Organic salt, resist composition containing the same, and pattern formation method using the same

Abstract

The present invention provides an organic salt, a resist composition containing the same, and a pattern formation method using the same. [Solution] An organic salt represented by the following chemical formula 1, a resist composition containing the same, and a pattern formation method using the same. TIFF2026109596000050.tif63140 (A 11 : Heteroatom-containing hydrocarbon group. k11: Integer from 1 to 4. L 11 , L 12 : Single associativity, O, S, etc. a11, a12: Integers from 0 to 4. R 11 :H, D, etc. b11: Integers from 0 to 10. n11: Integers from 1 to 5. M + : Counter-cation.

Description

[Technical Field]

[0001] The present invention relates to an organic salt, 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 problem that the present invention aims to solve is to provide an organic salt, a resist composition containing the same, and a pattern formation method using the same, which can provide improved sensitivity, improved resolution, and / or reduced defects. [Means for solving the problem]

[0005] The organic salt of the present invention is represented by the following chemical formula 1.

[0006] [ka]

[0007] In the above Chemical Formula 1, A 11 is a linear or cyclic hydrocarbon group selectively containing heteroatoms, being a C1-C 30 group, k11 is selected from integers of 1 to 4, L 11 and L 12 each independently represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 12 ; NR 12 C(=O); S(=O); S(=O)2; S(=O)2O; OS(=O)2; or a linear, branched or cyclic divalent hydrocarbon group selectively containing heteroatoms, being a C1-C 30 group; a11 and a12 are each independently selected from integers of 0 to 4, R 11 and R 12 each independently represents hydrogen; deuterium; halogen; cyano group; hydroxy group; or a linear, branched or cyclic monovalent hydrocarbon group selectively containing heteroatoms, being a C1-C 20 group; b11 is selected from integers of 0 to 10, R 11 and two adjacent ones of L 11 and L 12 can selectively bond to each other to form a ring, two adjacent ones of the plurality of R 11 can selectively bond to each other to form a ring, n11 is selected from integers of 1 to 5, M + is a counter cation.

[0008] The resist composition of the present invention contains the above organic salt, photoacid generator, and base resin.

[0009] The pattern formation method of the present invention includes the steps of: applying the resist composition onto a substrate 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]

[0010] Embodiments of the present invention can provide resist compositions having improved sensitivity, improved resolution, and / or reduced defects. [Brief explanation of the drawing]

[0011] [Figure 1] This is a flowchart showing a pattern formation method according to one embodiment of the present invention. [Figure 2A] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 2B] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 2C] This is a side cross-sectional view showing a pattern formation method according to one embodiment of the present invention. [Figure 3A] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3B] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3C] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3D] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 3E] This is a side cross-sectional view showing a method for forming a patterned structure according to one embodiment of the present invention. [Figure 4A] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4B] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4C]This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4D] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Figure 4E] This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment. [Modes for carrying out the invention]

[0012] The present invention can be subjected to various transformations and has many different embodiments. Specific embodiments are illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments; rather, it should be understood that the present invention includes all transformations, equivalents, or substitutes that fall within the spirit and technical scope of the present invention. If a specific description of related prior art in explaining the present invention is deemed to obscure the gist of the invention, such detailed description will be omitted.

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

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

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

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

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

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

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

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

[0021] In this specification, "halogenated alkyl group" means a group in which one or more hydrogen atoms of an alkyl group are substituted with halogens, and specific examples include CF3.

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

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

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

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

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

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

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

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

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

[0031] In this specification, "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, "alkenyloxy group" is defined as -OA 104 This refers to a monovalent group having the chemical formula A 104 This is an alkenyl group.

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

[0034] In this specification, "cycloalkenyloxy group" is defined as -OA 105 This refers to a monovalent group having the chemical formula A 105 This is a cycloalkenyl group.

[0035] 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.

[0036] In this specification, "heterocycloalkenyloxy group" is defined as -OA 106 This refers to a monovalent group having the chemical formula A106 This is a heterocycloalkenyl group.

[0037] 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.

[0038] In this specification, "alkynyloxy group" is defined as -OA 107 This refers to a monovalent group having the chemical formula A 107 This is an alkynyl group.

[0039] 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, and the like.

[0040] In this specification, "aryloxy group" is defined as -OA 108 This refers to a monovalent group having the chemical formula A 108 It is an aryl group.

[0041] 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.

[0042] In this specification, "heteroaryloxy group" is defined as -OA 109 This refers to a monovalent group having the chemical formula A 109 It is a heteroaryl group.

[0043] In this specification, "substituent" means deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether molecule, ester molecule, sulfonate molecule, carbonate molecule, amide molecule, lactone molecule, sultone molecule, carboxylic acid anhydride molecule, C1-C 20Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryl group, C1-C 20 Heteroaryloxy group, or C1-C 20 Heteroarylthio group; deuterium, halogen, hydroxyl group, cyano group, nitro group, carbonyl group, carboxylic acid group, amino group, ether molecule, ester 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 20 Heteroaryloxy group, C1-C 20 C1-C substituted with heteroarylthio groups and any combination thereof. 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20Alkoxy group, C1-C 20 Alkylthio group, C1-C 20 Halide alkoxy group, C1-C 20 Alkylthio halide group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C3-C 20 Cycloalkylthio group, C6-C 20 Aryl group, C6-C 20 Aryloxy group, C6-C 20 Arylthio group, C1-C 20 Heteroaryl group, C1-C 20 Heteroaryloxy group, and C1-C 20 Includes heteroarylthio groups; or any combination thereof.

[0044] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In this description with reference to the drawings, substantially identical or corresponding components will be assigned the same drawing number, and redundant explanations will be omitted. In the drawings, the thickness is shown enlarged to clearly represent multiple layers and regions. Furthermore, in the drawings, the thickness of some layers and regions is exaggerated for the sake of clarity. On the other hand, the embodiments described later are merely illustrative, and various modifications are possible from such embodiments.

[0045] [Organic salt] The organic salt according to the exemplary embodiment is represented by the following chemical formula 1.

[0046] [ka]

[0047] In the above chemical formula 1, A 11 This is a C1-C molecule that selectively contains heteroatoms. 30 It is a linear or cyclic hydrocarbon group, k11 is selected from integers between 1 and 4. L 11 and L 12is, independently of each other, a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 12 ; NR 12 C(=O); S(=O); S(=O)2; S(=O)2O; OS(=O)2; or a C1-C 30 linear, branched or cyclic divalent hydrocarbon group optionally containing a heteroatom; and a11 and a12 are each independently selected from the integers 0 to 4, R 11 and R 12 are each independently hydrogen; deuterium; halogen; cyano group; hydroxy group; or a C1-C 20 linear, branched or cyclic monovalent hydrocarbon group optionally containing a heteroatom; and b11 is selected from the integers 0 to 10, R 11 , L 11 and L 12 two adjacent ones of which can optionally be bonded to each other to form a ring, two adjacent ones of the plurality of R 11 can optionally be bonded to each other to form a ring, n11 is selected from the integers 1 to 5, M + is a counter cation.

