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

Abstract

The present invention provides a polymer, a resist composition containing the same, and a method for forming a pattern using the same. [Solution] A polymer comprising a first chain containing a first repeating unit of a specific structure having an acid-unstable group in its side chain, a second chain containing a second repeating unit of a specific structure having an acid-unstable group in its side chain, and a crosslinking unit represented by the following chemical formula 9 that connects the first chain and the second chain, a resist composition comprising the same, and a pattern formation method using the same. TIFF2026066973000048.tif35159

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 project] [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 of 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 chain containing a first repeating unit represented by the following chemical formula 1, a second chain containing a second repeating unit represented by the following chemical formula 2, and a crosslinking unit represented by the following chemical formula 9 that connects the first chain and the second chain. [Chemical formula]

[0006] [Chemical formula] [Chemical formula] In the chemical formulas 1, 2, and 9, 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)2O; OS(=O)2; or a C1-C 30 linear, branched or cyclic divalent hydrocarbon group optionally containing heteroatoms; and L 21 ~L 23 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 22 ; NR 22 C(=O); S(=O); S(=O)2O; OS(=O)2; or a C1-C 30 linear, branched or cyclic divalent hydrocarbon group optionally containing heteroatoms; and a11 to a13 and a21 to a23 are each independently an integer from 1 to 4, R 11 R 12 R 21 and R 22 are each independently hydrogen; deuterium; halogen; cyano group; hydroxy group; amino group; carboxylic acid group; thiol group; ester moiety; sulfonate ester moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic anhydride moiety; or a C1-C 30 linear, branched or cyclic monovalent hydrocarbon group optionally containing heteroatoms; and X 11 and X 21These are, independently, acid-labile groups; L 91 and L 92 Each of these C1-C atoms may independently contain a single bond or selectively contain a heteroatom. 30 A linear, branched, or cyclic divalent hydrocarbon group; a91 and a92 are each independent integers between 1 and 4. R 91 ~R 94 Each of these C1-C atoms may independently and selectively contain heteroatoms. 30 It is a linear, branched, or cyclic monovalent hydrocarbon group, R 91 and R 92 , or R 93 and R 94 They can selectively bond to each other to form a ring, X 91 C1-C may selectively contain heteroatoms. 30 It is a linear, branched, or cyclic divalent hydrocarbon group. c91 is an integer from 1 to 4. * indicates a bonding site with an adjacent atom.

[0007] A resist composition according to another aspect of the present invention made to achieve the above objective comprises the aforementioned polymer, photoacid generator, and solvent.

[0008] A pattern-forming method according to yet another aspect of the present invention, made to achieve the above objective, includes the steps of: applying the aforementioned resist composition to form a resist film; exposing at least a portion of the resist film with high-energy rays; and developing the exposed resist film using a developer. [Effects of the Invention]

[0009] According to the present invention, a resist composition having improved sensitivity and / or resolution can be provided. [Brief explanation of the drawing]

[0010] [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 5A] This diagram shows the change in film thickness after development using DUV doses for polymer HS / ECPMA, E-HS / ECPMA2, ​​and E-HS / ECPMA4. [Figure 5B]This figure shows the change in film thickness after development by EUV dose for polymer HS / ECPMA, E-HS / ECPMA2, ​​and E-HS / ECPMA4. [Figure 6] This figure shows the results of gel permeation chromatography analysis of polymer HS / ECPMA and E-HS / ECPMA2 after exposure. [Modes for carrying out the invention]

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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) Includes groups such as tetracyclododecanylmethyl and dicyclohexylmethyl groups; monounsaturated aliphatic hydrocarbon groups (alkenyl and alkynyl groups) (e.g., allyl group); monounsaturated cyclic aliphatic hydrocarbon groups (cycloalkenyl groups) (e.g., 3-cyclohexenyl); aryl groups (e.g., phenyl, 1-naphthyl, and 2-naphthyl groups); arylalkyl groups (e.g., benzyl and diphenylmethyl groups); heteroatom-containing monovalent hydrocarbon groups (e.g., tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl groups), 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.

[0018] 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.

[0019] 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.

[0020] 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. Here, the halogen is F, Cl, Br, or I.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] In this specification, "heteroarylalkyl group" means a group in which an alkyl group is substituted with a monovalent group having a heterocyclic aromatic system.

[0043] 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.

[0044] 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 20A heteroaryloxy group, or a C1-C 20 heteroarylthio group; Deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, 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 heteroarylthio group, or a C1-C substituted with any combination thereof 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, 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 20A heteroaryloxy group, and C1-C 20 a heteroarylthio group; or any combination thereof.

[0045] 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 assigned 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 thickness of some layers and regions is exaggerated. On the other hand, the embodiments described below are merely exemplary, and various modifications are possible from such embodiments.

[0046] [Polymer] The polymer according to a specific embodiment includes a first chain including a first repeating unit represented by the following Chemical Formula 1, a second chain including a second repeating unit represented by the following Chemical Formula 2, and a crosslinking unit represented by the following Chemical Formula 9 that links the first chain and the second chain.

[0047] [Chemical formula]

[0048] [Chemical formula]

[0049] [Chemical formula] <000068l> In Chemical Formulas 1, 2, and 9, 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)2O; OS(=O)2; or a C1-C that may selectively contain a heteroatom 30A linear, branched, or cyclic divalent hydrocarbon group; L 21 ~L 23 These are all independent single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 22 ;NR 22 C1-C may selectively contain C(=O);S(=O);S(=O)2O;OS(=O)2; or heteroatoms. 30 A linear, branched, or cyclic divalent hydrocarbon group; a11~a13 and a21~a23 are each independent integers between 1 and 4. R 11 , R 12 , R 21 and R 22 Each of these independently includes hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester moisture; sulfonic acid ester moisture; carbonate moisture; lactone moisture; sultone moisture; carboxylic acid anhydride moisture; or C1-C which may selectively contain heteroatoms 30 A linear, branched, or cyclic monovalent hydrocarbon group; X 11 and X 21 These are, independently, acid-labile groups. L 91 and L 92 Each of these may independently contain a single bond; or a C1-C which may selectively contain a heteroatom. 30 A linear, branched, or cyclic divalent hydrocarbon group; a91 and a92 are each independent integers between 1 and 4. R 91 ~R 94 Each of these C1-C atoms may independently and selectively contain heteroatoms. 30 It is a linear, branched, or cyclic monovalent hydrocarbon group, R 91 and R 92 , or R 93 and R 94They can selectively bond to each other to form a ring, X 91 C1-C may selectively contain heteroatoms. 30 It is a linear, branched, or cyclic divalent hydrocarbon group. c91 is an integer from 1 to 4. * indicates a bonding site with an adjacent atom.

