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

Abstract

Provided are a polymer, a resist composition containing the same, and a pattern forming method using the same. A polymer containing a first repeating unit represented by the following chemical formula, a resist composition containing the same, and a pattern forming method using the same. TIFF2026075072000030.tif42128 In the formula, L 11 and L 12 are each independently a single bond, O, S, C(=O), C(=O)O, etc., a11 and a12 are each independently an integer from 1 to 4, X 11 is a C6-C30 aryl group or a C1-C30 heteroaryl group, and X 12 is CN, C(=O)R 12 C(=O)OR 12 etc.

Description

[Technical Field]

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

[0002] During semiconductor manufacturing, resists that change their properties in response to light are used to form fine patterns. Among these, chemically amplified resists have been widely used. Chemically amplified resists enable patterning by reacting light with a photoacid generator to form an acid, which then reacts again with the base resin, changing the solubility of the base resin in the developer.

[0003] In particular, when using high-energy rays with relatively very high energies, such as EUV, there is a problem in that the number of photons is significantly lower even when irradiated with light of the same energy. This creates a need for resist compositions that can act effectively even when used in small quantities, and that can provide improved sensitivity, improved resolution, and / or reduced defects. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The present invention has been made in view of the above-mentioned conventional problems, and the object to be solved by the present invention is to provide a polymer that can provide improved sensitivity and / or resolution, a resist composition containing the same, and a pattern formation method using the same. [Means for solving the problem]

[0005] A polymer according to one aspect of the present invention, made to achieve the above objective, comprises a first repeating unit represented by the following chemical formula 1.

[0006] [ka]

[0007] In the above Chemical Formula 1, L 11 and L 12 each independently represents a single bond, O, S, C(=O), C(=O)O, OC(=O), C(=O)NR 11 NR 11 C(=O), S(=O), S(=O)2, S(=O)2O, OS(=O)2, or a substituted or unsubstituted C1-C 30 linear, branched or cyclic divalent hydrocarbon group optionally containing heteroatoms, a11 and a12 each independently represent an integer from 1 to 4, X 11 is a substituted or unsubstituted C6-C 30 aryl group or a substituted or unsubstituted C1-C 30 heteroaryl group, X 12 is CN, C(=O)R 12 C(=O)OR 12 C(=O)SR 12 or C(=O)NR 12 R 13 is, R 11 ~R 13 each independently represents hydrogen, deuterium, or a substituted or unsubstituted C1-C 30 linear, branched or cyclic monovalent hydrocarbon group optionally containing heteroatoms, * represents a bonding site with an adjacent atom.

[0008] According to another aspect, a resist composition containing the above polymer and solvent is provided.

[0009] According to still another aspect, a patterning method is provided, which includes the steps of coating the above resist composition on a substrate to form a resist film, exposing at least a part of the resist film with high energy rays, and developing the exposed resist film using a developer.

Effects of the Invention

[0010] Embodiments of the present invention can provide a resist composition having improved sensitivity and / or resolution. [Brief explanation of the drawing]

[0011] [Figure 1] This is a flowchart showing a pattern formation method according to one embodiment of the present invention. [Figure 2A] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 2B] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 2C] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 3A] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3B] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3C] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3D] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3E] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 4A] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4B] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4C] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4D] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4E] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 5]This graph shows the thin film thickness after development using the dose of Example 1-1. [Figure 6] This graph shows the thin film thickness after development using the doses of Examples 2-1 and 2-2. [Figure 7A] This is a pattern image of Example 3-1. [Figure 7B] This is a pattern image of Example 3-2. [Figure 7C] This is a pattern image of Example 3-3. [Modes for carrying out the invention]

[0012] The present invention can be subjected to various transformations and has many different embodiments. 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 specific embodiments; rather, it should be understood that the present invention includes all transformations, equivalents, or substitutes that fall within the spirit and technical scope of the present invention. If a specific description of related prior art in explaining the present invention is deemed to obscure the gist of the invention, such detailed description will be omitted.

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

[0014] In this specification, when a part such as a layer, film, region, or plate is described as being "on top of" or "above" another part, this includes not only parts that are immediately above, below, left, or right in contact, but also parts that are above, below, left, or right in non-contact.

[0015] Unless otherwise clearly stated in the context, singular expressions include plural expressions. Terms such as “includes” or “has” should be understood, unless otherwise stated, to indicate the presence of the features, numbers, stages, operations, components, parts, ingredients, materials, or combinations thereof described in the specification, and should not presuppose the presence or addition of one or more other features, numbers, stages, operations, components, parts, ingredients, materials, or combinations thereof.

[0016] Each time a range of values ​​is listed, that range includes all values ​​that fall within that range as explicitly recorded, and further includes the boundaries of the range. Therefore, the range "X~Y" includes all values ​​between X and Y, and also includes X and Y.

[0017] In this specification, "C x -C y " means that the substituent consists of x to y carbon atoms. For example, "C1-C6" means that the substituent consists of 1 to 6 carbon atoms, and "C6-C 20 This means that the substituent consists of 6 to 20 carbon atoms.

[0018] In this specification, "monovalent hydrocarbon group" means a monovalent residue derived from an organic compound or derivative thereof containing carbon and hydrogen, and specific examples include linear or branched alkyl groups (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, 2-ethylhexyl group, and nonyl group); monovalent saturated cyclic aliphatic hydrocarbon groups (cycloalkyl groups) (e.g., cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, 1-adamantyl group, 2-adamantyl group, 1-adamantylmethyl group, norbornyl group, norbornylmethyl group, tricyclodecanyl group, tetracyclododecanyl group) This includes groups such as 1-L group, tetracyclododecanylmethyl group, and dicyclohexylmethyl group; monounsaturated aliphatic hydrocarbon groups (alkenyl group, alkynyl group) (e.g., allyl group); monounsaturated cyclic aliphatic hydrocarbon groups (cycloalkenyl group) (e.g., 3-cyclohexenyl); aryl groups (e.g., phenyl group, 1-naphthyl group, and 2-naphthyl group); arylalkyl groups (e.g., benzyl group and diphenylmethyl group); heteroatom-containing monovalent hydrocarbon groups (e.g., tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, methylthiomethyl group, acetamidomethyl group, trifluoroethyl group, (2-methoxyethoxy)methyl group, acetoxymethyl group, 2-carboxy-1-cyclohexyl group, 2-oxopropyl group, 4-oxo-1-adamantyl group, and 3-oxocyclohexyl group), or any combination thereof.Furthermore, in these groups, some hydrogen atoms may be substituted by a molecule containing a heteroatom, such as oxygen, sulfur, nitrogen, phosphorus, or halogen atom, or some carbon atoms may be substituted by a molecule containing a heteroatom, such as oxygen, sulfur, nitrogen, or phosphorus. Thus, these groups may also include cyano groups, nitro groups, hydroxyl groups, thiol groups, amino groups, carboxylic acid groups, ether molecules, thioether molecules, carbonyl molecules, ester molecules, phosphonate molecules, sulfonate molecules, carbonate molecules, amide molecules, lactone molecules, sultone molecules, carboxylic acid anhydride molecules, and the like.