[0048] For example, in Chemical Formula 1, A 11 is a C1-C​​​​​​​​​​​​​​​​​​​​​These are methyl group, ethyl group, ethenyl group, cyclopentyl group, cyclohexyl group, tetrahydrofuran group, tetrahydropyran group, norbornyl group, norbornenyl group, norbornadienyl group, tricyclodecanyl group, tetracyclododecanyl group, adamantyl group, oxanorbornyl group, oxatricyclodecanyl group, oxatetracyclododecanyl group, oxadamantyl group, benzene group, naphthalene group, phenanthrene group, anthracene group, pyrrole group, furan group, thiophene group, indole group, benzofuran group, benzothiophene group, carbazole group, dibenzofuran group, or dibenzothiophene group.

[0050] More specifically, in chemical formula 1, A 11 The compound is selected from the following chemical formulas 9-1 to 9-10.

[0051] [ka]

[0052] In the above chemical formulas 9-1 to 9-14, n11 hydrogens are *-(L 12 ) a12 -SH, and one hydrogen is *-(L 11 ) a11 -SO3 - M + That is the case.

[0053] In chemical formula 1, k11 is A 11 (R 11 ) b11 This refers to the number of repetitions.

[0054] For example, in chemical formula 1, k11 is either 1 or 2.

[0055] For example, in chemical formula 1, L 11 and L 12 These are, independently, single bonds; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); and C1-C, either substituted or unsubstituted. 30Alkylene 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, substituted or unsubstituted C1-C 30 A heteroarylene group, or a combination thereof;

[0056] Specifically, in chemical formula 1, L 11 and L 12 Each is independently selected from single bonds; O; C(=O); C(=O)O; OC(=O); and methylene groups, ethylene groups, n-propylene groups, n-butyl groups, iso-butyl groups, phenyl groups, or any combination thereof, substituted or unsubstituted with deuterium, halogens, cyano groups, hydroxyl groups, amino groups, carboxylic acid groups, thiol groups, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, n-butyl groups, iso-butyl groups, sec-butyl groups, tert-butyl groups, methoxy groups, ethoxy groups, cyclopentyl groups, cyclohexyl groups, phenyl groups, or any combination thereof.

[0057] More specifically, in chemical formula 1, L 11 and L 12 These are independent single bonds;O;C(=O);C(=O)O;OC(=O); and [C(R 91 )(R 92 )] n91 ; is one or more selected from, R 91 and R 92 These are, independently, hydrogen, deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, and C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20Alkoxy group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, and C6-C 20 Selected from aryl groups; R 91 and R 92 They can selectively bond to form a ring, n91 is selected from integers between 1 and 3.

[0058] Here, n91 is C(R 91 )(R 92 This refers to the number of repetitions of the action.

[0059] In one embodiment, R 91 and R 92 These are, independently, hydrogen, deuterium, halogen, cyano group, hydroxyl group, and C1-C 20 Alkyl groups, and C1-C 20 It is selected from alkyl halogens, and n91 is selected from integers between 1 and 2.

[0060] a11 and a12 are L 11 and L 12 This refers to the number of repetitions; for example, a11 and a12 are independently 0, 1, or 2.

[0061] For example, in chemical formula 1, R 11 and R 12 These are, independently, hydrogen; deuterium; halogen; cyano group; hydroxyl group; and deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, ester moisture, sulfonate moisture, carbonate 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. 20Alkyl 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.

[0062] Specifically, in chemical formula 1, R 11 and R 12 These are, independently, hydrogen; deuterium; halogen; cyano group; hydroxyl group; and deuterium, halogen, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C3-C 20 Cycloalkyl groups, 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.

[0063] More specifically, in chemical formula 1, R 11 The group is selected from hydrogen, deuterium, halogens, and cyano groups.

[0064] More specifically, in chemical formula 1, R 12 It is hydrogen or deuterium.

[0065] In chemical formula 1, n11 is *-(L 12 ) a12 -This indicates the number of substitutions of SH.

[0066] For example, in chemical formula 1, n11 is either 1 or 2.

[0067] For example, in chemical formula 1, M + It is represented by the following chemical formula 2-1 or 2-2.

[0068] [ka]

[0069] In the above chemical formulas 2-1 and 2-2, R 21 ~R 23 Each of these independently contains a C1-C that selectively contains heteroatoms. 30 It is a linear, branched, or cyclic monovalent hydrocarbon group. R 21 ~R 23 Two adjacent elements can selectively bond to each other to form a ring.

[0070] For example, in chemical formulas 2-1 and 2-2, R 21 ~R 23 These are, independently, deuterium, halogen, cyano group, hydroxyl group, carboxyl group, ester moisture, sulfonate moisture, carbonate moisture, lactone moisture, sultone moisture, carboxylic acid anhydride moisture, and C1-C 20 Alkyl alkyl group, C1-C 30 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.

[0071] Specifically, in chemical formulas 2-1 and 2-2, R 21 ~R 23 Each of these is independently a C1-C molecule substituted or unsubstituted with a halogen, cyano group, hydroxyl group, ester molecule, sulfonate molecule, lactone molecule, sultone molecule, carboxylic acid anhydride molecule, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, halogenated methyl group, halogenated ethyl group, methoxy group, ethoxy group, phenyl group, or any combination thereof. 20 Alkyl, C3-C20 Cycloalkyl groups, and C6-C 20 Selected from aryl groups.

[0072] In one embodiment, R in chemical formula 2-1 21 ~R 23 At least one of the following, and R in chemical formula 2-2 21 and R 22 At least one of them is a C6-C that has been replaced with at least one halogen. 20 It is an aryl group.

[0073] In one embodiment, R in chemical formula 2-1 21 , R 22 or R 23 , and R in chemical formula 2-2 21 or R 22 It contains at least one halogen; R in chemical formula 2-1 21 or R 22 and R in chemical formula 2-2 21 It contains at least one halogen, and R in chemical formula 2-1 23 and R in chemical formula 2-2 22 It does not contain halogens; or R in chemical formula 2-1 21 ~R 23 and R in chemical formula 2-2 21 and R 22 Each contains at least one halogen.

[0074] In another embodiment, R in chemical formula 2-1 21 , R 22 or R 23 , and R in chemical formula 2-2 21 or R 22 It contains one or two halogens;

[0075] R in chemical formula 2-1 21 or R 22 and R in chemical formula 2-2 21 Each contains one or two halogens, and R in chemical formula 2-1 23 and R in chemical formula 2-2 22It does not contain halogens; or R in chemical formula 2-1 21 ~R 23 and R in chemical formula 2-2 21 and R 22 Each contains one or two halogens.

[0076] Specifically, in chemical formula 1, M + It is represented by the following chemical formula 2-11 or 2-12.

[0077] [ka]

[0078] In the above chemical formulas 2-11 and 2-12, R 21a ~R 21e Each of these C1-C atoms independently contains, selectively, hydrogen, deuterium, halogen, cyano group, hydroxyl group, or heteroatom. 20 A linear, branched, or cyclic monovalent hydrocarbon group; R 22 ~R 23 Each of these independently contains a C1-C that selectively contains heteroatoms. 30 It is a linear, branched, or cyclic monovalent hydrocarbon group. R 21a ~R 21e and R 22 ~R 23 Two adjacent elements can selectively bond to each other to form a ring.