[0051] For example, in chemical formulas 1 and 2, L 11 ~L 13 and L 21 ~L 23 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)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 group, substituted or unsubstituted C2-C 30 Alkenylene group, substituted or unsubstituted C3-C 30 Cycloalkenylene group, substituted or unsubstituted C3-C 30 Heterocycloalkenylene group, substituted or unsubstituted C6-C 30 Arylene group, or substituted or unsubstituted C1-C 30 It is a heteroarylene group.

[0052] Specifically, in chemical formulas 1 and 2, L 11 ~L 13 and L 21 ~L 23 These are, independently, single bonds; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); 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 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 A heteroarylene group is selected from the following.

[0053] More specifically, in chemical formulas 1 and 2, L 11 ~L 13 and L 21 ~L 23 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 to a13 are L 11 ~L 13 This refers to the number of repetitions.

[0055] In chemical formula 2, a21 to a23 are L 21 ~L 23This refers to the number of repetitions.

[0056] For example, in chemical formulas 1 and 2, a11 to a13 and a21 to a23 are each independent integers between 1 and 3.

[0057] Specifically, in chemical formulas 1 and 2, a11-a13 and a21-a23 are each independently equal to 1.

[0058] For example, in chemical formulas 1 and 2, R 11 and R 21 These are, independently, hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; 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.

[0059] Specifically, in chemical formulas 1 and 2, R 11 and R 21 These are, independently, hydrogen; deuterium; halogen; cyano group; and C1-C substituted or unsubstituted with deuterium, halogen, cyano group, or any combination thereof. 20 Selected from alkyl groups.

[0060] More specifically, in chemical formulas 1 and 2, R 11and R 21 These are, independently, 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.

[0061] For example, in chemical formulas 1 and 2, R 12 and R 22 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 halogens, C3-C 20 Cycloalkyl groups, or C6-C 20 It is an aryl group.

[0062] In this specification, an acid-unstable group refers to a group that is removed from the polymer by an acid to generate a polar group, and which acts to make the polymer more easily soluble in a developer, such as an aqueous TMAH solution.

[0063] For example, the acid dissociation constant (pKa) of the acid-unstable group is 13 or less, specifically between 3 and 13, and more specifically between 5 and 10 (calculated value).

[0064] Specifically, in chemical formulas 1 and 2, X 11 and X 21 Each of these independently comprises a group having a tertiary acyclic alkyl carbon, a group having a tertiary alicyclic carbon, or an acetal.

[0065] More specifically, in chemical formulas 1 and 2, X 11 and X 21 Each of these can be independently represented by one of the following chemical formulas 6-1 to 6-12.

[0066] [ka]

[0067] In chemical formulas 6-1 to 6-12, X 61 These are ester moieties, sulfonate moieties, carbonate moieties, or carbamate moieties. a61 is selected from integers between 0 and 6. R 61 and R 68 Each of these C1-C atoms may independently and selectively contain heteroatoms. 20 It is a linear, branched, or cyclic monovalent hydrocarbon group. R 62 ~R 67 Each of these independently includes hydrogen; 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; or C1-C which may selectively contain heteroatoms 30 A linear, branched, or cyclic monovalent hydrocarbon group; R 61 ~R 68 Two adjacent groups can selectively bond to each other to form a ring. b64 is selected from integers between 1 and 10. * indicates a bonding site with an adjacent atom.

[0068] For example, in chemical formulas 6-1 to 6-12, X 61 It is either ester moiety or carbonate moiety.

[0069] In particular, in chemical formulas 1 and 2, X 11 and X 21 Each of these can be independently represented by one of the following chemical formulas 6-21 to 6-46.

[0070] [ka]

[0071] In chemical formulas 6-21 to 6-46, * indicates a bonding site with an adjacent atom.

[0072] In one embodiment, the first repeating unit and the second repeating unit may be independently selected from the following group I.

[0073] [ka] TIFF2026066973000010.tif192152TIFF2026066973000011.tif240154

[0074] For example, in chemical formula 9, L 91 and L 92 Each of these is independently a single bond, substituted, or unsubstituted C1-C bond. 30 Alkylene group, substituted or unsubstituted C3-C 30 Cycloalkylene group, substituted or unsubstituted C3-C 30 Heterocycloalkylene group, substituted or unsubstituted C2-C 30 Alkenylene group, substituted or unsubstituted C3-C 30 Cycloalkenylene group, substituted or unsubstituted C3-C 30 Heterocycloalkenylene group, substituted or unsubstituted C6-C 30 Arylene group, or substituted or unsubstituted C1-C 30 It is a heteroarylene group.

[0075] Specifically, in chemical formula 9, L 91 and L 92 Each of these is independently a single bond, or a substituted or unsubstituted C1-C bond. 30 It is an alkylene group.

[0076] In chemical formula 9, a91 and a92 are L 91and L 92 This refers to the number of repetitions.

[0077] For example, in chemical formula 9, a91 and a92 are each independently equal to 1.

[0078] For example, in chemical formula 9, R 91 ~R 94 These are, independently, deuterium, a hydroxyl group, and a 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 alkyl group, C1-C 20 Alkoxy group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, and C6-C 20 Selected from aryl groups.

[0079] Specifically, in chemical formula 9, R 91 ~R 94 These are, independently, deuterium, a hydroxyl group, and a 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 It is an alkyl group.

[0080] For example, in chemical formula 9, X 91 These are deuterium, halogen, cyano group, nitro group, hydroxyl group, amino group, carboxylic acid group, thiol group, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C20 A C1-C group that is substituted or unsubstituted with an alkoxy group, or any combination thereof. 20 Alkylene group, C3-C 20 Cycloalkylene group, C2-C 20 Alkenylene group, C3-C 20 Cycloalkenylene group, and C6-C 20 Selected from arylene groups.

[0081] Specifically, in chemical formula 9, X 91 These are deuterium, halogen, cyano group, nitro group, hydroxyl group, amino group, carboxylic acid group, thiol group, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 A C3-C group that is substituted or unsubstituted with an alkoxy group, or any combination thereof. 20 Cycloalkylene group and C6-C 20 Selected from arylene groups.

[0082] For example, in chemical formula 9, c91 is 1.

[0083] In one embodiment, the crosslinking unit may be selected from the following group III.