[0019] In this specification, “divalent hydrocarbon group” means a divalent residue in which one hydrogen of a monovalent hydrocarbon group is replaced by a bonding site with an adjacent atom. Divalent hydrocarbon groups include, for example, linear or branched alkylene groups, cycloalkylene groups, alkenylene groups, alkylylene groups, cycloalkylene groups, arylene groups, and those in which some of their carbon atoms are replaced by heteroatoms.

[0020] In this specification, "alkyl group" means a linear or branched monovalent saturated aliphatic hydrocarbon group, and specific examples include methyl group, ethyl group, propyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, iso-amyl group, hexyl group, and the like. In this specification, "alkylene group" means a linear or branched divalent saturated aliphatic hydrocarbon group, and specific examples include methylene group, ethylene group, propylene group, butylene group, isobutylene group, and the like.

[0021] In this specification, "halogenated alkyl group" means a group in which one or more substituents of an alkyl group are substituted with halogens, and specific examples include CF3, where the halogen is F, Cl, Br, or I.

[0022] In this specification, "alkoxy group" is defined as -OA 101 This refers to a monovalent group having the chemical formula A101 These are alkyl groups. Specific examples include methoxy groups, ethoxy groups, and isopropyloxy groups.

[0023] In this specification, "alkylthio group" is defined as -SA 101 This refers to a monovalent group having the chemical formula A 101 It is an alkyl group.

[0024] In this specification, "halogenated alkoxy group" means a group in which one or more hydrogen atoms of an alkoxy group are substituted with halogens, and specific examples include -OCF3.

[0025] In this specification, "halogenated alkylthio group" means a group in which one or more hydrogen atoms of an alkylthio group are substituted with halogens, and specific examples include -SCF3.

[0026] In this specification, "cycloalkyl group" means a monovalent saturated hydrocarbon ring group, and specific examples include monocyclic groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group, and condensed polycyclic groups such as norbornyl group and adamantyl group. In this specification, "cycloalkylene group" means a divalent saturated hydrocarbon ring group, and specific examples include cyclopentylene group, cyclohexylene group, adamantylene group, adamantylmethylene group, norbornylene group, norbornylmethylene group, tricyclodecanylene group, tetracyclododecanylene group, tetracyclododecanylmethylene group, and dicyclohexylmethylene group.

[0027] In this specification, "cycloalkoxy group" is defined as -OA 102 This refers to a monovalent group having the chemical formula A 102 These are cycloalkyl groups. Specific examples include cyclopropoxy groups and cyclobutoxy groups.

[0028] In this specification, "cycloalkylthio group" is defined as -SA 102 This refers to a monovalent group having the chemical formula A 102It is a cycloalkyl group.

[0029] In this specification, "heterocycloalkyl group" is defined as a cycloalkyl group in which some carbon atoms are replaced by a heteroatom, such as oxygen, sulfur, or nitrogen, and heterocycloalkyl groups specifically include ether bonds, ester bonds, sulfonic acid ester bonds, carbonates, lactone rings, sultone rings, or carboxylic acid anhydride molecules. In this specification, "heterocycloalkylene group" is defined as a cycloalkylene group in which some carbon atoms are replaced by a heteroatom, such as oxygen, sulfur, or nitrogen.

[0030] In this specification, "heterocycloalkoxy group" is defined as -OA 103 This refers to a monovalent group having the chemical formula A 103 It is a heterocycloalkyl group.

[0031] In this specification, "heterocycloalkylthio group" is defined as -SA 103 This refers to a monovalent group having the chemical formula A 103 It is a heterocycloalkyl group.

[0032] In this specification, "alkenyl group" means a monovalent group of a linear or branched unsaturated aliphatic hydrocarbon containing one or more carbon-carbon double bonds. In this specification, "alkenylene group" means a divalent group of a linear or branched unsaturated aliphatic hydrocarbon containing one or more carbon-carbon double bonds.

[0033] In this specification, "cycloalkenyl group" means a monovalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds. In this specification, "cycloalkenylene group" means a divalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds.

[0034] In this specification, a "heterocycloalkenyl group" is defined as a cycloalkenylene group in which some of the carbon atoms are replaced by a heteroatom, such as oxygen, sulfur, or nitrogen.

[0035] In this specification, "alkynyl group" means a monovalent unsaturated aliphatic hydrocarbon group that is linear or branched and contains one or more carbon-carbon triple bonds.

[0036] In this specification, "aryl group" means a monovalent group having a carbocyclic aromatic system, and specific examples include phenyl group, naphthyl group, anthracenyl group, phenantrenyl group, pyrenyl group, chrysenyl group, etc. In this specification, "arylene group" means a divalent group having a carbocyclic aromatic system.

[0037] In this specification, "aryloxy group" is defined as -OA 104 This refers to a monovalent group having the chemical formula A 104 It is an aryl group.

[0038] In this specification, "arylthio group" is defined as -SA 104 This refers to a monovalent group having the chemical formula A 104 It is an aryl group.

[0039] In this specification, "heteroaryl group" means a monovalent group having a heterocyclic aromatic system, and specific examples include pyridinyl group, pyrimidinyl group, and pyrazinyl group. In this specification, "heteroarylene group" means a divalent group having a heterocyclic aromatic system.

[0040] In this specification, "heteroaryloxy group" is defined as -OA 105 This refers to a monovalent group having the chemical formula A 105 It is a heteroaryl group.

[0041] In this specification, "heteroarylthio group" is defined as -SA 105 This refers to a monovalent group having the chemical formula A 105 It is a heteroaryl group.

[0042] In this specification, "arylalkyl group" means a group in which an alkyl group is substituted with a monovalent group having a carbocyclic aromatic system, and specific examples include the benzyl group and the diphenylmethyl group.

[0043] In this specification, "heteroarylalkyl group" means a group in which an alkyl group is substituted with a monovalent group having a heterocyclic aromatic system.

[0044] In this specification, "heterocyclic group" means a monocyclic or polycyclic group having 1 to 60 carbon atoms that contains at least one heteroatom, and includes groups that are monovalent, divalent, trivalent, etc.