[0079] More specifically, in chemical formula 1, M + It can be represented by one of the following chemical formulas 2-21 to 2-23.

[0080] [ka]

[0081] In the above chemical formulas 2-21 to 2-23, R 21a ~R21e , R 22a ~R 22e and R 23a ~R 23e Each of these C1-C atoms independently contains, selectively, hydrogen, deuterium, halogen, cyano group, hydroxyl group, or heteroatom. 20 A linear, branched, or cyclic monovalent hydrocarbon group; R 21a ~R 21e , R 22a ~R 22e and R 23a ~R 23e Two adjacent rings can selectively bond to each other to form a fused ring. b22a and b23a are integers from 1 to 4, A 21 and A 22 Each is either absent or a benzene ring, independently of the others. The bond represented in TIFF2026109596000008.tif6128 is either a carbon-carbon single bond or a carbon-carbon double bond. L 21 These are single bonds, O, S, CO, SO, SO2, CRR', or NR. R and R' each independently contain a C1-C group that selectively contains hydrogen, deuterium, halogen, cyano group, hydroxyl group, or heteroatom. 20 It is a linear, branched, or cyclic monovalent hydrocarbon group.

[0082] In one embodiment, in chemical formula 1, M + It may contain at least one halogen.

[0083] In one embodiment, in chemical formula 1, M + It may contain at least one F or I.

[0084] In one embodiment, in chemical formula 1, M + It can contain one, two, or three I's.

[0085] In one embodiment, in chemical formula 1, M +The following can be selected from Group I.

[0086] [ka] TIFF2026109596000010.tif152170

[0087] In one embodiment, the organic salt represented by chemical formula 1 may be selected from the following group II.

[0088] [ka] TIFF2026109596000012.tif179153

[0089] In Group II, M + It is a counter-cation.

[0090] Typically, EUV (13.5 nm) light sources have a lower photon count compared to ArF immersion light sources. Therefore, as the exposure dose decreases, noise increases significantly in the boundary region between the exposed and unexposed areas. In lithography processes using EUV light sources, a higher concentration of photoacid generator must be used to compensate for this compared to lithography processes using other light sources of the same light intensity. However, if the resist composition contains a high concentration of photoacid generator, the glass transition temperature (Tg) of the base resin changes, reducing thermal stability. In addition, residual photoacid generator during the lithography process using EUV light sources reduces the resolution of the resist pattern formed.

[0091] Organic salts form disulfide bonds via secondary electrons during exposure, which can generate additional acid and thus improve acid efficiency. Furthermore, because organic salts have relatively large negative ion molecular sizes, the acid diffusion distance can be improved. As a result, resist compositions containing organic salts can exhibit properties such as improved developability and / or improved resolution.

[0092] [Resist composition] The resist composition according to the exemplary embodiment comprises the aforementioned organic salt, photoacid generator, and base resin.

[0093] In one embodiment, the organic salt is present in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the base resin. Specifically, the organic salt is present in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the base resin. If the above range is satisfied, an appropriate level of acid is generated, and any performance loss, such as the formation of foreign particles due to reduced uniformity and / or insufficient solubility, can be reduced.

[0094] In one embodiment, the organic salt is present in an amount of 0.01 to 70 parts by weight per 100 parts by weight of the photoacid generator. Specifically, the organic salt is present in an amount of 1 to 60 parts by weight per 100 parts by weight of the photoacid generator. If the above range is satisfied, the uniformity of the pattern is improved and the formation of foreign particles due to insufficient solubility can be reduced.

[0095] 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.

[0096] Furthermore, the resist composition according to one embodiment may use distilled water for the development process during resist pattern formation, and may be used for an alkaline development process using an alkaline developer, or for a solvent development process using a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0097] The following describes the base resin, photoacid generator, organic solvent, and optional components such as quenchers, if necessary.

[0098] <Base resin> The base resin may contain a first repeating unit represented by the following Chemical Formula 3.

[0099] [Chemical formula]

[0100] In Chemical Formula 3 above, L 31 ~L 33 each independently represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 32 ; NR 32 C(=O); S(=O); S(=O)2O; OS(=O)2; or a linear, branched or cyclic divalent hydrocarbon group containing a heteroatom selectively; and 30 a31 to a33 each independently represents an integer of 1 to 4, R R 31 and R 32 each independently represents hydrogen hydrogen hydrogen; deuterium; halogen; cyano group; hydroxy group; amino group; carboxylic acid group; thiol group; ester moiety; sulfonate moiety; carbonate moiety; lactone moiety; sultone moiety; carboxylic anhydride moiety; or a linear, branched or cyclic monovalent hydrocarbon group containing a heteroatom selectively; and 30 X is an acid labile group, 31 * is a bonding site with an adjacent atom. For example, in Chemical Formula 3, L

[0101] ~L 31 ~L 33 each independently represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); S(=O); S(=O)2O; OS(=O)2; a substituted or unsubstituted C1-C 30 alkylene group; a substituted or unsubstituted C3-C 30 cycloalkylene group; a substituted or unsubstituted C3-C30 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.

[0102] Specifically, in chemical formula 3, L 31 ~L 33 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 moiety, sulfonate moiety, carbonate moiety, carbamate moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, 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 Alkylene group, C3-C 20 Cycloalkylene group, C3-C 20 Heterocycloalkylene group, C2-C 20 Alkenylene group, C3-C 20 Cycloalkenylene group, C3-C 20 Heterocycloalkenylene group, C6-C 20 Arylene group, and C1-C 20 Selected from heteroarylene groups.

[0103] More specifically, in chemical formula 3, L 31 ~L 33These 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.

[0104] In chemical formula 3, a31 to a33 are L 31 ~L 33 This refers to the number of repetitions.

[0105] For example, in chemical formula 3, a31 to a33 are each independent integers from 1 to 3.

[0106] Specifically, in chemical formula 3, a31 to a33 are each independently equal to 1.

[0107] For example, in chemical formula 3, R 31 This includes hydrogen; deuterium; halogens; cyano groups; hydroxyl groups; amino groups; carboxylic acid groups; thiol groups; and deuterium, halogens, cyano groups, hydroxyl groups, amino groups, carboxylic acid groups, thiol groups, ester molecules, sulfonate molecules, carbonate molecules, carbamate molecules, lactone molecules, sultone molecules, carboxylic acid anhydride molecules, C1-C 20 Alkyl alkyl group, C1-C 20 Alkyl halogens, C1-C 20 Alkoxy group, C3-C 20 Cycloalkyl groups, C3-C 20 Cycloalkoxy group, C6-C 20 A C1-C group that is substituted or unsubstituted with an aryl group, or any combination thereof. 20 Alkyl, C3-C 20Cycloalkyl groups, and C6-C 20 Selected from aryl groups.

[0108] Specifically, in chemical formula 3, R 31 C1-C1 is a compound substituted or unsubstituted with hydrogen; deuterium; halogen; cyano group; and deuterium, halogen, cyano group, or any combination thereof. 20 Selected from alkyl groups.