[0084] [ka]

[0085] Any hydrogen atom in the first chain and any hydrogen atom in the second chain can each be linked to the cross-linking unit * represented by chemical formula 9. Specifically, the X of the first chain 11 One of the hydrogens and the X of the second chain 21 Any one of these hydrogen atoms can be linked to the * in the bridging unit represented by chemical formula 9.

[0086] In one embodiment, the polymer may include a substructure represented by the following chemical formula 11.

[0087] [ka]

[0088] In chemical formula 11, L 11 ~L 13 a11~a13 and R 11 The explanations for each are the same as those for chemical formula 1. L 21 ~L 23 a21~a23 and R 21 The explanations for each are the same as those for chemical formula 2. L 91 , L 92 a91, a92, X 91 , c91 and R 91 ~R 94 The explanations for each are the same as those for chemical formula 9. X 11a and X 21a These are each divalent acid-unstable groups.

[0089] Since the crosslinking units contain ester bonds, they can be chemically more stable than polymers that contain other acid-unstable groups, such as acetal bonds, in their crosslinking units. This makes it possible to form patterns using resist compositions containing the polymer with sufficient stability.

[0090] In one embodiment, the polymer contains 0.1 to 50 parts by weight, specifically 1 to 40 parts by weight, and more specifically 5 to 40 parts by weight, of crosslinking units based on 100 parts by weight of the polymer. If the crosslinking units are present in the above-mentioned range, a resist composition with improved resolution can be provided while satisfying appropriate coating properties.

[0091] In one embodiment, i) the first chain further comprises a third repeating unit represented by the following chemical formula 3, ii) The second chain further contains a fourth repeating unit represented by the following chemical formula 4, or iii) The first chain further comprises a third repeating unit represented by the following chemical formula 3, and the second chain further comprises a fourth repeating unit represented by the following chemical formula 4.

[0092] [ka]

[0093] [ka]

[0094] In chemical formulas 3 and 4, L 31 ~L 33 These are all independent single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 32 ;NR 32 C1-C may selectively contain C(=O);S(=O);S(=O)2O;OS(=O)2; or heteroatoms. 30 A linear, branched, or cyclic divalent hydrocarbon group; L 41 ~L 43 These are all independent single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 42 ;NR 42 C1-C may selectively contain C(=O);S(=O);S(=O)2O;OS(=O)2; or heteroatoms. 30 A linear, branched, or cyclic divalent hydrocarbon group; a31~a33 and a41~a43 are each independent integers between 1 and 4. R 31 , R 32 , R 41 and R 42 Each of these C1-C atoms may independently contain, selectively, hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester molecule; sulfonic acid ester molecule; carbonate molecule; lactone molecule; sultone molecule; carboxylic acid anhydride molecule; or heteroatoms.30 a linear, branched or cyclic monovalent hydrocarbon group; and X 31 and X 41 are each independently a non-acid labile group, * is a bonding site with an adjacent atom.

[0095] For example, when the first chain further includes a third repeating unit, any one hydrogen of the third repeating unit is linked to the * of the crosslinking unit represented by Chemical Formula 9. Specifically, any one hydrogen of X 31 in the first chain and any one hydrogen of X 21 in the second chain are each linked to the * of the crosslinking unit represented by Chemical Formula 9.

[0096] For example, when the second chain further includes a fourth repeating unit, any one hydrogen of the fourth repeating unit is linked to the * of the crosslinking unit represented by Chemical Formula 9. Specifically, any one hydrogen of X 11 in the first chain and any one hydrogen of X 41 in the second chain are each linked to the * of the crosslinking unit represented by Chemical Formula 9.

[0097] For example, when the first chain further includes a third repeating unit and the second chain further includes a fourth repeating unit, any one hydrogen of the third repeating unit and any one hydrogen of the fourth repeating unit are each linked to the * of the crosslinking unit represented by Chemical Formula 9. Specifically, any one hydrogen of X 31 in the first chain and any one hydrogen of X 41 in the second chain are each linked to the * of the crosslinking unit represented by Chemical Formula 9.

[0098] In one embodiment, the polymer may include a partial structure represented by the following Chemical Formula 12.

[0099]

Chemical Formula

[0100] In Chemical Formula 12, L 31 ~L 33 , a31 to a33 and R 31 The descriptions related to them are the same as the descriptions in Chemical Formula 3 respectively, L<000​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ X 41a It is a divalent non-acidic unstable group, * indicates a bonding site with an adjacent atom.

[0104] In one embodiment, the polymer may include a substructure represented by the following chemical formula 14.

[0105] [ka]

[0106] In chemical formula 14, L 31 ~L 33 a31~a33 and R 31 The explanations for each are the same as those for chemical formula 3. L 41 ~L 43 a41~a43 and R 41 The explanations for each are the same as those for chemical formula 4. L 91 , L 92 a91, a92, X 91 , c91 and R 91 ~R 94 The explanations for each are the same as those for chemical formula 9. X 31a and X 41a These are each divalent non-acidic unstable groups, * indicates a bonding site with an adjacent atom.

[0107] Specifically, the polymer may contain a substructure represented by the following chemical formula 14-1.

[0108] [ka]

[0109] In chemical formula 14-1, L 31 ~L 33 a31~a33 and R 31The descriptions related thereto are the same as those in Chemical Formula 3, L 41 ~L 43 、a41~a43 and R 41 The descriptions related thereto are the same as those in Chemical Formula 4, L 91 、L 92 、a91, a92, X 91 、c91 and R 91 ~R 94 The descriptions related thereto are the same as those in Chemical Formula 9, R 33 and R 43 are each independently a bonding site with an adjacent atom; hydrogen; deuterium; halogen; cyano group; hydroxy group; amino group; carboxylic acid group; thiol group; carbonyl moiety; ester moiety; sulfonate moiety; carbonate moiety; carbamate moiety; lactone moiety; sultone moiety; carboxylic anhydride moiety; or a C1-C 30 linear, branched or cyclic monovalent hydrocarbon group optionally containing heteroatoms; and b33 and b43 are each independently an integer from 1 to 4, * is a bonding site with an adjacent atom.

[0110] In Chemical Formulas 3 and 4, L 31 ~L 33 and L 41 ~L 43 The descriptions related thereto are the same as those of L in Chemical Formula 1 11 The descriptions related thereto.

[0111] In Chemical Formulas 3 and 4, the descriptions related to a31~a33 and a41~a43 are the same as those related to a11 in Chemical Formula 1.

[0112] In Chemical Formulas 3 and 4, R 31 and R4 The descriptions related thereto are the same as those of R in Chemical Formula 1 11 The descriptions related thereto.

