL of dioxane and reacted at 80 °C for 4 hours to obtain AHS / EAd. 1 g of hydrazine monohydrate was added to AHS / EAd and reacted at room temperature for 2 hours to obtain a reaction mixture. 50 mL of deionized water (DW) and 2 g of acetic acid were then added to the reaction mixture, which was extracted with ethyl acetate (EA). The resulting precipitate was then precipitated in hexane and dried at 40 °C for 24 hours to obtain a white powder of polymer HS / EAd. The resulting polymer HS / EAd had a number average molecular weight (Mn) of 4000 and a PDI of 1.3.

[0176] Evaluation example 1: Acid generation effect evaluation The acid generating effect was confirmed by the following method. 6.5 wt% of coumarin 6 (CAS No. 38215-36-0) was dissolved in acetonitrile (ACN), and PAG was added to the solution in the same molar amount as coumarin 6. The additives were then added in the amounts shown in Table 1 below, and the resulting solution was transferred to a quartz cell and irradiated with DUV (248 nm) at 0 to 100 mJ / cm. 2The absorbance was measured after exposure to 100 mJ / cm. Coumarin 6 was used as an acid indicator because, theoretically, it absorbs at 460 nm, but acid increases the absorbance of coumarin 6 at a wavelength of 522 nm. 2 The absorbance intensity after exposure was assumed to be 100% converted to Coumarin 6, and the absorbance intensity at each exposure dose was normalized to show the degree of acid generation, which was expressed as a relative value based on the value of Comparative Example 1-1.

[0177] [Table 1] [ka]

[0178] Referring to Table 1, it can be seen that Examples 1-1 to 1-3 have improved acid generation effects compared to Comparative Examples 1-1 to 1-3. That is, when additives are used as in Examples 1-1 to 1-3, it is expected that improved resolution can be achieved even when the same amount of photoacid generator is used.

[0179] Evaluation example 2: Thin film development evaluation 1 The polymer HS / EAd synthesized in Synthesis Example 1 was dissolved in a casting solvent of PGME / PGMEA = 7 / 3 (w / w) to a concentration of 1.6 wt %, and then 0.024 mmol of PAG and 0.016 mmol of PDQ were added. The additives listed in Table 2 below were added, and the mixture was filtered through a 0.2 μm separation membrane filter. The casting solution was spin-coated on a silicon wafer treated with HMDS at 1500 rpm, and then dried (PAB) at 110°C for 1 minute to form a film. Then, 13.5 nm wavelength EUV was irradiated at 0-50 mJ / cm. 2The photoresist was exposed to a dose of 10 ... op The resolution, IPU and sensitivity were measured, respectively.

[0180] The measured values ​​were substituted into the following Equation 1 to calculate the Z-factor, and the results were normalized and shown in Table 2 below. <Formula 1> Z-factor=(resolution) 3 ×(IPU) 2 × (sensitivity)

[0181] In Equation 1, resolution is CD size (half pitch), IPU is a value calculated from the CD distribution, and sensitivity is E op (dose), and the lower the Z-factor, the better the pattern performance at the same dose.

[0182] [Table 2] [ka]

[0183] Referring to Table 2, the photoresist patterns using the photoresist films formed with the photoresist compositions of Examples 2-1 to 2-3 had significantly higher Z-factors and / or E values ​​than the photoresist patterns using the photoresist films formed with the photoresist compositions of Comparative Examples 2-1 to 2-3. op It can be confirmed that is low.

[0184] Evaluation example 3: Thin film development evaluation 2 76 mg of the polymer HS / EAd synthesized in Synthesis Example 1, 23.13 mg of PAG, and 10.54 mg of PDQ were added to a casting solvent of PGME / PGMEA = 7 / 3 (w / w). The additives listed in Tables 3 and 4 below were added, and the mixture was filtered through a 0.2 μm separation membrane filter. The casting solution was spin-coated onto a silicon wafer treated with HMDS at 1500 rpm, and then dried (PAB) at 110°C for 1 minute to form a film. Subsequently, 248 nm wavelength DUV or 13.5 nm wavelength EUV were irradiated at 0-50 mJ / cm. 2 The resist pattern was formed by immersing the resist in a 2.38 wt% aqueous TMAH solution at 25°C for 20 seconds, then rinsing with deionized water for 10 seconds to remove the areas exposed to DUV or EUV, and then drying. The remaining film thickness of the photoresist pattern was measured using a 3D optical profiler (Bruker, Contour X-100), and E0 and E1 were measured, respectively, and are shown in Tables 3 and 4 below. Table 3 shows the data for DUV, and Table 4 shows the data for EUV.