[0109] More specifically, in chemical formula 3, R 31 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.

[0110] For example, in chemical formula 3, R 32 These are hydrogen, deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, thiol group, 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.

[0111] 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.

[0112] 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).

[0113] For example, in chemical formula 3, X 31This includes a group having a tertiary acyclic alkyl carbon, a group having a tertiary alicyclic carbon, or an acetal.

[0114] Specifically, in chemical formula 3, X 31 It can be represented by one of the following chemical formulas 6-1 to 6-12.

[0115] [ka]

[0116] In the above 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 independently contains a C1-C that selectively contains heteroatoms. 20 It is a linear, branched, or cyclic monovalent hydrocarbon group. R 62 ~R 67 Each of these independently contains hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester moisture; sulfonate moisture; carbonate moisture; carbamate moisture; lactone moisture; sultone moisture; carboxylic acid anhydride moisture; or a C1-C molecule selectively containing a heteroatom. 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.

[0117] For example, in chemical formulas 6-1 to 6-12, X 61 It is either ester moiety or carbonate moiety.

[0118] More specifically, in Chemical Formula 3, X 31 is represented by any one of the following Chemical Formulas 6-21 to 6-46.

[0119] [Chemical Formula]

[0120] In the above Chemical Formulas 6-21 to 6-46, * is a bonding site with an adjacent atom. In one embodiment, the first repeating unit can be selected from the following Group III.

[0121] [Chemical Formula] TIFF2026109596000017.tif205164TIFF2026109596000018.tif245156TIFF2026109596000019.tif245159

[0122] In one embodiment, the base resin may further contain a second repeating unit represented by the following Chemical Formula 4.

[0123] [Chemical Formula]

[0124] In the above Chemical Formula 4, L 41 ~L 43 are each independently a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR 42 ; NR 42 C(=O); S(=O); S(=O)2O; OS(=O)2; or a linear, branched or cyclic divalent hydrocarbon group selectively containing a heteroatom; and 30 a41 to a43 are each independently an integer from 1 to 4, and R 41and R 42 Each of these independently contains hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester molecule; sulfonate molecule; carbonate molecule; lactone molecule; sultone molecule; carboxylic acid anhydride molecule; or a C1-C molecule selectively containing a heteroatom. 30 A linear, branched, or cyclic monovalent hydrocarbon group; X 41 It is a non-acid labile group, * indicates a bonding site with an adjacent atom.

[0125] L in chemical formula 4 41 ~L 43 The explanation for this is that L in chemical formula 3 31 This is the same as the explanation related to [the relevant topic].

[0126] The explanation for a41 to a43 in chemical formula 4 is the same as the explanation for a31 in chemical formula 3.

[0127] R in chemical formula 4 41 The explanation for this is that R in chemical formula 3 31 This is the same as the explanation related to [the relevant topic].

[0128] R in chemical formula 4 42 The explanation for this is that R in chemical formula 3 32 This is the same as the explanation related to [the relevant topic].

[0129] For example, in chemical formula 4, X 41 C1-C selectively contains one or more polar molecules selected from hydrogen; deuterium; halogens; cyano groups; hydroxyl groups; amino groups; carboxylic acid groups; thiol 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;

[0130] Specifically, in chemical formula 4, X 41 The group is selected from hydrogen, a hydroxyl group, and a group represented by the following chemical formulas 5-1 to 5-16.

[0131] [ka]

[0132] In the above chemical formulas 5-1 to 5-16, a51 is either 1 or 2. R 51 ~R 56 Each of these is independently 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 C1-C selectively containing a heteroatom. 30 A linear, branched, or cyclic monovalent hydrocarbon group; R 51 ~R 53 One of them, R 54 one 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. b55 is selected from integers between 1 and 7. b54 is selected from integers between 1 and 5. 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.

[0133] More specifically, in chemical formula 4, X41 The group is selected from a hydroxyl group and chemical formulas 5-11.

[0134] In one embodiment, the second repeating unit may be selected from the following group IV.

[0135] [ka]

[0136] In one embodiment, the base resin contains 1 to 100 mol%, specifically 5 to 100 mol%, and particularly 10 to 100 mol%, of the first repeating units.

[0137] For example, the base resin may consist of a first repeating unit.

[0138] In other embodiments, the base resin contains 0 to 99 mol%, specifically 1 to 99 mol%, and more specifically 10 to 90 mol%, of the second repeating units.

[0139] In other embodiments, the base resin may consist of a first repeating unit and a second repeating unit. For example, the base resin may contain 1 to 99 mol%, specifically 10 to 90 mol%, of the first repeating unit and 1 to 99 mol%, specifically 10 to 90 mol%, of the second repeating unit.

[0140] The base resin has a weight-average molecular weight (Mw) of 1,000 to 500,000, specifically 3,000 to 100,000, and more specifically 5,000 to 50,000, as measured by gel permeation chromatography using tetrahydrofuran solvent and polystyrene as standard substances.

[0141] The polydispersity index (PDI: Mw / Mn) of the base resin is 1.0 to 3.0, specifically 1.0 to 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.

[0142] The base resin may be one type, or two or more different types may be mixed and used.

[0143] <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.

[0144] The photoacid generator includes sulfonium salts, iodonium salts, and combinations thereof.

[0145] In one embodiment, the photoacid generator is represented by the following chemical formula 7.

[0146] [7] B 71 + A 71 - ...chemical formula 7

[0147] In 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,

[0148] [ka]

[0149] 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 30Alkyl 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 independently contains a C1-C that selectively contains 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 independently contains a C1-C atom selectively containing hydrogen, halogen, or heteroatom. 30 A linear, branched, or cyclic monovalent hydrocarbon group;

[0150] 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.

[0151] 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. Satisfying the aforementioned ranges ensures adequate resolution and reduces problems associated with foreign particles after development or during stripping.

[0152] The photoacid generator may be of one type, or two or more different types may be mixed and used.

[0153] <Quencher> The resist composition may further contain a quencher.

[0154] Quenchers are salts that produce acids that are less acidic than the acids produced by photoacid generators.

[0155] Quenchers include ammonium salts, sulfonium salts, iodonium salts, and combinations thereof.

[0156] In one embodiment, the quencher is represented by the following chemical formula 8.

[0157] [8] B 81 + A 81 - ...chemical formula 8

[0158] In the above 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,

[0159] [ka]

[0160] In the above 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 independently contains a C1-C that selectively contains 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 selectively containing hydrogen; halogen; or heteroatoms 30 A linear, branched, or cyclic monovalent hydrocarbon group;

[0161] 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 above ranges are satisfied, appropriate resolution can be achieved and problems related to foreign particles after development or during stripping can be reduced.

[0162] Quencher may be used as a single type, or a mixture of two or more different types may be used.