[0045] In this specification, "substituent" means deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether molecule, thioether molecule, carbonyl molecule, ester molecule, phosphonate molecule, sulfonate molecule, carbonate molecule, amide molecule, lactone molecule, sultone molecule, carboxylic acid anhydride molecule, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryl group, C1-C 20Heteroaryloxy group, or C1-C 20 heteroarylthio group;

[0046] Deuterium, halogen, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylic acid group, ether moisture, thioether moisture, carbonyl moisture, ester moisture, phosphonate moisture, sulfonate moisture, carbonate moisture, amide moisture, lactone moisture, sultone moisture, carboxylic acid anhydride moisture, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryl group, C1-C 20 Heteroaryloxy group, C1-C 20 C1-C substituted with heteroarylthio groups, or any combination thereof. 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20Heteroaryl group, C1-C 20 Heteroaryloxy group, and C1-C 20 Heteroarylthio group; or any combination thereof.

[0047] Hereinafter, embodiments according to the present invention will be described in detail with reference to the drawings. When describing with reference to the drawings, substantially the same or corresponding components are given the same drawing numbers, and the overlapping descriptions thereof are omitted. In the drawings, the thickness is enlarged to clearly show a plurality of layers and regions. And, in the drawings, for convenience of explanation, the thicknesses of some layers and regions are exaggerated. On the other hand, the embodiments described below are merely exemplary, and various modifications are possible from such embodiments.

[0048] [Polymer] The polymer according to a specific embodiment includes a first repeating unit represented by the following Chemical Formula 1.

[0049] [Chemical formula]

[0050] In Chemical Formula 1, L 11 and L 12 are each independently a single bond, O, S, C(=O), C(=O)O, OC(=O), C(=O)NR 11 NR 11 C(=O), S(=O), S(=O)2, S(=O)2O, OS(=O)2, or a substituted or unsubstituted C1-C 30 linear, branched or cyclic divalent hydrocarbon group optionally containing a heteroatom, a11 and a12 are each independently an integer from 1 to 4, X 11 is a substituted or unsubstituted C6-C 30 aryl group or a substituted or unsubstituted C1-C 30 heteroaryl group, X 12 is CN, C(=O)R 12, C(=O)OR 12 , C(=O)SR 12 , or C(=O)NR 12 R 13 where R 11 ~R 13 are each independently hydrogen, deuterium, or a substituted or unsubstituted C1-C 30 linear, branched, or cyclic monovalent hydrocarbon group optionally containing heteroatoms, * is a bonding site with an adjacent atom.

[0051] For example, in Chemical Formula 1, L 11 and L 12 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, a substituted or unsubstituted C1-C 30 alkylene group, a substituted or unsubstituted C3-C 30 cycloalkylene group, a substituted or unsubstituted C3-C 30 heterocycloalkylene group, a substituted or unsubstituted C2-C 30 alkenylene group, a substituted or unsubstituted C3-C 30 cycloalkenylene group, a substituted or unsubstituted C3-C 30 heterocycloalkenylene group, a substituted or unsubstituted C6-C 30 arylene group, or a substituted or unsubstituted C1-C 30 heteroarylene group.

[0052] Specifically, in Chemical Formula 1, L 11 and L 12 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, sulfonic acid ester moiety, carbonate moiety, carbamate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 20Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C6-C 20 A C1-C group that is substituted or unsubstituted with an aryl group, or any combination thereof. 20 Alkylene group, C3-C 20 Cycloalkylene group, C3-C 20 Heterocycloalkylene group, C2-C 20 Alkenylene group, C3-C 20 Cycloalkenylene group, C3-C 20 Heterocycloalkenylene group, C6-C 20 Arylene group, and C1-C 20 Selected from heteroarylene groups.

[0053] More specifically, in chemical formula 1, L 11 and L 12 These are, independently, single bonds; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); and Deuterium, halogen, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 C1-C 20 Alkylene group, C3-C 20 Cycloalkylene group, C3-C 20 Selected from heterocycloalkylene groups, phenylene groups, and naphthylene groups.

[0054] In chemical formula 1, a11 and a12 are L 11 and L 12 This refers to the number of repetitions.

[0055] For example, in chemical formula 1, a11 and a12 are each independent integers between 1 and 3.

[0056] Specifically, in chemical formula 1, a11 and a12 are each independently equal to 1.

[0057] For example, in chemical formula 1, X 11 This includes deuterium, halogens, cyano groups, hydroxyl groups, amino groups, carboxylic acid groups, thiol groups, ester molecules, sulfonic acid ester molecules, carbonate molecules, carbamate molecules, lactone molecules, sultone molecules, carboxylic acid anhydride molecules, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C6-C 20 A C6-C group that is substituted or unsubstituted with an aryl group, or any combination thereof. 20 Aryl group and C1-C 20 Selected from heteroaryl groups.

[0058] Specifically, in chemical formula 1, X 11 These are deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, thiol group, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C6-C 20 A C6-C group that is substituted or unsubstituted with an aryl group, or any combination thereof. 20 Aryl group and C1-C 20 Selected from heteroaryl groups.

[0059] More specifically, in chemical formula 1, X 11 These are deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, thiol group, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C3-C20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C6-C 20 A C6-C group that is substituted or unsubstituted with an aryl group, or any combination thereof. 20 Selected from aryl groups.

[0060] In particular, in chemical formula 1, X 11 These are deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, thiol group, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 The group is selected from phenyl and naphthyl groups, which may be substituted or unsubstituted with an alkoxy group or any combination thereof.

[0061] In particular, in chemical formula 1, X 11 It is represented by the following chemical formula 3.

[0062] [ka]

[0063] In chemical formula 3, R 31 ~R 35 These are, independently, hydrogen, deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, thiol group, and C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogenated groups, or C1-C 20 It is an alkoxy group, * indicates a bonding site with an adjacent atom.

[0064] Specifically, in chemical formula 1, X 12 It can be represented by one of the following chemical formulas 4-1 to 4-4. [ka]

[0065] In chemical formulas 4-1 to 4-4, R 12 and R 13 These are the same as those described herein, * indicates a bonding site with an adjacent atom.

[0066] For example, in chemical formula 1, R 11 ~R 13 These are, independently, hydrogen; deuterium; and Deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, thiol group, ester moisture, sulfonic acid ester moisture, carbonate moisture, carbamate moisture, lactone moisture, sultone moisture, carboxylic acid anhydride moisture, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C6-C 20 A C1-C group that is substituted or unsubstituted with an aryl group, or any combination thereof. 20 Alkyl, C3-C 20 Cycloalkyl groups, and C6-C 20 Selected from aryl groups.