[0185] E0 means the exposure dose at which the thin film is completely developed (the thickness of the thin film does not become thinner), E1 means the exposure dose at which the thin film begins to develop, and γ is a value calculated from the contrast curve using the following equation 2.

number

[0186] [Table 3] [Table 4] [ka]

[0187] Referring to Table 3, it can be seen that Examples 3-1 and 3-2 exhibit smaller E1 values ​​and smaller E0 values ​​than Comparative Examples 3-1 to 3-3, which suggests that Examples 3-1 and 3-2 have improved sensitivity compared to Comparative Examples 3-1 to 3-3.

[0188] Referring to Table 4, it can be seen that Examples 4-1 and 4-2 have a larger γ value than Comparative Examples 4-1 to 4-3, which suggests that Examples 4-1 and 4-2 have improved sensitivity compared to Comparative Examples 4-1 to 4-3.

Claims

1. a polymer comprising a first repeating unit represented by the following formula 1 and not comprising a crosslinking group; An additive represented by the following chemical formula 2; A resist composition comprising: 【Chemistry 1】 In the above Chemical Formulas 1 and 2, L １１ ~L １３ are each independently a single bond; O; S; C(═O); C(═O)O; OC(═O); C(═O)NR １２ ;NR １２ C(=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 group of a11 to a13 each independently represent an integer of 1 to 4, R １１ and R １２ 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 moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon radical of X １１ is an acid labile group, A ２１ represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted C １ -C ３０ alkyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkyl groups, substituted or unsubstituted C １ -C ３０ Heterocycloalkyl groups, substituted or unsubstituted C ２ -C ３０ Alkenyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C １ -C ３０ heterocycloalkenyl group, substituted or unsubstituted C ２ -C ３０ Alkynyl group, substituted or unsubstituted C ６ -C ３０ an aryl group, or a substituted or unsubstituted C １ -C ３０ is a heteroaryl group, Said C １ -C ３０ Heterocycloalkyl group, １ -C ３０ heterocycloalkenyl group, and the C １ -C ３０ The heteroaryl group does not contain nitrogen (N) or sulfur (S) as ring members, L ２１ represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ２１ ;NR ２１ C(=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 group of a21 is 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; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon radical of n21 is an integer from 1 to 8, * 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 2. The resist composition according to claim 1, wherein the group is a heteroarylene group.

3. R １１ represents hydrogen; deuterium; halogen; cyano group; hydroxy group; amino group; carboxylic acid group; thiol group; and deuterium, halogen, cyano group, hydroxy group, amino group, carboxylic acid group, thiol group, ester moiety, sulfonate ester moiety, carbonate moiety, carbamate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, 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 2. The resist composition according to claim 1, wherein the aryl group is selected from the group consisting of aryl groups and aryl groups.

4. X １１ is represented by any one of the following chemical formulas 6-1 to 6-12: 【Chemistry 2】 In the chemical formulas 6-1 to 6-12, X ６１ is an ester moiety, a sulfonate ester moiety, a carbonate moiety, or a carbamate moiety; a61 is an integer from 0 to 6, R ６１ and R ６８ each independently represents a C which may optionally contain a heteroatom; １ -C 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 moiety; a sulfonate ester moiety; a carbonate moiety; a carbamate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a C group which may optionally contain a heteroatom. １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon radical of R ６１ ~R ６８ two adjacent groups among b64 is an integer from 1 to 10, * indicates a bonding site with an adjacent atom.