[0163] <organic solvents> The organic solvent included in the resist composition is not particularly limited, as long as it can dissolve or disperse any optional components such as organic salts, base resins, photoacid generators, and quenchers, if any. One organic solvent may be used, or two or more different organic solvents may be used in combination. A mixed solvent of water and an organic solvent may also be used.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] Examples of ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-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 silacetate, methylcyclohexylacetate, and n-nonylacetate; 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 Examples include polyhydric alcohol-containing ether carboxylate solvents such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone and δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; lactate ester solvents such as methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate; glycol diacetate, 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.

[0170] Examples of sulfoxide solvents include dimethyl sulfoxide and diethyl sulfoxide.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] The organic solvent is used in an amount of 200 to 20,000 parts by weight, specifically 2,000 to 10,000 parts by weight, per 100 parts by weight of the base resin.

[0175] <Optional ingredients> The resist composition may further contain, as needed, surfactants, crosslinking agents, leveling agents, colorants, or any combination thereof.

[0176] The resist composition may further contain surfactants to improve coating properties, developability, and other characteristics. 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.).

[0177] The surfactant is present in an amount of 0 to 20 parts by weight per 100 parts by weight of polymer.

[0178] A single surfactant may be used, or two or more different surfactants may be used in combination.

[0179] 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.

[0180] [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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] While not limited to any specific theory, exposure causes the additives to react with each other, forming disulfide bonds and further generating acids. Therefore, it is possible to create patterns of improved quality using the same or even smaller amounts of photoacid generator.

[0191] In some cases, this exposure is performed by irradiating a surface with high-energy rays through a mask having a predetermined pattern, using a liquid such as water as a medium. Examples of high-energy rays include electromagnetic waves such as ultraviolet rays, far ultraviolet rays (DUV), extreme ultraviolet rays (EUV, wavelength 13.5 nm), X-rays, and gamma rays; and charged particle beams such as electron beams (EB) and alpha rays. The process of irradiating with these high-energy rays is collectively referred to as "exposure."

[0192] 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.

[0193] 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.

[0194] 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.

[0195] Next, the exposed resist film 110 can be developed using a developer to form a resist pattern 115. In this process, the exposed areas 111 are washed away and removed by the developer, while the unexposed areas 112 remain without being washed away by the developer.

[0196] 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.

[0197] 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 also contain surfactants.

[0198] 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.

[0199] After development, the resist pattern can be washed with ultrapure water, and then any remaining water on the substrate and pattern can be removed.

[0200] As the organic solvent contained in the organic developer, for example, one similar to the organic solvent exemplified in the <organic solvent> section of the [resist composition] can be used.

[0201] Specifically, organic developers such as nBA (n-butyl acetate), PGME, PGMEA, ethyl lactate, GBL (γ-butyrolactone), and IPA (isopropanol) can be used. The organic developer may also contain organic acids such as acetic acid, formic acid, and citric acid.

[0202] 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.

[0203] In one embodiment, the developer includes distilled water, an alkaline developer, or any combination thereof, and the exposed area 111 is removed by the developer.

[0204] 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.

[0205] The resist pattern can be further cleaned after development. Ultrapure water, rinsing solutions, etc., can be used as cleaning solutions. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern; a general organic solvent solution can be used. For example, the rinsing solution may be an alcohol-based solvent or an ester-based solvent. After cleaning, any remaining rinsing solution on the substrate and pattern can be removed. Furthermore, if ultrapure water is used, any remaining water on the substrate and pattern can be removed.

[0206] Furthermore, the developing solution can be used individually or in combination of two or more types.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] As shown in Figure 3A, a material layer 130 can be formed on the substrate 100 before the resist film 110 is formed 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.

[0213] 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 exposed areas 111 and unexposed areas 112.

[0214] As shown in Figure 3C, the exposed resist film 110 is developed using a developer (e.g., a developer). The exposed areas 111 are washed away by the developer, while the unexposed areas 112 remain unwashed by the developer.

[0215] As shown in Figure 3D, the resist pattern 115 can be used as a mask to etch the exposed portion of the material layer 130, thereby forming a material pattern 135 on the substrate 100.

[0216] As shown in Figure 3E, the resist pattern 115 can be removed.

[0217] Figures 4A to 4E are side cross-sectional views showing a method for forming a semiconductor device according to one embodiment.

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] Figures 4A to 4E show examples of transistor formation, but the present invention is not limited thereto.

[0224] A resist composition according to one embodiment can be used in a patterning process for forming other types of semiconductor devices.

[0225] 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]

[0226] Synthesis Example 1: Synthesis of Organic Salt 1 [ka]

[0227] 4-Mercaptobenzoic acid (0.776 g, 5.03 mmol) and sodium 1,1-difluoro-2-hydroxyethanesulfonate (0.926 g, 5.03 mmol) were dissolved in 50 ml of dichloromethane and 1 ml of dimethylformamide. Then, dicyclohexylcarbodiimide (1.141 g, 5.53 mmol), 4-dimethylaminopyridine (0.673 g, 5.53 mmol), and triethylamine (0.78 ml, 5.53 mmol) were added, and the mixture was reacted at room temperature for 16 hours. After the reaction was complete, the precipitate was removed by filtration, washed twice with saturated brine, and the organic layer was collected. After removing the solvent, the mixture was purified by column chromatography under dichloromethane (DCM):methanol (MeOH) = 20:1 (volume:volume) eluent conditions.

[0228] The purified compound was dissolved in 30 ml of tetrahydrofuran, and sodium borohydride (0.572 g, 15.09 mmol) was gradually added while stirring at 0°C for 2 hours, followed by a reaction at room temperature for 4 hours. After the reaction was complete, the solvent was removed, the compound was dissolved in DCM, washed three times with 0.1 M hydrochloric acid aqueous solution and three times with water, and the organic layer was dried over magnesium sulfate. The solvent was removed from the organic layer to obtain intermediate 1-1 (0.805 g, 49%). The resulting compound 1 This was confirmed by 1H-NMR and LC-MS.

[0229] 1 H-NMR (500MHz, CD2Cl2): δ7.89(d,2H),7.50(d,2H),4.63(t,2H),3.34(s,1H), LC-MS m / z = 296.97 (anion).

[0230] (2) Synthesis of Organic Salt 1 Intermediate 1-1 (0.32 g, 1 mmol) and triphenylsulfonium triflate (0.41 g, 1 mmol) were mixed with 10 mL of dichloromethane and 1 mL of water, and the mixture was stirred for 4 hours. The organic layer was then separated, dried over MgSO4, and filtered. The resulting filtrate was then reduced under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain organic salt 1 (0.38 g, 67.9%). The resulting compound was... 1 Confirmed by 1H-NMR and MALDI. 1 H-NMR (500MHz, CD2Cl2): δ7.89(d,2H),7.75(m,15H),7.50(d,2H),4.63(t,2H),3.34(s,1H), HRMS(MALDI)calcd for C 27 H 22 F2O5S3:m / z 560.06 Found:560.05

[0231] Synthesis Example 2: Synthesis of Organic Salt 2 [ka]

[0232] (1) Synthesis of intermediate 2-1 Intermediate 2-1 was manufactured with reference to Korean Published Patent No. 10-2022-0074627.