[0113] In Chemical Formulas 3 and 4, R 32 and R42 The explanation for this is R in chemical formula 1. 12 This is the same as the explanation related to [the relevant topic].

[0114] For example, in chemical formulas 3 and 4, X 31 and X 41 Each C1-C may independently contain one or more polar molecules selected from hydrogen; halogens; cyano groups; hydroxyl groups; carboxylic acid groups; thiol groups; amino groups; or halogens, cyano groups, hydroxyl groups, carboxylic acid groups, thiol groups, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), lactone molecules, sultone molecules, and carboxylic acid anhydride molecules. 30 A linear, branched, or cyclic monovalent hydrocarbon group;

[0115] Specifically, in chemical formulas 3 and 4, X 31 and X 41 Each of these is independently selected from hydrogen, a hydroxyl group, and a group represented by the following chemical formulas 5-1 to 5-16.

[0116] [ka]

[0117] In chemical formulas 5-1 to 5-16, a51 is either 1 or 2. R 51 ~R 56 Each of these C1-C atoms may independently contain a bonding site with an adjacent atom; hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; carbonyl moiety; ester moiety; sulfonate moiety; carbonate moiety; carbamate moiety; lactone moiety; sultone moiety; carboxylic acid anhydride moiety; or a heteroatom. 30 A linear, branched, or cyclic monovalent hydrocarbon group; R 51 ~R 53 One of them, R 54one of the following, and R 55 and R 56 One of these is a bonding site with an adjacent atom. b51 is selected from integers between 1 and 4. b52 is selected from integers between 1 and 10. b53 is selected from integers between 1 and 8. b54 is selected from integers between 1 and 5. b55 is selected from integers between 1 and 7. b56 is selected from integers between 1 and 11. b57 is selected from integers between 1 and 13. b58 is selected from integers between 1 and 15. b59 is selected from integers between 1 and 2. m51 is selected from integers between 1 and 4.

[0118] More specifically, in chemical formulas 3 and 4, X 31 and X 41 Each of these is independently selected from a hydroxyl group and chemical formulas 5-11.

[0119] In one embodiment, the third repeating unit and the fourth repeating unit may be independently selected from the following group II.

[0120] [ka]

[0121] In one embodiment, the first chain of the polymer contains 1 to 100 mol%, specifically 5 to 100 mol%, and particularly 10 to 100 mol%, of the first repeating units.

[0122] In one embodiment, the second chain of the polymer contains 1 to 100 mol%, specifically 5 to 100 mol%, and particularly 10 to 100 mol%, of the second repeating units.

[0123] In one embodiment, the first chain of the polymer contains 0 to 99 mol%, specifically 1 to 99 mol%, and more specifically 10 to 90 mol%, of third repeating units.

[0124] In one embodiment, the second chain of the polymer contains 0 to 99 mol%, specifically 1 to 99 mol%, and more specifically 10 to 90 mol%, of third repeating units.

[0125] In one embodiment, the first chain of the polymer consists of a first repeating unit and a third repeating unit. For example, the first chain of the polymer contains 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 third repeating unit.

[0126] In one embodiment, the second chain of the polymer consists of a second repeating unit and a fourth repeating unit. For example, the second chain of the polymer contains 1 to 99 mol%, specifically 10 to 90 mol%, of the second repeating unit and 1 to 99 mol%, specifically 10 to 90 mol%, of the fourth repeating unit.

[0127] 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.

[0128] The polydispersity index (PDI: Mw / Mn) of the polymer is between 1.0 and 3.0, specifically between 1.0 and 2.5. 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.

[0129] Furthermore, since the polymer has acid-unstable groups in its side chains, the side chains are decomposed by the acid generated from the photoacid generator, which increases its solubility in developing solutions, especially basic developing solutions that do not use organic solvents.

[0130] Since the molecular weight of a polymer increases through crosslinking units, the solubility of the unexposed areas in the developer is relatively reduced compared to polymers without crosslinking. As a result, the exposed areas of the polymer dissolve sufficiently in the developer, while the unexposed areas have improved resistance to dissolution in the developer, thus improving the resolution of the polymer.

[0131] The polymer has relatively high resistance to oxygen and / or moisture, a relatively high Tg (e.g., Tg above 80°C), and its physical properties change only when exposed to high-energy rays, thus providing a resist composition with improved storage stability, process stability, and other properties.

[0132] The polymer is produced by any suitable method, for example, by dissolving an unsaturated bond-containing monomer in an organic solvent and then thermally polymerizing it under a radical initiator.

[0133] 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.

[0134] [Resist composition] In other respects, a resist composition comprising the aforementioned polymer, photoacid generator, and organic solvent is provided. The resist composition may have properties such as improved developability and / or improved resolution.

[0135] 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.

[0136] Furthermore, the resist composition according to one embodiment may be for an alkaline development process that uses an alkaline developer for the development treatment during resist pattern formation, 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 treatment. In particular, the resist composition according to one embodiment is for an alkaline development process.

[0137] 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.

[0138] 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.

[0139] Furthermore, the polymer used in the resist composition may be a single type, or two or more different types may be used in combination.

[0140] As the polymer is as described above, the following will explain the photoacid generator, organic solvent, and any optional components such as quenchers that may be included as needed.

[0141] <Photoacid Generator> A photoacid generator is any compound that generates acid upon exposure to high-energy rays, such as UV, DUV, EB, EUV, X-rays, alpha rays, gamma rays, etc.

[0142] The photoacid generator includes sulfonium salts, iodonium salts, and combinations thereof.

[0143] In one embodiment, the photoacid generator is represented by the following chemical formula 7.

[0144] [7] B 71+ A 71 -

[0145] In the above chemical formula 7, B 71 + It is represented by the following chemical formula 7A, A 71 - It is represented by one of the following chemical formulas 7B to 7D: B 71 + and A 71 - They are selectively linked through carbon-carbon covalent bonds, [ka] In the above chemical formulas 7A to 7D, L 71 ~L 73 Each of these is independently a single bond or a CRR', R and R' are independently hydrogen, deuterium, halogen, cyano group, hydroxyl group, and C1-C 30 Alkyl alkyl group, C1-C 30 Alkyl halogens, C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl groups, or C3-C 30 It is a cycloalkoxy group, n71~n73 are each independently 1, 2, or 3. x71 and x72 are independently either 0 or 1. R 71 ~R 73 Each of these C1-C atoms may independently and selectively contain heteroatoms. 30 It is a linear, branched, or cyclic monovalent hydrocarbon group. R 71 ~R 73 Two adjacent rings can selectively bond to each other to form a fused ring. R 74 ~R 76 Each of these C1-C atoms may independently and selectively contain hydrogen, halogens, or heteroatoms. 30A linear, branched, or cyclic monovalent hydrocarbon group;

[0146] For example, in chemical formula 7, B 71 + It is represented by the chemical formula 7A, A 71 - It is represented by chemical formula 7B. Specifically, in chemical formula 7A, R 71 ~R 73 These are each phenyl groups.