[0067] Specifically, in chemical formula 1, R 11 ~R 13 These are, independently, hydrogen; deuterium; and deuterium, halogen, cyano group, C1-C 20 Alkyl alkyl group, C6-C 20 A C1-C group that is substituted or unsubstituted with an aryl group, or any combination thereof. 20 Alkyl and C6-C 20 Selected from aryl groups.

[0068] More specifically, in chemical formula 1, R 11 ~R 13 These are, independently, hydrogen; deuterium; and deuterium, halogen, cyano group, C1-C 10 Alkyl alkyl group, C6-C 10A C1-C group that is substituted or unsubstituted with an aryl group, or any combination thereof. 10 Alkyl and C6-C 10 Selected from aryl groups.

[0069] In particular, in chemical formula 1, R 11 ~R 13 These are, independently, H, D, F, Cl, CH3, C2H5, C3H7, C4H9, CH(CH3)2, C(CH3)3, CH2C(CH3)3, CH2F, CHF2, CF3, CHFCH3, CHFCH2F, CHFCHF2, CHFCF3, CH2CF3, CF2CH3, CF2CH2F, CF2CHF2, CF2CF3, CH2Cl, CHCl2, CCl3, CHClCH3, CHClCH2Cl, CHClCHCl2, CHClCCl3, CH2CCl3, CCl2CH3, CCl2CH2Cl, CCl2CHCl2, CCl2CCl3, C6H5, C6F5, C6Cl5, CH2C6H5, CH2C6F5, or CH2C6Cl5.

[0070] In one embodiment, the first repeating unit may be selected from the following group I.

[0071] [ka] TIFF2026075072000007.tif220152

[0072] In Group I, * represents a bonding site with an adjacent atom.

[0073] In one embodiment, the polymer may further contain a second repeating unit represented by the following chemical formula 2.

[0074] [ka]

[0075] In chemical formula 2, L 21 and L 22These are, independently, single bonds, O, S, C(=O), C(=O)O, OC(=O), and C(=O)NR. 21 , NR 21 Substituted or unsubstituted C1-C selectively containing C(=O), S(=O), S(=O)2, S(=O)2O, OS(=O)2, or heteroatoms. 30 It is a linear, branched, or cyclic divalent hydrocarbon group. a21 and a22 are each independent integers between 1 and 4. X 21 It is an electron-withdrawing group, X 22 , CN, C(=O)R 22 , C(=O)OR 22 , C(=O)SR 22 , or C(=O)NR 22 R 23 And, R 21 ~R 23 Each of these is independently a substituted or unsubstituted C1-C molecule selectively containing hydrogen, deuterium, or a heteroatom. 30 It is a linear, branched, or cyclic monovalent hydrocarbon group. * indicates a bonding site with an adjacent atom.

[0076] In chemical formula 2, L 21 and L 22 The explanation for this is L in chemical formula 1. 11 This is the same as the explanation related to [the relevant topic].

[0077] In chemical formula 2, the explanations for a21 and a22 are the same as the explanations for a11 in chemical formula 1.

[0078] In chemical formula 2, X 22 The explanation for this is X in chemical formula 1. 21 This is the same as the explanation related to [the relevant topic].

[0079] In chemical formula 2, R 21 ~R 23 The explanation for this is R in chemical formula 1. 11 ~R 13This is the same as the explanation related to [the relevant topic].

[0080] For example, in chemical formula 2, X 21 is halogen; cyano group; halogen, cyano group, C1-C 20 C1-C substituted with halogenated alkyl groups or any combination thereof 30 Alkyl, C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl group, C3-C 30 Cycloalkenyl group, C2-C 30 Alkynyl group, C6-C 30 Aryl group, and C7-C 30 Arylalkyl groups; and OSO2R x Selected from, R x C1-C is either substituted or non-substituted. 10 Alkyl group or substituted or unsubstituted C6-C 10 It is an aryl group.

[0081] Specifically, in chemical formula 2, X 21 is halogen; cyano group; halogen, cyano group, C1-C 20 C1-C substituted with halogenated alkyl groups or any combination thereof 20 Alkyl and C6-C 20 Aryl group; and OSO2R x Selected from, R x C1-C is either substituted or non-substituted. 10 Alkyl group or substituted or unsubstituted C6-C 10 It is an aryl group.

[0082] More specifically, in chemical formula 2, X 21These are F, CH2F, CHF2, CF3, CHFCH3, CHFCH2F, CHFCHF2, CHFCF3, CH2CF3, CF2CH3, CF2CH2F, CF2CHF2, CF2CF3, Cl, CH2Cl, CHCl2, CCl3, CHClCH3, CHClCH2Cl, CHClCHCl2, CHClCCl3, CH2CCl3, CCl2CH3, CCl2CH2Cl, CCl2CHCl2, CCl2CCl3, C6F5, C6Cl5, CN, OSO2CH3, OSO2CF3, or OSO2C6H4(CH3).

[0083] Specifically, in chemical formula 1, X 22 It can be represented by one of the following chemical formulas 5-1 to 5-4. [ka]

[0084] In chemical formulas 5-1 to 5-4, R 22 and R 23 These are the same as those described herein, * indicates a bonding site with an adjacent atom. In chemical formula 2, R 21 ~R 23 The explanation for this is R in chemical formula 1. 11 This is the same as the explanation related to [the relevant topic].

[0085] In one embodiment, the second repeating unit may be selected from the following group II.

[0086] [ka] TIFF2026075072000011.tif125151

[0087] In Group II, OMs are OSO2CH3, OTf is OSO2CF3, OTs are OSO2C6H4(CH3), and * indicates a bonding site with an adjacent atom.

[0088] In one embodiment, the polymer may consist of a first repeating unit.

[0089] In one embodiment, the polymer may consist of a first repeating unit and a second repeating unit.

[0090] For example, the polymer contains 1 to 99 mol%, specifically 10 to 90 mol%, more specifically 20 to 80 mol%, particularly 30 to 70 mol%, and even more particularly 30 to 50 mol%, of the first repeating units, and 1 to 99 mol%, specifically 10 to 90 mol%, more specifically 20 to 80 mol%, particularly 30 to 70 mol%, and even more particularly 50 to 70 mol%, of the second repeating units.

[0091] In particular, the polymer is contained in a molar ratio of 5:1 to 1:5 for the second repeating unit relative to the first repeating unit, specifically a molar ratio of 3:1 to 1:3, and more specifically a molar ratio of 2:1 to 1:2, especially a molar ratio of 1:1 to 3:7.

[0092] The polymers have 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 standard materials.