5. 2. The resist composition of claim 1, wherein the first repeating unit is selected from Group I: <Group I> 【Chemistry 3A】 【Chemistry 3B】 【Chemicals 3C】 [3D Transformation] 。

6. 2. The resist composition of claim 1, further comprising a second repeating unit represented by the following chemical formula 3: 【Chemistry 4】 In the above Chemical Formula 3, L ３１ ~L ３３ are each independently a single bond; O; S; C(═O); C(═O)O; OC(═O); C(═O)NR ３２ ;NR ３２ C(=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 group of a31 to a33 each independently represent an integer of 1 to 4, R ３１ and R ３２ 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 moiety; a sulfonate ester moiety; a carbonate moiety; a lactone moiety; a sultone moiety; a carboxylic acid anhydride moiety; or a C which may optionally contain a heteroatom. １ -C ３０ is a linear, branched, or cyclic monovalent hydrocarbon radical of X ３１ is a non-acid labile group, * indicates a bonding site with an adjacent atom.

7. X ３１ is selected from hydrogen, a hydroxy group, and groups represented by the following chemical formulas 5-1 to 5-16: 【Transformation 5】 In the chemical formulas 5-1 to 5-16, a51 is 1 or 2; R ５１ ~R ５６ are each independently a bonding site with 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 moiety; an ester moiety; a sulfonate ester moiety; a carbonate moiety; a carbamate moiety; a lactone moiety; a sultone moiety; a carboxylic anhydride moiety; 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 an integer from 1 to 4, b52 is an integer from 1 to 10, b53 is an integer from 1 to 8, b55 is an integer from 1 to 7, b54 is an integer from 1 to 5, b56 is an integer from 1 to 11, b57 is an integer from 1 to 13, b58 is an integer from 1 to 14, b59 is an integer of 1 to 2, m51 is an integer of 1 to 4.

8. X ３１ The resist composition according to claim 7, wherein is selected from a hydroxy group and a group represented by any one of the chemical formulas 5 to 11.

9. 7. The resist composition of claim 6, wherein the second repeating unit is selected from Group II: 【Transformation 6】 。

10. A ２１ represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted C １ -C ３０ alkyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkyl groups, substituted or unsubstituted C １ -C ３０ Heterocycloalkyl groups, substituted or unsubstituted C ２ -C ３０ Alkenyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C １ -C ３０ heterocycloalkenyl group, substituted or unsubstituted C ２ -C ３０ Alkynyl group, substituted or unsubstituted C ６ -C ３０ an aryl group, or a substituted or unsubstituted C １ -C ３０ is a heteroaryl group, Said C １ -C ３０ Heterocycloalkyl group, １ -C ３０ heterocycloalkenyl group, and the C １ -C ３０ 2. The resist composition according to claim 1, wherein the heteroaryl group may contain oxygen (O), selenium (Se), or phosphorus (P) as a heteroatom constituting the ring.

11. A ２１ represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted C １ -C ３０ alkyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkyl groups, substituted or unsubstituted C ２ -C ３０ Alkenyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C ２ -C ３０ an alkynyl group, or a substituted or unsubstituted C ６ -C ３０ 2. The resist composition according to claim 1, wherein the group is an aryl group.

12. L ２１ represents a single bond; O; C(=O); C(=O)O; OC(=O); a substituted or unsubstituted C １ -C ３０ Alkylene group; substituted or unsubstituted C ３ -C ３０ Cycloalkylene group; substituted or unsubstituted C ２ -C ３０ Alkenylene group; substituted or unsubstituted C ３ -C ３０ a cycloalkenylene group; or a substituted or unsubstituted C ６ -C ３０ 2. The resist composition according to claim 1, wherein the group is an arylene group.

13. 2. The resist composition according to claim 1, wherein n21 is an integer of 1 to 6.

14. 2. The resist composition of claim 1, wherein the additive is selected from the following Group III: 【Transformation 7】

15. 2. The resist composition according to claim 1, wherein the additive is contained in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the polymer.

16. The resist composition according to claim 1 , further comprising a photoacid generator.

17. 17. The resist composition according to claim 16, wherein the additive is contained in an amount of 0.01 to 70 parts by weight relative to 100 parts by weight of the photoacid generator.

18. Applying the photoresist composition of claim 1 onto a substrate to form a photoresist film; exposing at least a portion of the photoresist film to high energy radiation; developing the exposed photoresist film using a developer; A pattern forming method comprising:

19. 20. The pattern formation method according to claim 18, wherein the exposing step is performed by irradiating with ultraviolet light, deep ultraviolet light (DUV), extreme ultraviolet light (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.

Images