[0147] The photoacid generator is included in amounts of 0.01 to 40 parts by weight, 0.1 to 40 parts by weight, or 0.1 to 20 parts by weight per 100 parts by weight of polymer. If the above ranges are satisfied, appropriate resolution can be achieved and problems related to foreign particles after development or during stripping can be reduced.

[0148] The photoacid generator may be of one type, or two or more different types may be mixed and used.

[0149] <Solvent> The solvent included in the resist composition is not particularly limited, as long as it is capable of dissolving or dispersing the polymer, photoacid generator, and any optional components such as quenchers, if necessary.

[0150] The solvent may be a single type, or a combination of two or more different types may be used.

[0151] The solvent may be an organic solvent, or a mixed solvent consisting of water and an organic solvent.

[0152] 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.

[0153] 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, 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.

[0154] Examples of ether-based 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] Examples of sulfoxide solvents include dimethyl sulfoxide and diethyl sulfoxide.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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. <Quencher>

[0163] The resist composition may further contain a quencher.

[0164] Quenchers are salts that produce acids that are less acidic than the acids produced by photoacid generators.

[0165] Quenchers include ammonium salts, sulfonium salts, iodonium salts, and combinations thereof.

[0166] In one embodiment, the quencher is represented by the following chemical formula 8.

[0167] [8] B 81 + A 81 -

[0168] In chemical formula 8, B 81 + It is represented by one of the following chemical formulas 8A to 8C, A 81 - It is represented by one of the following chemical formulas 8D to 8F: B 81 + and A 81 - They are selectively linked through carbon-carbon covalent bonds, [ka] In chemical formulas 8A to 8F, L 81 and L 82 Each of these is independently a single bond or a CRR', R and R' are independently hydrogen, deuterium, halogen, cyano group, hydroxyl group, and C1-C 30 Alkyl alkyl group, C1-C 30 Alkyl halogens, C1-C 30 Alkoxy group, C3-C 30 Cycloalkyl groups, or C3-C 30 It is a cycloalkoxy group, n81 and n82 are independently 1, 2, or 3. x81 is either 0 or 1. R 81 ~R 84 Each of these C1-C atoms may independently and selectively contain heteroatoms. 30 It is a linear, branched, or cyclic monovalent hydrocarbon group. R 81 ~R 84 Two adjacent rings can selectively bond to each other to form a fused ring. R 85 and R 86 C1-C may selectively contain hydrogen; halogens; or heteroatoms. 30 A linear, branched, or cyclic monovalent hydrocarbon group;

[0169] 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 per 100 parts by weight of polymer. If the aforementioned ranges are satisfied, appropriate resolution can be achieved and problems associated with foreign particles after development or during stripping can be reduced.

[0170] Quencher may be used as a single type, or a mixture of two or more different types may be used.

[0171] <Optional ingredients> The resist composition may further contain, as needed, surfactants, crosslinking agents, leveling agents, colorants, or any combination thereof.

[0172] 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.).

[0173] The surfactant is present in an amount of 0 to 20 parts by weight per 100 parts by weight of polymer.

[0174] A single surfactant may be used, or two or more different surfactants may be used in combination.

[0175] The method for producing the resist composition is not particularly limited, and for example, a method can be used in which an amine compound, a polymer, a photoacid generator, and any optional components added as needed are mixed in an organic solvent. The temperature and time during mixing are not particularly limited. Filtration can be performed after mixing as needed.

[0176] [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.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] Although not limited to any particular theory, the physical properties of the resist composition may change as the main chain of the polymer in the exposed area 111 is decomposed by the acid generated by exposure.

[0187] 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 a surface with these high-energy rays is collectively referred to as "exposure."

[0188] 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.

[0189] 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.

[0190] 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.

[0191] Next, the exposed resist film 110 can be developed using a developer. The exposed areas 111 are washed away by the developer, while the unexposed areas 112 remain unwashed by the developer.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] After development, the resist pattern 115 can be washed with ultrapure water, and then any remaining water on the substrate and pattern can be removed.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] The resist pattern 115 can be further cleaned after development. Ultrapure water, a rinsing solution, etc., can be used as the cleaning solution. 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.

[0200] Furthermore, the developing solution can be used individually or in combination of two or more types.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] In one embodiment, the wiring substrate can also be formed by a method in which a resist pattern is formed, a metal is deposited in a vacuum, and then the resist pattern is dissolved in a solution, i.e., the lift-off method.

[0205] Figures 3A to 3E are side cross-sectional views illustrating a method for forming a patterned structure according to one embodiment of the present invention.

[0206] As shown in Figure 3A, a material layer 130 can be formed on the substrate 100 before forming the resist film 110 on the substrate 100. The resist film 110 may be formed on top of the material layer 130. The material layer 130 may contain insulating materials (e.g., silicon oxide, silicon nitride), semiconductor materials (e.g., silicon), or metals (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.

[0207] As shown in Figure 3B, the resist film 110 undergoes a pre-exposure baking process and is exposed to high-energy rays through the mask 120. Thereafter, the resist film 110 includes an exposed region 111 and an unexposed region 112.

[0208] As shown in Figure 3C, the exposed resist film 110 is developed using a developer (for example, a developer). The exposed areas 111 are washed away by the developer, while the unexposed areas 112 remain unwashed by the developer.

[0209] As shown in Figure 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.

[0210] As shown in Figure 3E, the resist pattern 115 can be removed.

[0211] Figures 4A to 4E are side cross-sectional views showing a method for forming a semiconductor device according to one embodiment.

[0212] As shown in Figure 4A, a gate dielectric 505 (e.g., silicon oxide) is formed on the 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.

[0213] As shown in Figure 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 contain an organic solvent.

[0214] As shown in Figure 4C, the gate layer 515 and the gate dielectric 505 can be etched to form the hard mask pattern 520a, the gate electrode pattern 515a, and the gate dielectric pattern 505a.

[0215] As shown in Figure 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 vapor deposition process (e.g., CVD). The spacer layer can be etched to form a spacer 535a (e.g., silicon nitride) on the sidewalls of the gate electrode pattern 515a and the gate dielectric pattern 505a. After forming the spacer 535a, ions can be implanted into the substrate 500 to form a source / drain impurity region S / D.