[0233] 4-iodobenzene (2.246 g, 11.01 mmol), thionyl chloride (0.655 g, 5.51 mmol), and sodium perchlorate (0.117 g, 1.10 mmol) were placed in 12 mL of tetrahydrofuran and stirred for 3 hours. The reaction solvent was then removed by vacuum distillation, and the resulting organic layer was extracted with 30 mL of water and 30 mL of dichloromethane. The resulting organic layer was dried over Na2SO4 and filtered. The filtrate was then removed under reduced pressure, and the residue was separated and purified by column chromatography to obtain intermediate 2-2 (4,4'-sulfinylbis(iodobenzene)). The resulting compound was... 1 Confirmed by 1H-NMR.

[0234] 1 H-NMR (500MHz, CDCl3): δ7.05(d,4H),7.42(d,4H),LC-MS m / z=454.85(M+H)

[0235] Intermediate 2-2 (3.73 g, 8.20 mmol) was dissolved in 15 mL of benzene, and then trifluoromethanesulfonic anhydride (2.778 g, 9.85 mmol) was added dropwise at 0°C, followed by stirring at room temperature for 1 hour. The resulting organic layer was then extracted with 20 mL of water and 50 mL of ethyl acetate, washed with saturated aqueous NaHCO3 solution, dried over MgSO4, and filtered. The resulting filtrate was then distilled under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain intermediate 2-1 (4.92 g, 90%). The resulting compound 1 This was confirmed by 1H-NMR and LC-MS.

[0236] 1 H-NMR (500MHz, CD2Cl2): δ8.08(d,4H),7.84(t,1H),7.74(t,2H),7.69(d,2H),7.41(d,4H), LC-MS m / z = 514.88 (Cation)

[0237] (2) Synthesis of Organic Salt 2 Except for using intermediate 2-1 instead of triphenylsulfonium triflate, organic salt 2 (64.3% yield) was obtained using the same method as for the synthesis of organic salt 1 in Synthesis Example 1. 1 Confirmed by 1H-NMR and MALDI.

[0238] 1 H-NMR(500MHz,CD2Cl2):δ8.08(d,4H),7.89(d,2H),7.84(t,1H),7.74(t,2H),7.69(d,2H),7.50(d,2H),7.41(d,4H),4.63(t,2H),3.34(s,1H), HRMS(MALDI)calcd for C 27 H 20F2I2O5S3:m / z 811.85 Found:811.85

[0239] Synthesis Example 3: Synthesis of Organic Salt 3 [ka]

[0240] Except for using bis(3,5-difluorophenyl)(phenyl)sulfonium triflate instead of triphenylsulfonium triflate, organic salt 3 (72.7% yield) was obtained using the same method as for the synthesis of organic salt 1 in Synthesis Example 1. 1 Confirmed by 1H-NMR and MALDI.

[0241] 1 H-NMR (500MHz, CD2Cl2): δ7.89(m,3H),7.80(m,4H),7.50(d,2H),7.38(m,4H),7.30(m,2H),4.63(t,2H),3.34(s,1H), HRMS(MALDI)calcd for C 27 H 18 F6O5S3:m / z 632.02 Found:632.01

[0242] Synthesis Example 4: Synthesis of Organic Salt 4 [ka]

[0243] (1) Synthesis of intermediate 4-1

[0244] Intermediate 4-1 (73.2% yield) was obtained using the same method as the synthesis of intermediate 1-1 in Synthesis Example 1, except that 3-(mercaptomethyl)adamantane-1-carboxylic acid was used instead of 4-mercaptobenzoic acid. 1 This was confirmed by 1H-NMR and LC-MS.

[0245] 1H-NMR (500MHz, CD2Cl2): δ4.63(t,2H),2.35(d,2H),2.15(m,2H),1.89(m,2H),1.81(m,2H),1.60(m,8H),1.14(t,1H), LC-MS m / z = 369.06 (anion).

[0246] (2) Synthesis of Organic Salt 4 Except for using intermediate 4-1 instead of intermediate 1-1, organic salt 4 (66.5% yield) was obtained using the same method as for the synthesis of organic salt 2 in synthesis example 2. The resulting compound 1 Confirmed by 1H-NMR and MALDI.

[0247] 1 H-NMR (500MHz, CD2Cl2): δ8.08(d,4H),7.84(t,1H),7.74(t,2H),7.69(d,2H),7.41(d,4H), 4.63(t,2H),2.35(d,2H),2.15(m,2H),1.89(m,2H),1.81(m,2H),1.60(m,8H),1.14(t,1H), HRMS(MALDI)calcd for C 32 H 32 F2I2O5S3:m / z 833.95 Found:833.94

[0248] Synthesis Example 5: Synthesis of Organic Salt 5 [ka]

[0249] (1) Synthesis of intermediate 5-1 Except for using 3-iodo-4-(mercaptomethyl)benzoic acid instead of 4-mercaptobenzoic acid, intermediate 5-1 (52.8% yield) was obtained using the same method as for the synthesis of intermediate 1-1 in Synthesis Example 1. The resulting compound 1 This was confirmed by 1H-NMR and LC-MS.

[0250] 1H-NMR (500MHz, CD2Cl2): δ8.33(d,1H),7.89(d,1H),7.58(d,1H),4.63(t,2H),1.42(t,1H), LC-MS m / z = 369.06 (anion).

[0251] (2) Synthesis of Organic Salt 5 Except for using intermediate 5-1 instead of intermediate 1-1, organic salt 5 (62.4% yield) was obtained using the same method as for the synthesis of organic salt 2 in Synthesis Example 2. 1 Confirmed by 1H-NMR and MALDI.

[0252] 1 H-NMR(500MHz,CD2Cl2):δ8.33(d,1H),8.08(d,4H),7.89(d,1H),7.84(t,1H), 7.74(t,2H),7.69(d,2H),7.58(d,1H),7.41(d,4H),4.63(t,2H),1.42(t,1H), HRMS(MALDI)calcd for C 28 H 21 F2I3O5S3:m / z 951.77 Found:951.76

[0253] Synthesis Example 6: Synthesis of Polymer HS / EAd [ka]

[0254] 1.5 g (9.3 mmol) of acetoxystyrene (AHS), 2.3 g (9.3 mmol) of 2-ethyl-2-adamantyl methacrylate (EAd-MA), and 0.2 g (0.9 mmol) of azo initiator (V601) were dissolved in 18 mL of dioxane and reacted at 80°C for 4 hours to obtain AHS / EAd. 1 g of hydrazine monohydrate was added to AHS / EAd and reacted at room temperature for 2 hours to obtain a reaction product. Next, 50 mL of deionized water (DW) and 2 g of acetic acid were added to the reaction product, and after extraction with ethyl acetate (EA), the product was precipitated on hexane. The resulting precipitate was dried at 40°C for 24 hours to obtain a white powder polymer HS / EAd. The number-average molecular weight (Mn) of the obtained polymer HS / EAd was 5000, and the PDI was 1.3. In this case, the molar ratio of HS to EAd in the obtained polymer HS / EAd was 50:50.