[0093] The polydispersity index (PDI: Mw / Mn) of the polymer is between 1.0 and 4.0, specifically between 1.0 and 3.5. Satisfying this range reduces the likelihood of foreign matter remaining on the pattern or minimizes degradation of the pattern profile. This makes the resist composition even more suitable for forming fine patterns.

[0094] Polymers can undergo changes in their properties due to high-energy radiation. Specifically, as the main chain of the polymer decomposes, the molecular weight of the polymer decreases, which can increase its solubility in the developer. Since polymers do not change in properties due to acid, pattern degradation due to acid diffusion does not occur, which is advantageous for fine patterning.

[0095] Also, the polymer is X 12 Because it contains such a structure, the stability of the reactive intermediates produced during the polymer degradation process is improved, thereby promoting the formation of the final degradation product.

[0096] Furthermore, the polymer is X 11 Because it contains a structure like this, the stability of the reactive intermediate produced in the polymer degradation process is improved by the resonance effect, X 11 The steric effect can minimize side reactions.

[0097] While not limited to any particular theory, polymers can produce their final decomposition products via a reactive intermediate of chemical formula A shown below. Therefore, the more stable the reactive intermediate of chemical formula A is, the more the formation of the final decomposition products is promoted, and the more side reactions can be minimized.

[0098] [ka]

[0099] The energy of the lowest energy state of the reactive intermediate represented by chemical formula A was calculated using density functional theory (DFT) and is shown in Table 1 below.

[0100] [Table 1] [ka]

[0101] Polymers are produced by any suitable method. For example, polymers are produced by radical polymerization.

[0102] The polymer structure (composition) can be determined by methods such as 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, and thermal analysis. Detailed confirmation methods are described in the examples.

[0103] [Resist composition] In another embodiment, a resist composition comprising the aforementioned polymer and solvent is provided. The resist composition may have properties such as improved developability and / or improved resolution.

[0104] The solubility of the resist composition in the developer changes upon exposure to high-energy rays. The resist composition may be a positive-type resist composition in which the exposed areas of the resist film are dissolved and removed to form a positive-type resist pattern, or it may be a negative-type resist composition in which the unexposed areas of the resist film are dissolved and removed to form a negative-type resist pattern. Specifically, the resist composition is a positive-type resist composition.

[0105] Furthermore, the resist composition according to one embodiment may be for a dry development process that does not use a solvent for the development process during resist pattern formation, for an alkaline development process that uses an alkaline developer, or for a solvent development process that uses a developer containing an organic solvent (hereinafter also referred to as an organic developer) for the development process. In particular, the resist composition according to one embodiment is for a solvent development process.

[0106] Since the properties of the polymer change upon exposure, the resist composition substantially does not contain any compounds with a molecular weight of 1,000 or more other than the polymer.

[0107] Furthermore, the resist composition is substantially free of photoacid generators.

[0108] The resist composition does not contain organometallic compounds.

[0109] The polymer is 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 above range is satisfied, any performance loss, such as a decrease in sensitivity and / or the formation of foreign particles due to insufficient solubility, can be reduced.

[0110] Furthermore, the polymer used in the resist composition may be a single type, or two or more different types may be used in combination.

[0111] As the polymer has been described above, the solvent and any optional components that may be included will be described below. <Solvent>

[0112] The solvent included in the resist composition is not particularly limited, as long as it is capable of dissolving or dispersing the polymer and any optional components such as photoacid generators and quenchers that may be included.

[0113] The solvent may be a single type, or a combination of two or more different types may be used.

[0114] The solvent may be an organic solvent, or a mixed solvent consisting of water and an organic solvent.

[0115] Examples of organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, and hydrocarbon-based solvents.

[0116] More specifically, alcoholic solvents include, for example, 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, 2,6-dimethyl-4-heptanol Monoalcohol solvents such as tanol, 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; polyhydric alcohol 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 include polyhydric alcohol-containing ether solvents such as 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, propylene glycol monomethyl ether (PGME), 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.

[0117] Examples of ether-based solvents include diethylene glycol dimethyl ether, propylene glycol dimethyl ether; 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.

[0118] Examples of ketone solvents include linear 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.

[0119] Examples of amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methyl-2-pyrrolidone; and chain-like amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.

[0120] 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 Examples include polyhydric alcohol-containing ether carboxylate solvents such as noethyl 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, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetate, ethyl acetate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

[0121] Examples of sulfoxide solvents include dimethyl sulfoxide and diethyl sulfoxide.

[0122] 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.

[0123] Specifically, the organic solvent is selected from alcohol-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based 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.

[0124] On the other hand, if an acid-unstable group in acetal form is used, a high-boiling point alcohol, such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, or 1,3-butanediol, may be further added to the organic solvent to accelerate the deprotection reaction of the acetal.

[0125] The solvent is used in an amount of 200 to 20,000 parts by weight, specifically 2,000 to 10,000 parts by weight, per 100 parts by weight of polymer.

[0126] <Optional ingredients> The resist composition may further contain, as needed, an acid generator, a quencher, a dissolution enhancer, a dissolution inhibitor, a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof.

[0127] The resist composition may further contain a surfactant to improve its applicability, developability, etc. Specific examples of surfactants 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, for example, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75 and POLYFLOW No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP EF301, FTOP EF303 and FTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE® F171, MEGAFACE F173, R40, R41 and R43 (manufactured by DIC Corporation), Fluorad® FC430 and Fluorad FC431 (manufactured by 3M Company), AsahiGuard AG710 (manufactured by AGC Inc.), Surflon® S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105 and Surflon Examples include SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.).

[0128] The surfactant is present in an amount of 0 to 20 parts by weight per 100 parts by weight of polymer.

[0129] A single surfactant may be used, or two or more different surfactants may be used in combination.

[0130] The method for producing the resist composition is not particularly limited, and for example, a method of mixing the polymer and any optional components added as needed in an organic solvent can be used. The temperature and time during mixing are not particularly limited. Filtration can be performed after mixing as needed.

[0131] [Pattern formation method] The pattern formation method according to an exemplary embodiment will be described in more detail below with reference to Figures 1 and 2A to 2C. Figure 1 is a flowchart showing the pattern formation method according to an exemplary embodiment, and Figures 2A to 2C are side cross-sectional views showing the pattern formation method according to an exemplary embodiment. The following description will specifically explain the case where the resist composition is a positive-type resist composition as an example, but will not be limited to this.

[0132] As shown in Figure 1, the pattern formation method includes the steps of: applying a resist composition onto a substrate to form a resist film (S101); exposing at least a portion of the resist film with high-energy rays (S102); and developing the exposed resist film using a developer (S103). The steps can be omitted as needed, and the order in which they are performed can also be changed.