[0216] As shown in Figure 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 spacer 535a. Then, electrical contact portions 570a, 570b, and 570c are formed in the interlayer insulating film 560, which are connected to the gate electrode 515a and the S / D region. The electrical contact portions 570a, 570b, and 570c are formed of a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewall of the interlayer insulating film 560 and the electrical contact portions 570a, 570b, and 570c.

[0217] Figures 4A to 4E show examples of transistor formation, but the present invention is not limited thereto.

[0218] A resist composition according to one embodiment can be used in patterning processes for forming other types of semiconductor devices.

[0219] 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]

[0220] Comparative Synthesis Example 1: Synthesis of Polymer HS / ECPMA [ka]

[0221] Acetoxystyrene (AHS) (1.5 g, 9.3 mmol), 2-ethyl-2-cyclopentyl methacrylate (ECPMA) (1.7 g, 9.3 mmol), and V601 (0.2 g, 0.9 mmol) were dissolved in 18 mL of dioxane and reacted at 80°C for 4 hours. Hydrazine monohydrate (1 g) was added to the reaction mixture and the mixture was reacted further at room temperature for 2 hours. After adding 50 mL of distilled water and 2 g of acetic acid, the mixture was extracted with ethyl acetate, the solvent was removed from the collected organic layer, and precipitation was performed again using hexane. The resulting solid was dried at 40°C for 24 hours to obtain polymer HS / ECPMA (molar ratio = 50 / 50) with Mw: 5,056 g / mol and PDI: 1.3.

[0222] Synthesis Example 1: Synthesis of Polymer E-HS / ECPMA1 [ka]

[0223] The polymer HS / ECPMA obtained in Comparative Synthesis Example 1 and DCA were dissolved in DMF in a weight ratio of 1:0.05. Sodium carbonate was then added to the mixture at a molar ratio of 10 times that of the DCA. The reaction was then allowed to proceed for 24 hours. After the reaction, the mixture was precipitated in water, extracted with ethyl acetate, the solvent was removed from the collected organic layer, and precipitation was performed again using hexane. The resulting solid was dried at 40°C for 24 hours to obtain polymer E-HS / ECPMA1.

[0224] Synthesis Examples 2 to 4: Synthesis of Polymer E-HS / ECPMA2 to Polymer E-HS / ECPMA4 Polymers E-HS / ECPMA2, ​​E-HS / ECPMA3, and E-HS / ECPMA4 were synthesized using the same method as in Synthesis Example 1, except that DCA was used in the weight ratio shown in Table 1 below.

[0225] [Table 1]

[0226] In Table 1 above, -OH blocking (%) represents the percentage of each polymer. 1 This value was calculated from the percentage of peaks corresponding to "OH" in the 1H-NMR data. As shown in Table 1, it was confirmed that as the amount of DCA added during the reaction increases, it reacts more with the -OH of hydroxystyrene, and the -OH blocking (%) increases.

[0227] Comparative Synthesis Example 2: Synthesis of Polymer X To synthesize polymer X, in which the ester group in the linker of polymer E-HS / ECPMA1 is replaced with an acetal group, HS / ECPMA and 1,4-cyclohexanedimethanol divinyl ether were dissolved in dimethylformamide (DMF) in a weight ratio of 1:0.05, and the reaction was carried out at 130°C. After about 1 hour, gelation occurred, and the final polymer X could not be obtained. Since polymer X could not be obtained, thin film development evaluation and other procedures could not be performed. [ka]

[0228] Evaluation Example 1: Thin Film Development Evaluation In a casting solvent with a PGME / PGMEA ratio of 7 / 3 (wt / wt), the polymers HS / ECPMA, E-HS / ECPMA2, ​​and E-HS / ECPMA4 synthesized in Comparative Synthesis Examples 1, 2, and 4 were dissolved to a concentration of 1.6 wt% each. Then, 0.024 mmol of PAG and 0.016 mmol of PDQ were added. The casting solution was spin-coated onto an HMDS-treated silicon wafer at a speed of 1500 rpm, and the film was prepared by drying at 110°C for 1 minute (PAB). Subsequently, 0-50 mJ / cm² of 248 nm wavelength DUV or 13.5 nm wavelength EUV was applied. 2 The film was exposed to a specific dose, post-exposure baking was performed at 90°C for 60 seconds, immersed in a 2.38 wt% TMAH aqueous solution at 25°C for 20 seconds, washed with DI (deionized) water for 10 seconds, removed and dried the portion exposed to high-energy rays, and the remaining film thickness was measured using a film thickness analyzer (Filmetrics®, F-20), as shown in Figures 5A and 5B. Figure 5A shows the DUV results, and Figure 5B shows the EUV results.

[0229] [ka]

[0230] From this, we were able to confirm that the polymers E-HS / ECPMA2 and E-HS / ECPMA4 undergo a change in solubility similar to that of HS / ECPMA when exposed to DUV or EUV.

[0231] Evaluation Example 2: Evaluation of Molecular Weight Change The polymers synthesized in Comparative Synthesis Example 1 and Synthesis Example 2 were dissolved in a casting solvent with a PGME / PGMEA ratio of 7 / 3 (wt / wt) to a concentration of 1.6 wt%, and then 0.024 mmol of PAG and 0.016 mmol of PDQ were added. EUV light at a wavelength of 13.5 nm was then applied at a rate of 0-50 mJ / cm². 2After exposure with the specified dose, gel permeation chromatography (GPC) analysis was performed, and the molecular weight changes are shown in Figure 6.

[0232] As shown in Figure 6, it can be confirmed that the molecular weight of polymer HS / ECPMA decreases due to the elimination of acid-unstable groups, and polymer E-HS / ECPMA2 has a molecular weight of 10 mJ / cm³. 2 After changing to the molecular weight level of HS / ECPMA with a given dose, we were able to confirm that the molecular weight ultimately decreased due to the elimination of the acid-unstable group.

[0233] Evaluation Example 3: Solubility evaluation in developer The polymers synthesized in Comparative Synthesis Example 1, Synthesis Example 2, and 4 were dissolved in a casting solvent of PGME / PGMEA = 7 / 3 (wt / wt) to a concentration of 1.6 wt%, and then 0.024 mmol of PAG and 0.016 mmol of PDQ were added. The casting solution was spin-coated onto an HMDS-treated silicon wafer at a speed of 1500 rpm, and then dried at 110°C for 1 minute (PAB) to produce a film. Subsequently, 248 nm wavelength DUV or 13.5 nm wavelength EUV was applied at 0-50 mJ / cm². 2 The thin film was prepared by exposing it with a dose of [specified amount] and performing a post-exposure bake at 90°C for 60 seconds.