[0255] Evaluation Example 1: Evaluation of Acid Generation Effect Cyclohexanone was mixed with 10% by weight of poly(4-vinylphenol) (Mw approximately 11,000, source: Sigma-Aldrich), 5% by weight of coumarin 6 (CAS No. 38215-36-0), and 5% by weight of a photoacid generator. Next, the solution obtained by adding the additives in the amounts listed in Table 1 below was spin-coated to a thickness of 400 nm onto a 1 inch x 1 inch quartz plate and dried at 130°C for 2 minutes to form a thin film. The thin film was then exposed to DUV (248 nm) at a rate of 10 mJ / cm². 2 After exposure, the absorbance was measured. Theoretically, coumarin 6 absorbs at 460 nm, but since the absorbance of coumarin 6 increases at a wavelength of 535 nm due to acid, coumarin 6 was used as an acid indicator. 10 mJ / cm 2 After assuming that 100% of the coumarin 6 was switched off, the absorbance intensity at each exposure dose was normalized to indicate the degree of acid generation. In this case, the degree of acid generation was shown as a relative value based on the value of Comparative Example 1-1.

[0256] [Table 1]

[0257] [ka] [ka]

[0258] As shown in Table 1, it can be confirmed that Examples 1-1 to 1-8 have an improved acid generation effect compared to Comparative Examples 1-1 to 1-2. In other words, it can be expected that when additives containing SH are used, as in Examples 1-1 to 1-8, even with the same amount of photoacid generator, an even higher resolution can be provided.

[0259] Evaluation Example 2: Evaluation of Acid Diffusion Length (ADL) The ADL assessment was based on the method disclosed in Macromolecules, 43(9)4275 (2010).

[0260] First, a 12-inch circular silicon wafer substrate was pre-treated for 10 minutes under a UV ozone cleaning system. A mixture prepared by dissolving HS / EAd in a propylene glycol methyl ether / propylene glycol methyl ether acetate (PGME / PGMEA) 7 / 3 (weight / weight) solution at 1.6 wt% was spin-coated onto the silicon wafer substrate to a thickness of 100 nm at 1500 rpm for 30 seconds to form the first film.

[0261] On a PDMS that had been hydrophilized using a UVO cleaner, HS / EAd was dissolved in a PGME / PGMEA 7 / 3 (weight / weight) solution at a thickness of 1.6 wt% to a thickness of 100 nm, and a photoacid generator was added at a concentration of 50 wt% relative to the HS / EAd. Next, the mixture prepared by adding the additives listed in Table 2 below at a concentration of 5 wt% relative to the HS / EAd was spin-coated at 1500 rpm for 30 seconds, and then treated with 248 nm wavelength DUV (Deep UV) at a density of 100-200 mJ / cm². 2 The second film was formed by exposure. Upon exposure, acid was generated from the photoacid generator in the second film.

[0262] Next, the second film was placed on top of the first film so that it was in contact with it, and pressure was applied to transfer the second film to the first film and remove the PDMS, thereby obtaining a laminate consisting of a silicon wafer substrate, the first film, and the second film. The laminate was maintained at 90°C for 60 seconds to allow the acid generated in the second film to diffuse into the first film. The laminate was then washed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, and the thickness of the remaining first film was measured to evaluate the ADL. In this case, the ADL was expressed as a relative value based on the value of Comparative Example 2-1.

[0263] [Table 2]

[0264] [ka] [ka]

[0265] As shown in Table 2, it was confirmed that Examples 2-1 to 2-5 showed significantly lower ADL values ​​compared to Comparative Examples 2-1 and 2-2. It can be inferred that the additives in Examples 2-1 to 2-5 made the acid diffusion more uniform compared to Comparative Examples 2-1 and 2-2 when the acid generated by exposure diffused.

[0266] Evaluation Example 3: Thin Film Development Evaluation (EUV) A polymer HS / EAd was dissolved in a casting solvent of PGME / PGMEA = 7 / 3 (w / w) to a concentration of 1.6 wt%, and then 0.024 mmol of PAG and 0.016 mmol of PDQ were added. Additives were then added as shown in Table 3 below, and the mixture was filtered through a 0.2 μm separation membrane filter to produce a casting solution. A 12-inch diameter silicon wafer was treated with O2 plasma for 30 minutes, then the casting solution was spin-coated at a speed of 1500 rpm for 1 minute, followed by PAB at 110°C for 1 minute to produce a film with an initial thickness of approximately 20.0 nm. Next, a 1 cm thick mask (4 cm × 4 cm) with rectangular holes (1 cm × 1 cm) was placed on top, and 13.5 nm wavelength EUV was applied to each hole at 0-50 mJ / cm². 2 The photoresist was exposed to a specific dose and subjected to PEB at 90°C for 60 seconds. Next, a 2.38 wt% TMAH aqueous solution was used as the developer, and the photoresist was immersed at 25°C for 20 seconds, then washed with DI (deionized) water for 10 seconds to remove the areas exposed to EUV and dry to form a resist pattern. The photoresist pattern was then subjected to EUV analysis using a CD-SEM (Critical Dimension Measurement Scanning Electron Microscope). op Resolution, IPU, and sensitivity were measured, respectively. op The values ​​are shown in Table 3 below as relative values, based on the values ​​in Comparative Example 3-1.

[0267] The measured resolution, IPU, and sensitivity values ​​were substituted into Equation 1 below to calculate the Z-factor, and the results are shown in Table 3 below as relative values ​​based on the values ​​of Comparative Example 3-1.

[0268] <Number 1> Z-factor=(resolution) 3 ×(IPU) 2 × (Sensitivity) ···Formula 1

[0269] In the above formula 1, the resolution is CD size (half pitch), IPU is a value calculated from CD scattering, and sensitivity is Eop (dose) indicates that a lower Z-factor indicates better pattern performance for the same dose.

[0270] [Table 3]

[0271] [ka] [ka]

[0272] As shown in Table 3 above, the patterns of Examples 3-1 to 3-6 have higher Z-factor and E than the pattern of Comparative Example 3-1. op It can be confirmed that the value is low.

Claims

1. An organic salt represented by the following chemical formula 1. 【Chemistry 1】 In the aforementioned chemical formula 1, A １１ C selectively contains heteroatoms. １ -C ３０ It is a linear or cyclic hydrocarbon group, k11 is selected from integers between 1 and 4. L １１ and L １２ each independently represents a single bond; O; S; C(=O); C(=O)O; OC(=O); C(=O)NR １２ ; NR １２ C(=O); S(=O); S(=O) ２ ; S(=O) ２ O; OS(=O) ２ ; or a linear, branched or cyclic divalent hydrocarbon group containing a heteroatom selectively; C １ -C ３０ ; and is a11 and a12 are each independently selected from integers between 0 and 4. R １１ and R １２ Each of these independently contains a C that selectively contains hydrogen, deuterium, halogen, cyano group, hydroxyl group, or heteroatom. １ -C ２０ A linear, branched, or cyclic monovalent hydrocarbon group; b11 is selected from integers between 0 and 10. R １１ , L １１ and L １２ Two adjacent elements can selectively bond to each other to form a ring. Multiple R １１ Two adjacent elements can selectively bond to each other to form a ring. n11 is selected from integers between 1 and 5. M ＋ This is a counter cation.