[0133] First, prepare the substrate 100. The substrate 100 can be a semiconductor substrate such as a silicon substrate or a germanium substrate, or it can be glass, quartz, ceramic, copper, etc. In some embodiments, the substrate 100 may also contain a III-V compound such as GaP, GaAs, or GaSb.

[0134] A resist composition can be applied to the substrate 100 to a desired thickness, specifically by a coating method, to form a resist film 110. If necessary, post-application bake (PAB) can be performed to remove any remaining organic solvent from the resist film 110.

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

[0136] The lower limit of the PAB temperature is 60°C or higher, specifically 80°C or higher. The upper limit of the PAB temperature is 150°C or lower, specifically 140°C or lower. The lower limit of the PAB duration is 5 seconds or higher, specifically 10 seconds or higher. The upper limit of the PAB duration is 600 seconds or lower, specifically 300 seconds or lower.

[0137] Before applying the resist composition to the substrate 100, an etchable film (not shown) may be further formed on the substrate 100. The etchable film refers to a layer on which an image is transferred from the resist pattern and converted into a predetermined pattern. In one embodiment, the etchable film may be formed to contain an insulating material such as silicon oxide, silicon nitride, or silicon oxynitride. In some embodiments, the etchable film may be formed to contain a conductive material such as metal, metal nitride, metal silicide, or metal silicide nitride. In some embodiments, the etchable film may be formed to contain a semiconductor material such as polysilicon.

[0138] In one embodiment, an anti-reflective film may be further formed on the substrate 100 to maximize the efficiency of the resist. The anti-reflective film is an organic or inorganic anti-reflective film.

[0139] In one embodiment, a protective film may be further provided on the resist film 110 to reduce the influence of alkaline impurities and other elements contained during the process. Furthermore, when performing immersion lithography, a protective film for immersion lithography may be placed on the resist film 110, for example, to avoid direct contact between the immersion medium and the resist film 110.

[0140] Next, at least a portion of the resist film 110 can be exposed with high-energy rays. For example, high-energy rays that have passed through the mask 120 are irradiated onto at least a portion of the resist film 110. As a result, the resist film 110 can have exposed portions 111 and unexposed portions 112.

[0141] Although not limited to any particular theory, exposure generates radicals in the exposed area 111, which can change the properties of the resist composition as the polymer's main chain is decomposed.

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

[0143] A variety of light sources can be used for exposure, including those that emit ultraviolet laser light such as KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm); those that convert the wavelength of laser light from solid-state laser sources (such as YAG or semiconductor lasers) 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 drawing without using a mask.

[0144] The cumulative dose of high-energy radiation, for example, when using extreme ultraviolet light as the high-energy radiation, is 2000 mJ / cm². 2 Below, specifically 500 mJ / cm² 2 The following also applies. Furthermore, when using electron beams as high-energy beams, the cumulative dose is 5000 μC / cm². 2 Below, specifically 1000 μC / cm 2 It is also the following.

[0145] Furthermore, 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, the exposed resist film 110 can be developed using a developer.

[0147] Examples of developing solutions include distilled water, alkaline developers, and developers containing organic solvents (hereinafter also referred to as "organic developers"). Examples of developing methods include dipping, paddle, spray, and dynamic dosing. The developing temperature is, for example, 5°C or higher and 60°C or lower, and the developing 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 surfactants.

[0149] The lower limit of the alkaline compound content in the alkaline developer is 0.1% by weight or more, specifically 0.5% by weight or more, and more specifically 1% by weight or more. Furthermore, the upper limit of the alkaline compound content in the alkaline developer is 20% by weight or less, specifically 10% by weight or less, and more specifically 5% by weight or less.

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

[0151] As the organic solvent contained in the organic developer, for example, one similar to the organic solvent exemplified in the <solvent> section of the [resist composition] can be used.

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

[0153] In one embodiment, the developer includes distilled water, an alkaline developer, or any combination thereof, and the exposed area 111 can be removed by the developer.

[0154] The organic developer may contain a surfactant. It may also contain a small amount of water. Furthermore, development can be stopped by substituting the organic developer with a different type of solvent during development.

[0155] The resist pattern can be further cleaned after development. Ultrapure water, rinsing solutions, etc., can be used as cleaning solutions. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern; a general organic solvent solution can be used. For example, the rinsing solution may be an alcohol-based solvent or an ester-based solvent. After cleaning, any remaining rinsing solution on the substrate and pattern can be removed. Furthermore, if ultrapure water is used, any remaining water on the substrate and pattern can be removed.

[0156] Furthermore, the developing solution can be used individually or in combination of two or more types.

[0157] As described above, a patterned wiring substrate is obtained by etching after forming a resist pattern. The etching method is carried out by known methods such as dry etching using plasma gas and wet etching using alkaline solutions, cupric chloride solutions, ferric chloride solutions, etc.

[0158] After forming the resist pattern, plating can also be performed. While not particularly limited, the plating method can include, for example, copper plating, solder plating, nickel plating, or gold plating.

[0159] The residual resist pattern after etching can be removed with an organic solvent. Examples of such organic solvents are not limited, but include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and ethyl lactate (EL). The removal method is not limited, but examples include immersion and spraying. Furthermore, the wiring substrate on which the resist pattern is formed can be a multilayer wiring substrate and may have small-diameter through-holes.

[0160] In one embodiment, the wiring board can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern in a solution, that is, a lift-off method.

[0161] Figures 3A to 3E are cross-sectional side views showing a method of forming a patterning structure according to an embodiment of the present invention.

[0162] As shown in FIG. 3A, before forming the resist film 110 on the substrate 100, a material layer 130 can be formed on the substrate 100. The resist film 110 can 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 is also a multilayer structure. The material of the material layer 130 is different from the material of the substrate 100.

[0163] As shown in FIG. 3B, the resist film 110 is exposed with high-energy rays through the mask 120 after a pre-exposure baking process, and thereafter, the resist film 110 includes an exposed region 111 and an unexposed region 112.

[0164] As shown in FIG. 3C, the exposed resist film 110 is developed using a developer (e.g., a developer). The exposed portion 111 is washed away by the developer, and the unexposed portion 112 remains without being washed away by the developer.

[0165] As shown in FIG. 3D, the exposed portion of the material layer 130 can be etched using the resist pattern 115 as a mask to form a material pattern 135 on the substrate 100.

[0166] As shown in FIG. 3E, the resist pattern 115 can be removed.

[0167] Figures 4A to 4E are cross-sectional side views showing a method of forming a semiconductor device according to an embodiment.

[0168] As shown in FIG. 4A, a gate dielectric 505 (e.g., silicon oxide) is formed on a substrate 500. The substrate 500 is also 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.