[0234] Subsequently, the thin films were supported in a 2.38 wt% TMAH solution for intervals of 20 seconds, 40 seconds, and 60 seconds, respectively. The gradient obtained from the graph of the change in the thickness of the thin films with respect to the support time was then examined to derive Rmin.

[0235] Furthermore, thin films were supported in a 0.00238 wt% TMAH solution at intervals of 10 seconds, 20 seconds, and 30 seconds, respectively. Rmax was derived by examining the gradient obtained from the graph of the change in the thickness of the thin film with respect to the support time. Here, Rmin represents the dissolution rate in the unexposed area, and Rmax represents the dissolution rate after exposure.

[0236] Subsequently, Rmin and Rmax obtained from E-HS / ECPMA2 and E-HS / ECPMA4 were calculated as relative values ​​to Rmin and Rmax obtained from polymer HS / ECPMA, respectively, and are shown in Table 2 below as R.Rmin and R.Rmax.

[0237] [Table 2]

[0238] As shown in Table 2, polymers E-HS / ECPMA2 and E-HS / ECPMA4, whose molecular weight increased through crosslinking, showed significantly lower solubility in the developer in the unexposed region compared to polymer HS / ECPMA, while showing significantly increased solubility in the developer in the exposed region. This suggests that polymers E-HS / ECPMA2 and E-HS / ECPMA4 can exhibit significantly improved resolution compared to polymer HS / ECPMA.

Claims

1. A first chain containing a first repeating unit represented by the following chemical formula 1, The second chain contains a second repeating unit represented by the chemical formula 2 below, A polymer comprising a crosslinking unit represented by the following chemical formula 9, which connects the first chain and the second chain. 【Chemistry 1】 【Chemistry 2】 【Chemistry 9】 In the aforementioned chemical formulas 1, 2, and 9, L １１ ~L １３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR １２ NR １２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; L ２１ ~L ２３ each independently represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ２２ ; NR ２２ C(=O); S(=O); S(=O) ２ O; OS(=O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; a11 to a13 and a21 to a23 are each independent integers from 1 to 4. R １１ , R １２ , R ２１ and R ２２ Each of these independently includes hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester moisture; sulfonic acid ester moisture; carbonate moisture; lactone moisture; sultone moisture; carboxylic acid anhydride moisture; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group; X １１ and X ２１ These are, independently, acid-unstable groups. L ９１ and L ９２ Each of these may independently contain a single bond; or selectively contain a heteroatom. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; a91 and a92 are each independent integers between 1 and 4. R ９１ ~R ９４ Each of these C elements may independently selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group, R ９１ and R ９２ , or R ９３ and R ９４ They can selectively bond to each other to form a ring, X ９１ C may selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic divalent hydrocarbon group. c91 is an integer from 1 to 4, * indicates a bonding site with an adjacent atom.

2. R １１ and R ２１ These are, independently, hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; 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, 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 Aryl group, or In any combination of these, C １ -C ２０ alkyl group, C ３ -C ２０ Cycloalkyl groups, and C ６ -C ２０ Selected from: aryl group; R １２ and R ２２ These are, independently, hydrogen, deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, thiol group, and C １ -C ２０ alkyl group, C １ -C ２０ Alkyl halogenated compounds, C ３ -C ２０ Cycloalkyl groups, or C ６ -C ２０ It is an aryl group, X １１ and X ２１ The polymer according to claim 1, wherein each of these is independently represented by one of the following chemical formulas 6-1 to 6-12. 【Chemistry (6-1)-(6-12)】 In the aforementioned chemical formulas 6-1 to 6-12, X ６１ These are ester moieties, sulfonate moieties, carbonate moieties, or carbamate moieties. a61 is selected from integers between 0 and 6. R ６１ and R ６８ Each of these C elements may independently selectively contain heteroatoms. １ -C ２０ It is a linear, branched, or cyclic monovalent hydrocarbon group. R ６２ ~R ６７ Each of these independently includes hydrogen; 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; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group; R ６１ ~R ６８ Two adjacent groups can selectively bond to each other to form a ring. b64 is selected from integers between 1 and 10. * indicates a bonding site with an adjacent atom.

3. The polymer according to claim 1, wherein the first repeating unit and the second repeating unit are each independently selected from the following group I. 【GroupI】 【change】 【change】

4. L ９１ and L ９２ are each independently a single bond, a substituted or unsubstituted C １ -C ３０ alkylene group, a substituted or unsubstituted C ３ -C ３０ cycloalkylene group, a substituted or unsubstituted C ３ -C ３０ heterocycloalkylene group, a substituted or unsubstituted C ２ -C ３０ alkenylene group, a substituted or unsubstituted C ３ -C ３０ cycloalkenylene group, a substituted or unsubstituted C ３ -C ３０ heterocycloalkenylene group, a substituted or unsubstituted C ６ -C ３０ arylene group, or a substituted or unsubstituted C １ -C ３０ heteroarylene group, and the polymer according to claim 1 is characterized in that.

5. X ９１ Deuterium, halogen, cyano group, nitro 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 C １ -C ２０ Alkylene group, C ３ -C ２０ Cycloalkylene group, C ２ -C ２０ Alkenylene group, C ３ -C ２０ Cycloalkenylene group, and C ６ -C ２０ The polymer according to claim 1, selected from arylene groups.

6. The polymer according to claim 1, wherein c91 is 1.

7. The polymer according to claim 1, wherein the crosslinking units are selected from the following group III. 【Chemical Group III】

8. The polymer according to claim 1, wherein the polymer contains 0.1 to 50 parts by weight of the crosslinking units based on 100 parts by weight of the polymer.

9. i) The first chain further comprises a third repeating unit represented by the following chemical formula 3, ii) The second chain further comprises a fourth repeating unit represented by the following chemical formula 4, or iii) The polymer according to claim 1, wherein the first chain further comprises a third repeating unit represented by the following chemical formula 3, and the second chain further comprises a fourth repeating unit represented by the following chemical formula 4. 【Transformation 3】 【Chemistry 4】 In the aforementioned chemical formulas 3 and 4, L ３１ ~L ３３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ３２ NR ３２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; L ４１ ~L ４３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ４２ NR ４２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; a31 to a33 and a41 to a43 are each independent integers from 1 to 4. R ３１ , R ３２ , R ４１ and R ４２ Each of these independently includes hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester moisture; sulfonic acid ester moisture; carbonate moisture; lactone moisture; sultone moisture; carboxylic acid anhydride moisture; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group; X ３１ and X ４１ These are, independently, non-acid unstable groups. * indicates a bonding site with an adjacent atom.