2. A １１ C １ -C ３０ alkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkyl groups, C ３ -C ３０ Heterocycloalkyl groups, C ３ -C ３０ Cycloalkenyl group, C ３ -C ３０ Heterocycloalkenyl group, C ６ -C ３０ Aryl group, or C １ -C ３０ The organic salt according to claim 1, wherein the group is a heteroaryl group.

3. A １１ The organic salt according to claim 1, wherein is a methyl group, an ethyl group, an ethenyl group, a cyclopentyl group, a cyclohexyl group, a tetrahydrofuran group, a tetrahydropyran group, a norbornyl group, a norbornenyl group, a norbornadienyl group, a tricyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, an oxanorbornyl group, an oxatricyclodecanyl group, an oxatetracyclododecanyl group, an oxadamantyl group, a benzene group, a naphthalene group, a phenanthrene group, anthracene group, a pyrrole group, a furan group, a thiophene group, an indole group, a benzofuran group, a benzothiophene group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group.

4. L １１ and L １２ Each of these independently represents a single bond; O; C(=O); C(=O)O; OC(=O); C(=O)NH; NHC(=O); or a substituted or unsubstituted C. １ -C ３０ Alkylene group, substituted or unsubstituted C ３ -C ３０ Cycloalkylene group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkylene group, substituted or unsubstituted C ２ -C ３０ Alkenylene group, substituted or unsubstituted C ３ -C ３０ Cycloalkenylene group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylene group, substituted or unsubstituted C ６ -C ３０ Arylene group, substituted or unsubstituted C １ -C ３０ The organic salt according to claim 1, wherein the group is a heteroarylene group or a combination thereof.

5. R １１ and R １２ These are, independently, hydrogen; deuterium; halogen; cyano group; hydroxyl group; and deuterium, halogen, cyano group, hydroxyl group, amino group, carboxylic acid group, ester moisture, sulfonate moisture, carbonate 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 A C that is substituted or unsubstituted with an aryl group, or any combination thereof. １ -C ２０ alkyl group, C １ -C ２０ Alkoxy group, C ３ -C ２０ Cycloalkyl groups, C ３ -C ２０ Cycloalkoxy group, and C ６ -C ２０ An organic salt according to claim 1, selected from an aryl group.

6. The organic salt according to claim 1, wherein n11 is 1 or 2.

7. M ＋ The organic salt according to claim 1, wherein is represented by the following chemical formula 2-1 or 2-2. 【Chemistry (2-1)(2-2)】 In the aforementioned chemical formulas 2-1 and 2-2, R ２１ ~R ２３ Each of these independently contains a C that selectively contains heteroatoms. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group. R ２１ ~R ２３ Two adjacent elements can selectively bond to each other to form a ring.

8. R ２１ to R ２３ represents, independently of one another, deuterium, a halogen, a cyano group, a hydroxy group, a carboxyl group, an ester moiety, a sulfonate moiety, a carbonate moiety, a lactone moiety, a sultone moiety, a carboxylic anhydride moiety, C １ -C ２０ alkyl group, C １ -C ３０ halogenated alkyl group, C １ -C ２０ alkoxy group, C ３ -C ２０ cycloalkyl group, C ３ -C ２０ cycloalkoxy group, C ６ -C ２０ aryl group, or a C １ -C ２０ alkyl group, C ３ -C ２０ cycloalkyl group, and C ６ -C ２０ aryl group, which is selected from any combination thereof, substituted or unsubstituted, the organic salt according to claim 7.

9. M ＋ The organic salt according to claim 1, wherein is represented by the following chemical formula 2-11 or 2-12. 【Chemistry (2-11)(2-12)】 In the aforementioned chemical formulas 2-11 and 2-12, R ２１ａ ~R ２１ｅ Each of these independently contains a C that selectively contains hydrogen, deuterium, halogen, cyano group, hydroxyl group, or heteroatom. １ -C ２０ A linear, branched, or cyclic monovalent hydrocarbon group; R ２２ ~R ２３ Each of these independently contains a C that selectively contains heteroatoms. １ -C ３０ It is a linear, branched, or cyclic monovalent hydrocarbon group. R ２１ａ ~R ２１ｅ and R ２２ ~R ２３ Two adjacent elements can selectively bond to each other to form a ring.

10. M ＋ The organic salt according to claim 1, wherein is represented by any one of the following chemical formulas 2-21 to 2-23. 【Chemistry (2-21)(2-22)(2-23)】 In the aforementioned chemical formulas 2-21 to 2-23, R ２１ａ ~R ２１ｅ , R ２２ａ ~R ２２ｅ and R ２３ａ ~R ２３ｅ Each of these independently contains a C that selectively contains hydrogen, deuterium, halogen, cyano group, hydroxyl group, or heteroatom. １ -C ２０ It is a linear, branched, or cyclic monovalent hydrocarbon group. R ２１ａ ~R ２１ｅ , R ２２ａ ~R ２２ｅ and R ２３ａ ~R ２３ｅ Two adjacent rings can selectively bond to each other to form a fused ring. b22a and b23a are integers from 1 to 4, A ２１ and A ２２ Each is either absent or a benzene ring, independently of the others. 【change】 The bond represented is either a carbon-carbon single bond or a carbon-carbon double bond. L ２１ These are single bonds: O, S, CO, SO, SO ２ , CRR', or NR, R and R' each independently contain a C that selectively contains hydrogen, deuterium, halogen, cyano group, hydroxyl group, or heteroatom. １ -C ２０ A linear, branched, or cyclic monovalent hydrocarbon group;

11. M ＋ The organic salt according to claim 1, wherein the salt comprises at least one halogen.

12. M ＋ The organic salt according to claim 1, wherein is selected from the following group I. 【Chemical Group-I】 【change】

13. The organic salt represented by the chemical formula 1 is selected from the following group II, according to claim 1. [Chemical Group II] 【change】 Here, in group II, M ＋ It is a counter-cation.

14. A resist composition comprising the organic salt, photoacid generator, and base resin described in claim 1.

15. The resist composition according to claim 14, wherein the organic salt is contained in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the base resin.

16. The resist composition according to claim 14, wherein the organic salt is contained in an amount of 0.01 to 70 parts by weight per 100 parts by weight of the photoacid generator.

17. The resist composition according to claim 14, wherein the base resin comprises a first repeating unit represented by the following chemical formula 3. 【Transformation 3】 In the aforementioned chemical formula 3, 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 selectively containing heteroatoms １ -C ３０ A linear, branched, or cyclic divalent hydrocarbon group; a31 to a33 are each independent integers from 1 to 4. R ３１ and R ３２ Each of these independently contains hydrogen; deuterium; halogen; cyano group; hydroxyl group; amino group; carboxylic acid group; thiol group; ester molecule; sulfonate molecule; carbonate molecule; lactone molecule; sultone molecule; carboxylic acid anhydride molecule; or a C molecule selectively containing a heteroatom. １ -C ３０ A linear, branched, or cyclic monovalent hydrocarbon group; X ３１ It is an acid-unstable group. * indicates a bonding site with an adjacent atom.

18. The steps of 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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