[0169] As shown in FIG. 4B, a resist pattern 540b can be formed on the hard mask layer 520. The resist pattern 540b is formed using a resist composition according to an embodiment of the present invention. The resist composition may include an organic solvent.

[0170] As shown in FIG. 4C, the gate layer 515 and the gate dielectric 505 can be etched to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a.

[0171] As shown in FIG. 4D, a spacer layer can be formed on the gate electrode pattern 515a and the gate dielectric pattern 505a. The spacer layer is formed using a deposition process (e.g., CVD). The spacer layer can be etched to form spacers 535a (e.g., silicon nitride) on the sidewalls of the gate electrode pattern 515a and the gate dielectric pattern 505a. After forming the spacers 535a, ions can be implanted into the substrate 500 to form source / drain impurity regions S / D.

[0172] As shown in FIG. 4E, an interlayer insulating film 560 (e.g., oxide) can be formed on the substrate 500 to cover the gate electrode pattern 515a, the gate dielectric pattern 505a, and the spacers 535a. Next, electrical contact portions 570a, 570b, 570c connected to the gate electrode 515a and the S / D regions are formed in the interlayer insulating film 560. The electrical contact portions 570a, 570b, 570c are formed 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 contact portions 570a, 570b, 570c.

[0173] Figures 4A to 4E show examples of transistor formation, but the present invention is not limited thereto.

[0174] A resist composition according to one embodiment can be used in patterning processes for forming other types of semiconductor devices.

[0175] 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. [Examples]

[0176] Synthesis Example 1: Synthesis of Polymer P-1 [ka]

[0177] Monomer M-1 (1.62 g, 10.0 mmol), V601 (0.5 mmol), monomer M-2 (1.20 g, 10.0 mmol), and 1,4-dioxane (0.7 g) were placed in a vial and the reaction was carried out at 60°C for 20 hours under a nitrogen atmosphere. After the reaction was complete, the polymer P-1 (1.14 g, yield 41%) was synthesized by precipitation using n-hexane. The synthesized polymer was 1 Analysis was performed via 1H-NMR and gel permeation chromatography (GPC). 1 H-NMR analysis ratio M-1:M-2=45:55, GPC analysis Mw: 6.2k, PDI: 1.37)

[0178] Synthesis Examples 2-5: Synthesis of Polymers P-2-P-4 and X-1

[0179] Polymers P-2 to P-4 and X-1 were synthesized using the same method as in Synthesis Example 1, except that the monomers listed in Table 2 below were used in the input ratios shown in Table 2 below, instead of monomers M-1 and M-2 below.

[0180] [Table 2]

Chem.

[0181] Evaluation Example 1: Thin Film Development Evaluation (1) Terms Here, after measuring the thickness of the resist film before and after development respectively, the ratio (normalized remaining thickness: NRT) was plotted against the dose to obtain a contrast curve, and then E0, E1 and γ were obtained.

[0182] NRT = (thickness after development) / (thickness before development)

[0183] Here, E0 means the exposure dose at the point where the resist film is completely developed (the thickness of the resist film does not decrease any further), and E1 means the exposure dose at the point where the resist film starts to be developed. γ is the sensitivity and is the value calculated by the following formula 1.

[0184]

Math.

[0185] (2) EUV thin film development evaluation Polymer P-1 was dissolved in a propylene glycol methyl ether acetate (PGMEA) solvent at a concentration of 2 wt% to prepare a resist solution. The solution was spin-coated on an 8-inch silicon wafer treated with HMDS at a speed of 1500 rpm, and then heated at 120 °C for 60 seconds to form a resist film with a thickness of 40 nm. Then, EUV exposure was performed using an EUVES-9000 equipment manufactured by LTJ (Litho Tech Japan). The exposure area was 1 × 1 cm 2 and exposure was performed at 18 points within a dose range of 0 - 80 mJ / cm[[ID=​​​​The results are shown in Figure 5 and Table 3 below.

[0187] [Table 3]

[0188] As shown in Table 3, polymer P-1 exhibits improved contrast (γ) characteristics compared to polymer X-1.

[0189] (3) E-beam thin film development evaluation 1 A resist solution was prepared by dissolving polymer P-1 in propylene glycol methyl ether acetate (PGMEA) solvent at a concentration of 2 wt%. The solution was spin-coated onto an HMDS-treated 8-inch silicon wafer at a speed of 1500 rpm, and then heated at 120°C for 60 seconds to form a 40 nm thick resist film. Subsequently, E-beam exposure was performed using a JEOL JBX-8100FS system. The exposure area was 30 × 30 μm. 2 It is 10-700 μC / cm². 2 Exposure was performed at 35 points within the specified dose range, and no further PEB (photo-etched beam) was performed afterward. Subsequently, development was carried out for 30 seconds using pentyl acetate or hexyl acetate as the developer. The results are shown in Figure 6 and Table 4 below.

[0190] Similarly, polymers P-2, P-3, and X-1 were developed in the same manner as polymer P-1, except that the developer shown in Table 4 below was used, and the results are shown in Table 4 below.

[0191] [Table 4]

[0192] As shown in Table 4, polymers P-1, P-2, and P-3 were confirmed to have improved contrast characteristics (γ) compared to polymer X-1. Furthermore, it was confirmed that they showed even greater sensitivity when pentyl acetate was used as the developer. Polymer P-1 is propylene glyco

[0193] (4) E-beam thin film development evaluation 2 A resist solution was prepared by dissolving the resist in methyl ether acetate (PGMEA) solvent at a concentration of 2 wt%. The solution was spin-coated onto an HMDS-treated 8-inch silicon wafer at a speed of 1500 rpm, and then heated at 120°C for 60 seconds to form a 40 nm thick resist film. Next, E-beam exposure was performed using a JEOL JBX-8100FS system. Line and space (LS) patterns were exposed with the intensity doses listed in Table 5 below, and no further PEB was performed. Then, the wafers were developed for 30 seconds with the developer listed in Table 5 below. The widths of multiple LS patterns and the spacing between them were measured using a Hitachi CG4000, and the critical dimension (CD) was calculated. The results are shown in Figures 7A to 7C and Table 5 below.

[0194] [Table 5]

[0195] As shown in Table 5, polymers P-1 and P-2 can form a more uniform pattern compared to polymer X-1.