10. X ３１ and X ４１ Each of these independently consists of hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; or C may selectively contain one or more polar molecules selected from halogens, cyano groups, hydroxyl groups, carboxylic acid groups, thiol groups, O, C=O, C(=O)O, OC(=O), S(=O)O, OS(=O), lactone molecules, sultone molecules, and carboxylic acid anhydride molecules. １ -C ３０ The polymer according to claim 9, wherein the group is a linear, branched, or cyclic monovalent hydrocarbon group.

11. The polymer according to claim 9, characterized in that the third repeating unit and the fourth repeating unit are each independently selected from the following group II. 【Chemical Group II】

12. The polymer according to claim 1, wherein the polymer includes a substructure represented by any one of the following chemical formulas 11 to 14. 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 In the aforementioned chemical formulas 11 to 14, L １１ ~L １３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR １２ NR １２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; L ２１ ~L ２３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ２２ NR ２２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; L ３１ ~L ３３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ３２ NR ３２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; L ４１ ~L ４３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ４２ NR ４２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; a11-a13, a21-a23, a31-a33, and a41-a43 are each independent integers from 1 to 4. R １１ , R １２ , R ２１ , R ２２ , R ３１ , R ３２ , R ４１ and R ４２ Each of these independently includes hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester moisture; sulfonic acid ester moisture; carbonate moisture; lactone moisture; sultone moisture; carboxylic acid anhydride moisture; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group; L ９１ and L ９２ Each is independent, single bonded; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; a91 and a92 are each independent integers between 1 and 4. R ９１ ~R ９４ Each of these C elements may independently selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group, R ９１ and R ９２ , or R ９３ and R ９４ They can selectively bond to each other to form a ring, X ９１ C may selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic divalent hydrocarbon group. c91 is an integer from 1 to 4, X １１ａ and X ２１ａ These are, independently, divalent acid-unstable groups, X ３１ａ and X ４１ａ These are, independently, divalent non-acidic unstable groups, * indicates a bonding site with an adjacent atom.

13. The polymer according to claim 1, wherein the polymer includes a substructure represented by the following chemical formula 14-1. 【Chemistry 14-1】 In the aforementioned chemical formula 14-1, L ３１ ~L ３３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ３２ NR ３２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; L ４１ ~L ４３ These are, independently, single bonds; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR ４２ NR ４２ C(=O);S(=O);S(=O) ２ O; OS (= O) ２ ; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; a31 to a33 and a41 to a43 are each independent integers from 1 to 4. R ３１ , R ３２ , R ４１ and R ４２ Each of these C molecules may independently contain, selectively, hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester molecule; sulfonic acid ester molecule; carbonate molecule; lactone molecule; sultone molecule; carboxylic acid anhydride molecule; or a heteroatom. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group; L ９１ and L ９２ Each is independent, single bonded; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; a91 and a92 are each independent integers between 1 and 4. R ９１ ~R ９４ Each of these C elements may independently selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group, R ９１ and R ９２ , or R ９３ and R ９４ They can selectively bond to each other to form a ring, X ９１ C may selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic divalent hydrocarbon group. c91 is an integer from 1 to 4, R ３３ and R ４３ Each of these independently includes hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; carbonyl moisture; ester moisture; sulfonate moisture; carbonate moisture; carbamate moisture; lactone moisture; sultone moisture; carboxylic acid anhydride moisture; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group; b33 and b43 are each independent integers between 1 and 4. * indicates a bonding site with an adjacent atom.

14. The polymer according to claim 1, Photoacid generator, A resist composition comprising a solvent.

15. The photoacid generator is represented by the following chemical formula 7, the resist composition according to claim 14. [Chem.7] B ７１ ＋ A ７１ － In the aforementioned chemical formula 7, B ７１ ＋ It is represented by the following chemical formula 7A, A ７１ － It is represented by one of the following chemical formulas 7B to 7D: B ７１ ＋ and A ７１ － They are selectively linked through carbon-carbon covalent bonds, 【Chemistry 7A-7D】 In the above chemical formulas 7A to 7D, L ７１ ~L ７３ Each of these is independently a single bond or a CRR', R and R' are independently hydrogen, deuterium, halogen, cyano group, hydroxyl group, and C １ -C ３０ alkyl group, C １ -C ３０ Alkyl halogenated compounds, C １ -C ３０ Alkoxy group, C ３ -C ３０ Cycloalkyl groups, or C ３ -C ３０ It is a cycloalkoxy group, n71 to n73 are each independently 1, 2, or 3. x71 and x72 are independently either 0 or 1. R ７１ ~R ７３ Each of these C elements may independently selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group. R ７１ ~R ７３ Two adjacent rings can selectively bond to each other to form a fused ring. R ７４ ~R ７６ These are, independently, hydrogen; halogen; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group;

16. The resist composition according to claim 14, further comprising a quencher.

17. The resist composition according to claim 16, wherein the quencher is represented by the following chemical formula 8. [Chem.8] B ８１ ＋ A ８１ － In the aforementioned chemical formula 8, B ８１ ＋ It is represented by one of the following chemical formulas 8A to 8C, A ８１ － It is represented by one of the following chemical formulas 8D to 8F: B ８１ ＋ and A ８１ － They are selectively linked through carbon-carbon covalent bonds, 【Chemical Engineering 8A-8F】 In the aforementioned chemical formulas 8A to 8F, L ８１ and L ８２ Each of these is independently a single bond or a CRR', R and R' are independently hydrogen, deuterium, halogen, cyano group, hydroxyl group, and C １ -C ３０ alkyl group, C １ -C ３０ Alkyl halogenated compounds, C １ -C ３０ Alkoxy group, C ３ -C ３０ Cycloalkyl groups, or C ３ -C ３０ It is a cycloalkoxy group, n81 and n82 are independently 1, 2, or 3. x81 is either 0 or 1. R ８１ ~R ８４ Each of these C elements may independently selectively contain heteroatoms. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group. R ８１ ~R ８４ Two adjacent rings can selectively bond to each other to form a fused ring. R ８５ and R ８６ is hydrogen; halogen; or C may selectively contain heteroatoms. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group;

18. The steps include: applying the resist composition according to claim 14 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.

19. The pattern forming method according to claim 18, wherein the exposure step is carried out by irradiating with ultraviolet light, far 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 an unexposed portion. The pattern forming method according to claim 18, wherein the exposed portion is removed during the developing step.

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