Claims

1. A polymer containing a first repeating unit represented by the following chemical formula 1. 【Chemistry 1】 In the aforementioned chemical formula 1, L １１ and L １２ each independently represents a single bond, O, S, C(=O), C(=O)O, OC(=O), C(=O)NR １１ , NR １１ C(=O), S(=O), S(=O) ２ , S(=O) ２ O, OS(=O) ２ , or a substituted or unsubstituted C １ -C ３０ linear, branched or cyclic divalent hydrocarbon group containing heteroatoms selectively, a11 and a12 are each independent integers between 1 and 4. X １１ C is either substituted or non-substituted. ６ -C ３０ Aryl group or substituted or unsubstituted C １ -C ３０ It is a heteroaryl group, X １２ is CN, C(=O)R １２ , C (=O) OR １２ , C(=O)SR １２ , or C(=O)NR １２ R １３ And, R １１ ~R １３ Each of these independently contains a substituted or unsubstituted C that selectively contains hydrogen, deuterium, or a heteroatom. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group. * indicates a bonding site with an adjacent atom.

2. L １１ and L １２ These are, independently, single bonds: 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 , substitution or non-substitution of 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 Arylene group, or substituted or unsubstituted C １ -C ３０ The polymer according to claim 1, wherein the group is a heteroarylene group.

3. X １１ This includes deuterium, halogens, cyano groups, hydroxyl groups, amino groups, carboxylic acid groups, thiol groups, ester molecules, sulfonic acid ester molecules, carbonate molecules, carbamate molecules, lactone molecules, sultone molecules, carboxylic acid anhydride molecules, C １ -C ２０ alkyl group, C １ -C ２０ Alkyl halogenated compounds, C １ -C ２０ Alkoxy group, C ３ -C ２０ Cycloalkyl groups, C ３ -C ２０ Cycloalkoxy group, C ６ -C ２０ A C that is substituted or unsubstituted with an aryl group, or any combination thereof. ６ -C ２０ Aryl group and C １ -C ２０ The polymer according to claim 1, selected from heteroaryl groups.

4. X １１ Deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, thiol group, C １ -C ２０ alkyl group, C １ -C ２０ Alkyl halogenated compounds, C １ -C ２０ Alkoxy group, C ３ -C ２０ Cycloalkyl groups, C ３ -C ２０ Cycloalkoxy group, C ６ -C ２０ A C that is substituted or unsubstituted with an aryl group, or any combination thereof. ６ -C ２０ Aryl group and C １ -C ２０ The polymer according to claim 1, selected from heteroaryl groups.

5. X １２ The polymer according to claim 1, which is represented by any one of the following chemical formulas 4-1 to 4-4. 【Chemistry (4-1)-(4-4)】 In the aforementioned chemical formulas 4-1 to 4-4, R １２ and R １３ Each of these is defined similarly to the definition in Chemical Formula 1 above, * indicates a bonding site with an adjacent atom.

6. R １１ ~R １３ are each independently hydrogen; deuterium; 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 group, or a C １ -C ２０ alkyl group, C ３ -C ２０ cycloalkyl group, and C ６ -C ２０ aryl group; selected from, the polymer according to claim 1.

7. The polymer according to claim 1, wherein the first repeating unit is selected from the following group I. 【Chemistry (Group I)】 【change】 In group I, * represents a bonding site with an adjacent atom.

8. The polymer according to claim 1, further comprising a second repeating unit represented by the following chemical formula 2. 【Chemistry 2】 In the aforementioned chemical formula 2, L ２１ and L ２２ These are, independently, single bonds, 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 substituted or unsubstituted C selectively containing heteroatoms １ -C ３０ It is a linear, branched, or cyclic divalent hydrocarbon group. a21 and a22 are each independent integers between 1 and 4. X ２１ It is an electron-withdrawing group, X ２２ is CN, C(=O)R ２２ , C (=O) OR ２２ , C(=O)SR ２２ , or C(=O)NR ２２ R ２３ And, R ２１ ~R ２３ Each of these independently contains a substituted or unsubstituted C that selectively contains hydrogen, deuterium, or a heteroatom. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group. * indicates a bonding site with an adjacent atom.

9. X ２１ is halogen; cyano group; halogen, cyano group, C １ -C ２０ C substituted with halogenated alkyl groups, or any combination thereof. １ -C ３０ alkyl group, C ３ -C ３０ Cycloalkyl groups, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkenyl group, C ２ -C ３０ Alkynyl group, C ６ -C ３０ Aryl group, and C ７ -C ３０ Arylalkyl groups; and OSO ２ R ｘ Selected from, R ｘ C is either substituted or non-substituted. １ -C １０ Alkyl alkyl group or substituted or unsubstituted C ６ -C １０ The polymer according to claim 8, wherein the group is an aryl group.

10. X ２１ is halogen; cyano group; halogen, cyano group, C １ -C ２０ C substituted with halogenated alkyl groups, or any combination thereof. １ -C ２０ Alkyl and C ６ -C ２０ Aryl group; and OSO ２ R ｘ Selected from, R ｘ C is either substituted or non-substituted. １ -C １０ Alkyl alkyl group or substituted or unsubstituted C ６ -C １０ The polymer according to claim 8, wherein the group is an aryl group.

11. X ２２ The polymer according to claim 8, wherein is represented by any one of the following chemical formulas 5-1 to 5-4. 【Chemistry (5-1)-(5-4)】 In the aforementioned chemical formulas 5-1 to 5-4, R ２２ and R ２３ The definitions of each are the same as those in chemical formula 2 above, * indicates a bonding site with an adjacent atom.

12. The polymer according to claim 8, wherein the second repeating unit is selected from the following group II. 【Chemistry (Group II)】 【change】 In the aforementioned group II, OMs is OSO ２ CH ３ And OTf is OSO ２ CF ３ And OTs is OSO ２ C ６ H ４ (CH ３ ) and * indicates a bonding site with an adjacent atom.

13. A resist composition comprising the polymer and solvent according to any one of claims 1 to 12.

14. The resist composition according to claim 13, wherein the resist composition does not contain any compounds with a molecular weight of 1,000 or more other than the polymer.

15. The resist composition according to claim 13, wherein the resist composition substantially does not contain a photoacid generator.

16. The resist composition according to claim 13, wherein the resist composition does not contain an organometallic compound.

17. The steps include: applying the resist composition according to claim 13 onto a substrate to form a resist film; A step of exposing at least a portion of the resist film with a high-energy beam, A pattern formation method comprising the step of developing an exposed resist film using a developer.

18. The pattern forming method according to claim 17, wherein the exposure step is performed by irradiating with ultraviolet light, far ultraviolet light (DUV), extreme ultraviolet light (EUV), X-rays, gamma rays, electron beams (EB) and / or alpha rays.

19. The pattern forming method according to claim 17, wherein the main chain of the polymer is decomposed by the exposure.

20. The exposed resist film includes an exposed portion and an unexposed portion. The pattern forming method according to claim 17, wherein the exposed portion is removed during the developing step.

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